US20030008998A1 - Interlayer dielectric film - Google Patents

Interlayer dielectric film Download PDF

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US20030008998A1
US20030008998A1 US10/128,296 US12829602A US2003008998A1 US 20030008998 A1 US20030008998 A1 US 20030008998A1 US 12829602 A US12829602 A US 12829602A US 2003008998 A1 US2003008998 A1 US 2003008998A1
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interlayer dielectric
sites
organic
dielectric film
film
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Nobuo Aoi
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Panasonic Corp
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Matsushita Electric Industrial Co Ltd
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    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
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    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/7682—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing the dielectric comprising air gaps
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
    • H01L21/3124—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds layers comprising hydrogen silsesquioxane
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31695—Deposition of porous oxides or porous glassy oxides or oxide based porous glass
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
    • H01L2221/1005—Formation and after-treatment of dielectrics
    • H01L2221/1042—Formation and after-treatment of dielectrics the dielectric comprising air gaps
    • H01L2221/1047—Formation and after-treatment of dielectrics the dielectric comprising air gaps the air gaps being formed by pores in the dielectric
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12361—All metal or with adjacent metals having aperture or cut
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542—More than one such component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to an interlayer dielectric film with a low dielectric constant capable of preventing diffuision of copper, that is, a material for interconnects.
  • a siloxane film such as a methylsilsesquioxane (MSQ) film (with a dielectric constant of approximately 2.9) and a hydrogenated silsesquioxane (HSQ) film (with a dielectric constant of approximately 3.0), including SiO 2 as a principal constituent has been proposed.
  • FIG. 14 shows the chemical structure of methylsilsesquioxane, that is, an example of conventional organic siloxane in which an organic group is bonded to siloxane. In FIG. 14, a methyl group is bonded to a Si atom included in the main chain of the siloxane.
  • an organic polymer film including an aromatic compound polymer such as a polyimide derivative, a polyalyl ether derivative, a polyquinoline derivative or a polyparaxylene derivative, having a low dielectric constant and high heat resistance has been proposed as the low dielectric interlayer dielectric film.
  • an organic polymer film has a low dielectric constant because it includes carbon as a principal constituent, and hence, the polarizability of molecules included in the film is lower than that of a conventionally used interlayer dielectric film including SiO 2 as a principal constituent.
  • an object of the invention is preventing copper used as the material for interconnects from diffusing into an interlayer dielectric film so as to prevent the breakdown voltage of the interlayer dielectric film from lowering over a long period of use.
  • the interlayer dielectric film attains a low dielectric constant by reducing the density of the interlayer dielectric film, for example, by making it porous.
  • the mechanism of the drift of copper ions in an interlayer dielectric film with low density is different from that of the drift of copper ions in a conventional dense interlayer dielectric film.
  • the interaction between molecules included in the interlayer dielectric film and copper ions is probably dominant in the interlayer dielectric film with low density. Specifically, the interaction between molecules included in a polymer film is smaller in the interlayer dielectric film with low density than in a dense interlayer dielectric film (that is, a bulk solid).
  • the present invention was devised on the basis of these findings and utilizes the interaction between copper ions and siloxane larger than that between copper ions and an organic molecule.
  • the first interlayer dielectric film of the invention comprises an organic/inorganic hybrid film having a main chain in which a first site of siloxane and a second site of an organic molecule are alternately bonded to each other.
  • the second interlayer dielectric film of the invention comprises an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and the plurality of first sites are bonded to the plurality of second sites alone and the plurality of second sites are bonded to the plurality of first sites alone.
  • the third interlayer dielectric film of the invention comprises an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and each of the plurality of first sites is surrounded with the plurality of second sites.
  • the fourth interlayer dielectric film of the invention comprises an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and each of the plurality of second sites is surrounded with the plurality of first sites.
  • the potential energy required for, namely, the barrier height to be cleared by, copper ions drifting in the organic/inorganic hybrid film from a copper film used as an interconnect material and moving along the main chain of the polymer included in the organic/inorganic hybrid film is much larger than the potential energy required for, namely, the barrier height to be cleared by, copper ions moving along the main chain of a polymer included in a conventional interlayer dielectric film. Therefore, the copper ions are easily trapped by the first sites of siloxane in the interlayer dielectric film. Accordingly, the copper ions are minimally diffused into the interlayer dielectric film. As a result, the breakdown voltage of the interlayer dielectric film of any of the first through fourth interlayer dielectric films is minimally lowered even when used for a long period of time.
  • pores are preferably dispersed in the organic/inorganic hybrid film.
  • the dielectric constant of the first, second, third or fourth interlayer dielectric film can be lowered.
  • the fifth interlayer dielectric film of the invention comprises a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and the plurality of second sites together form an organic polymer film and the plurality of first sites are dispersed in the organic polymer film.
  • the first site of siloxane may or may not be bonded to the second site of an organic molecule.
  • the first sites of siloxane are dispersed in the organic polymer film made from the organic molecules. Therefore, copper interconnects disposed with the interlayer dielectric film sandwiched therebetween are never electrically connected to each other through the first sites of siloxane. Accordingly, copper ions drifting from the copper interconnects into the interlayer dielectric film are easily trapped by the first sites of siloxane, and hence the copper ions are minimally diffused into the interlayer dielectric film. As a result, the breakdown voltage of the fifth interlayer dielectric film is minimally lowered even when used for a long period of time.
  • a largest distance between the plurality of first sites is preferably smaller than a distance between a pair of copper interconnects disposed with the organic polymer film sandwiched therebetween.
  • the copper interconnects adjacent to each other with the interlayer dielectric film sandwiched therebetween can be definitely prevented from being electrically connected through the first sites of siloxane. Therefore, copper ions drifting from one of the adjacent copper interconnects into the interlayer dielectric film minimally pass by the vicinity of the first sites of siloxane to reach the other copper interconnect. Accordingly, the copper ions drifting from one copper interconnect can be prevented from reaching the other copper interconnect, and hence, the copper interconnects can be prevented from being electrically connected to each other through the copper ions.
  • pores are preferably dispersed in the organic polymer film.
  • the dielectric constant of the fifth interlayer dielectric film can be lowered.
  • the first site is preferably represented by the following general formula (1):
  • R 1 , R 2 and R 3 are an oxygen atom or an organic group.
  • the copper ions can be definitely prevented from passing by the vicinity of the first sites of siloxane to diffuse into the interlayer dielectric film.
  • the first site is preferably represented by the following general formula (2):
  • R is an organic group
  • R 1 and R 2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
  • the copper ions can be definitely prevented from passing by the vicinity of the first sites of siloxane to diffuise into the interlayer dielectric film.
  • the second site is preferably polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers.
  • the sixth interlayer dielectric film of the invention comprises a multi-layer film, in which a first layer of siloxane and a second layer of an organic molecule are alternately stacked on each other.
  • a lower copper interconnect and an upper copper interconnect disposed below and on the interlayer dielectric film are never connected to each other through the first layer of siloxane or the second layer of the organic molecule. Therefore, copper ions drifting from the lower or upper copper interconnect into the interlayer dielectric film are easily trapped by siloxane included in the first layer. Accordingly, the copper ions are minimally diffused into the interlayer dielectric film, and hence, the lower copper interconnect and the upper copper interconnect can be prevented from being electrically connected to each other through the copper ions.
  • FIG. 1 is a diagram for showing the molecular structure of an organic/inorganic hybrid film corresponding to an interlayer dielectric film according to Embodiment 1 of the invention
  • FIG. 2 is a conceptual diagram for showing the molecular structure of the organic/inorganic hybrid film corresponding to the interlayer dielectric film of Embodiment 1;
  • FIG. 3 is a diagram for roughly showing the molecular structure of a region A of FIG. 2;
  • FIG. 4 is a schematic diagram for showing the molecular structure of the region A of FIG. 2;
  • FIG. 5 is a diagram for three-dimensionally showing a bond between a first site composed of siloxane and a second site composed of an organic molecule in the organic/inorganic hybrid film of Embodiment 1;
  • FIG. 6 is a diagram for two-dimensionally showing the bond between the first site composed of siloxane and the second site composed of the organic molecule in the organic/inorganic hybrid film of Embodiment 1;
  • FIG. 7( a ) is a characteristic diagram for showing the relationship between a coordinate axis corresponding to a distance from the center of the main chain of a polymer included in the organic/inorganic hybrid film of Embodiment 1 and the potential energy required for movement of a copper ion and
  • FIG. 7( b ) is a schematic diagram of the main chain of the polymer of the organic/inorganic hybrid film of Embodiment 1;
  • FIG. 8( a ) is a characteristic diagram for showing the relationship between a coordinate axis corresponding to a distance from the center of the main chain of a polymer included in a conventional organic polymer film and the potential energy required for movement of a copper ion and FIG. 8( b ) is a schematic diagram of the main chain of the polymer of the conventional organic polymer film;
  • FIG. 9( a ) is a characteristic diagram for showing the relationship between a coordinate axis corresponding to a distance from the center of the main chain of a polymer included in a conventional ladder type siloxane film and the potential energy required for movement of a copper ion and FIG. 9( b ) is a schematic diagram of the main chain of the polymer of the conventional ladder type siloxane film;
  • FIG. 10 is a characteristic diagram for showing the height of a barrier and the drift rate of copper ions in the organic/inorganic hybrid film of Embodiment 1, the conventional organic polymer film and the conventional siloxane film;
  • FIGS. 11 ( a ), 11 ( b ) and 11 ( c ) are diagrams for showing chemical reactions occurring in forming the organic/inorganic hybrid film of Embodiment 1;
  • FIG. 12 is a cross-sectional view of an interlayer dielectric film according to Embodiment 2 of the invention.
  • FIG. 13 is a cross-sectional view of an interlayer dielectric film according to Embodiment 3 of the invention.
  • FIG. 14 is a diagram of general formula representing the chemical structure of conventional organic siloxane.
  • FIG. 1 shows the molecular structure of an organic/inorganic hybrid film corresponding to the interlayer dielectric film of Embodiment 1.
  • a indicates a first site composed of siloxane
  • b indicates a second site composed of an organic molecule
  • c indicates a free volume.
  • FIG. 2 is a conceptual diagram for showing the molecular structure of the organic/inorganic hybrid film corresponding to the interlayer dielectric film of Embodiment 1.
  • FIG. 3 roughly shows the molecular structure of a region A of FIG. 2, wherein a indicates the first site composed of siloxane, b indicates the second site composed of the organic molecule and c indicates the free volume.
  • FIG. 4 schematically shows the molecular structure of the region A of FIG. 2.
  • FIG. 5 three-dimensionally shows a bond between the first site a composed of siloxane and the second site b composed of the organic molecule in the organic/inorganic hybrid film of Embodiment 1.
  • FIG. 6 two-dimensionally shows the bond between the first site a composed of siloxane and the second site b composed of the organic molecule in the organic/inorganic hybrid film of Embodiment 1.
  • the organic/inorganic hybrid film of Embodiment 1 includes a plurality of first site a each composed of siloxane, a plurality of second sites b each composed of the organic molecule and a plurality of third sites c disposed dispersedly.
  • the first sites a each composed of siloxane and the second sites b each composed of the organic molecule together forming a main chain are alternately bonded to each other.
  • the first site a is bonded to the second site b alone and the second site b is bonded to the first site a alone.
  • each of the first sites a is surrounded with the plural second sites b.
  • each of the second sites b is surrounded with the plural first sites a.
  • the first sites a and the second sites b are alternately bonded to each other in FIGS. 1, 3, 5 and 6 , the first sites a and the second sites b may not be bonded to each other.
  • the organic/inorganic hybrid film of Embodiment 1 may have the third or fourth characteristic without having the first and second characteristics.
  • FIG. 7( a ) shows the relationship between the coordinate axis (x-axis) corresponding to a distance from the center of the main chain of a polymer included in the organic/inorganic hybrid film of Embodiment 1 and the potential energy required for a copper ion to move along the main chain.
  • FIG. 7( b ) is a schematic diagram of the main chain of the polymer included in the organic/inorganic hybrid film of Embodiment 1. As is understood from FIGS.
  • the potential energy required for a copper ion to move from the vicinity of an oxygen atom (O) of siloxane (i.e., the first site a) to the vicinity of a carbon atom (C) of the organic molecule (i.e., the second site b) is very high and is specifically approximately 3 kcal/mol.
  • a barrier to be cleared by the copper ion in moving from the first site a to the second site b is very high. Therefore, the copper ion drifting in the organic/inorganic hybrid film is easily trapped by the first site a.
  • FIG. 8( a ) shows the relationship between the coordinate axis (x-axis) corresponding to a distance from the center of the main chain of a polymer included in a conventional organic polymer film and the potential energy required for a copper ion to move along the main chain.
  • FIG. 8( b ) is a schematic diagram of the main chain of the polymer included in the organic polymer film.
  • the potential energy required for a copper ion to move from the vicinity of one carbon atom (C) included in the organic polymer to the vicinity of another carbon atom (C) is low and is specifically approximately 1.3 kcal/mol. Therefore, the copper ion drifting in the organic polymer film is minimally trapped.
  • FIG. 9( a ) shows the relationship between the coordinate axis (x-axis) corresponding to a distance from the center of the main chain of a polymer included in a conventional ladder type siloxane film and the potential energy required for a copper ion to move along the main chain.
  • FIG. 9( b ) is a schematic diagram of the main chain of the polymer included in the ladder type siloxane film.
  • the potential energy required for a copper ion to move from the vicinity of an oxygen atom (O) of siloxane to the vicinity of silicon (Si) is low and is specifically approximately 0.5 kcal/mol. Therefore, the copper ion drifting in the ladder type siloxane film is minimally trapped.
  • the film when a hydrogen atom bonded to a Si atom is replaced with an organic group, the film is an organic siloxane film. Also in the organic siloxane film, the potential energy required for a copper ion to move from the vicinity of an oxygen atom (O) of siloxane to the vicinity of silicon (Si) is the same as that shown in FIG. 9( b ). Therefore, the copper ion drifting in the organic siloxane film is minimally trapped.
  • FIG. 10 shows the barrier height and the drift rate of copper ions in the organic/inorganic hybrid film of Embodiment 1 shown in FIG. 7( b ), the conventional organic polymer film shown in FIG. 8( b ) and the conventional siloxane film shown in FIG. 9( b ).
  • the data obtained in the experiment are varied.
  • the barrier height for copper ions is large and the drift rate is low in the organic/inorganic hybrid film of Embodiment 1.
  • the potential energy required for, namely, the barrier height to be cleared by, a copper ion moving along the main chain of the polymer included in the organic/inorganic hybrid film of Embodiment 1 is much higher than the potential energy required for, namely, the barrier height to be cleared by, a copper ion moving along the main chain of the organic polymer or the ladder type siloxane. Therefore, the copper ions are easily trapped and difficult to drift in the organic/inorganic hybrid film of Embodiment 1. Accordingly, copper (copper ions) used as the material for interconnects is minimally diffused into the interlayer dielectric film of Embodiment 1. As a result, the breakdown voltage of the interlayer dielectric film is minimally lowered even when used for a long period of time.
  • 1,6-(bistrichlorosilyl)hexane (a trichlorosilane derivative; a first silane derivative) shown on the left hand side of FIG. 11( a ) and methyltrichlorosilane (a second silane derivate) shown on the right hand side of FIG. 11( a ) are hydrolyzed in a ratio of 1:1 in an alcohol solution, so as to obtain two silanols as shown in FIG. 11( b ).
  • the two silanols are polymerized through a dehydration condensation reaction, so as to give a silanol condensate as shown in FIG. 11( c ).
  • a solution including the silanol condensate of FIG. 11( c ) is applied on a semiconductor substrate by spin coating and the resultant substrate is annealed.
  • the interlayer dielectric film of the organic/inorganic hybrid film having the structure as shown in FIG. 1 in which methylsilsesquioxanes in a cage structure (i.e., the first sites a) are bonded via methylene of hexane (i.e., the second site b) in a network structure is formed.
  • trichlorosilane derivative is used as the first silane derivative in the above-described method for forming the interlayer dielectric film of Embodiment 1, a trialkoxysilane derivative may be used instead.
  • silane derivative in which silicon atoms are crosslinked via hexane including six methylene groups is used as the second silane derivative, the number of methylene groups is not specified. Also, an organic molecule other than the methylene groups, such as phenylene, may be used as the crosslinking molecule.
  • any siloxane represented by the following general formula (1) may be widely used as the first site a included in the organic/inorganic hybrid film of Embodiment 1:
  • R 1 , R 2 and R 3 are an oxygen atom or an organic group.
  • any siloxane represented by the following general formula (2) may be widely used as the first site a included in the organic/inorganic hybrid film of Embodiment 1:
  • R is an organic group
  • R 1 and R 2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
  • polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers may be widely used as the second site b included in the organic/inorganic hybrid film of Embodiment 1.
  • the interlayer dielectric film of Embodiment 2 includes a plurality of first sites a each composed of siloxane and a plurality of second sites b each composed of an organic molecule.
  • the plural second sites b together form an organic polymer film, in which the plural first sites a and a plurality of holes c are dispersed.
  • the first site a composed of siloxane may be or may not be bonded to the second site b composed of the organic molecule.
  • FIG. 12 shows the cross-sectional structure of the interlayer dielectric film of Embodiment 2.
  • a plurality of silica fine particles 12 each corresponding to the first site a and a plurality of holes 13 are dispersed in an organic polymer film 11 formed from the plural second sites b.
  • the largest distance between the first sites a of siloxane forming the silica fine particles 12 is preferably smaller than the distance between the copper interconnects 14 adjacent to each other.
  • the copper interconnects 14 adjacent to each other can be definitely prevented from being electrically connected through the first sites a of siloxane, and therefore, copper ions drifting in the organic polymer film 11 from one copper interconnect 14 can never pass by the vicinity of the first sites a of siloxane to reach the other adjacent copper interconnect 14 . Accordingly, the copper ions drifting from one copper interconnect 14 can be prevented from reaching the other copper interconnect 14 , and hence, the dielectric property of the interlayer dielectric film is never degraded.
  • Silica fine particles with an average particle size of 10 nm are dispersed in, for example, a polymer solution of the polyalyl ether family. Then, the solution in which the silica fine particles are dispersed is applied on a semiconductor substrate by spin coating, and the resultant semiconductor substrate is annealed. In this manner, the interlayer dielectric film as shown in FIG. 12 in which the plural silica fine particles 12 and the plural holes 13 are dispersed in the organic polymer film 11 formed from the plural second sites b can be obtained.
  • the interlayer dielectric film may be formed by using a solution including a silanol condensate obtained through hydrolysis and dehydration condensation of 1,6-(bistrichlorosily)hexane (first silane derivative) and methyltrichlorosilane as in Embodiment 1.
  • any siloxane represented by the above-described general formula (1) or (2) may be widely used.
  • the second site b polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers may be widely used.
  • FIG. 13 shows the cross-sectional structure of the interlayer dielectric film of Embodiment 3.
  • a lower interlayer dielectric film 21 and an upper interlayer dielectric film 22 are successively formed on a semiconductor substrate 20 .
  • a lower copper interconnect 23 is buried in the lower interlayer dielectric film 21
  • an upper copper interconnect 24 is buried in the upper interlayer dielectric film 22 .
  • each of the lower and upper interlayer dielectric films 21 and 22 is made from a multi-layer film composed of a first layer d of siloxane and a second layer e of an organic molecule alternately stacked.
  • the lower copper interconnect 23 and the upper copper interconnect 24 are never electrically connected to each other through the first layer d of siloxane and the second layer e of the organic molecule. Therefore, copper ions drifting from the lower or upper copper interconnect 23 or 24 into the upper interlayer dielectric film 22 are trapped by siloxane included in the first layer d and hence are minimally diffused into the upper interlayer dielectric film 22 . Accordingly, the lower copper interconnect 23 and the upper copper interconnect 24 can be prevented from being electrically connected to each other through the copper ions.

Abstract

An interlayer dielectric film is made from an organic/inorganic hybrid film. The organic/inorganic hybrid film has a main chain in which a first site of siloxane and a second site of an organic molecule are alternately bonded to each other.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to an interlayer dielectric film with a low dielectric constant capable of preventing diffuision of copper, that is, a material for interconnects. [0001]
  • In an interlayer dielectric film of a VLSI, reduction of design rule has led to a problem of increase of parasitic capacitance between adjacent interconnects, and it is significant to lower the dielectric constant of the interlayer dielectric film in order to reduce the parasitic capacitance between interconnects. [0002]
  • As a low dielectric interlayer dielectric film, a siloxane film, such as a methylsilsesquioxane (MSQ) film (with a dielectric constant of approximately 2.9) and a hydrogenated silsesquioxane (HSQ) film (with a dielectric constant of approximately 3.0), including SiO[0003] 2 as a principal constituent has been proposed. FIG. 14 shows the chemical structure of methylsilsesquioxane, that is, an example of conventional organic siloxane in which an organic group is bonded to siloxane. In FIG. 14, a methyl group is bonded to a Si atom included in the main chain of the siloxane.
  • Alternatively, an organic polymer film including an aromatic compound polymer, such as a polyimide derivative, a polyalyl ether derivative, a polyquinoline derivative or a polyparaxylene derivative, having a low dielectric constant and high heat resistance has been proposed as the low dielectric interlayer dielectric film. Such an organic polymer film has a low dielectric constant because it includes carbon as a principal constituent, and hence, the polarizability of molecules included in the film is lower than that of a conventionally used interlayer dielectric film including SiO[0004] 2 as a principal constituent.
  • Therefore, such an organic polymer film is regarded as a promising low dielectric interlayer dielectric film. [0005]
  • However, when copper is used as the material for interconnects, copper ions are diffused by an electric field or heat into such a low dielectric interlayer dielectric film. Therefore, the breakdown voltage of the interlayer dielectric film is disadvantageously lowered when it is used for a long period of time. When the breakdown voltage of the interlayer dielectric film is lowered, dielectric failure is caused, which may result in failure of the operation of the VLSI. [0006]
    • SUMMARY OF THE INVENTION
  • In consideration of the aforementioned conventional problem, an object of the invention is preventing copper used as the material for interconnects from diffusing into an interlayer dielectric film so as to prevent the breakdown voltage of the interlayer dielectric film from lowering over a long period of use. [0007]
  • The mechanism of the diffusion of copper into an interlayer dielectric film has not been completely solved. Probably, copper atoms included in the interconnect material are ionized to dissolve in the interlayer dielectric film, so that the copper ions dissolved in the interlayer dielectric film can drift in the interlayer dielectric film due to an electric field. [0008]
  • Also, the interlayer dielectric film attains a low dielectric constant by reducing the density of the interlayer dielectric film, for example, by making it porous. The mechanism of the drift of copper ions in an interlayer dielectric film with low density is different from that of the drift of copper ions in a conventional dense interlayer dielectric film. The interaction between molecules included in the interlayer dielectric film and copper ions is probably dominant in the interlayer dielectric film with low density. Specifically, the interaction between molecules included in a polymer film is smaller in the interlayer dielectric film with low density than in a dense interlayer dielectric film (that is, a bulk solid). Therefore, the degeneracy of electron orbitals between the molecules is solved, so that the molecules included in the polymer film can behave as if they were individual molecules also in the interlayer dielectric film. Furthermore, copper ions drift in the interlayer dielectric film dominantly through the interaction between the molecules and the copper ions. Accordingly, drift paths of the copper ions are along the surfaces of the molecules included in the interlayer dielectric film. [0009]
  • The present invention was devised on the basis of these findings and utilizes the interaction between copper ions and siloxane larger than that between copper ions and an organic molecule. [0010]
  • Specifically, the first interlayer dielectric film of the invention comprises an organic/inorganic hybrid film having a main chain in which a first site of siloxane and a second site of an organic molecule are alternately bonded to each other. [0011]
  • The second interlayer dielectric film of the invention comprises an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and the plurality of first sites are bonded to the plurality of second sites alone and the plurality of second sites are bonded to the plurality of first sites alone. [0012]
  • The third interlayer dielectric film of the invention comprises an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and each of the plurality of first sites is surrounded with the plurality of second sites. [0013]
  • The fourth interlayer dielectric film of the invention comprises an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and each of the plurality of second sites is surrounded with the plurality of first sites. [0014]
  • In any of the first through fourth interlayer dielectric films, the potential energy required for, namely, the barrier height to be cleared by, copper ions drifting in the organic/inorganic hybrid film from a copper film used as an interconnect material and moving along the main chain of the polymer included in the organic/inorganic hybrid film is much larger than the potential energy required for, namely, the barrier height to be cleared by, copper ions moving along the main chain of a polymer included in a conventional interlayer dielectric film. Therefore, the copper ions are easily trapped by the first sites of siloxane in the interlayer dielectric film. Accordingly, the copper ions are minimally diffused into the interlayer dielectric film. As a result, the breakdown voltage of the interlayer dielectric film of any of the first through fourth interlayer dielectric films is minimally lowered even when used for a long period of time. [0015]
  • In any of the first through fourth interlayer dielectric films, pores are preferably dispersed in the organic/inorganic hybrid film. [0016]
  • Thus, the dielectric constant of the first, second, third or fourth interlayer dielectric film can be lowered. [0017]
  • The fifth interlayer dielectric film of the invention comprises a plurality of first sites of siloxane and a plurality of second sites of an organic molecule, and the plurality of second sites together form an organic polymer film and the plurality of first sites are dispersed in the organic polymer film. [0018]
  • In the fifth interlayer dielectric film, the first site of siloxane may or may not be bonded to the second site of an organic molecule. [0019]
  • In the fifth interlayer dielectric film, the first sites of siloxane are dispersed in the organic polymer film made from the organic molecules. Therefore, copper interconnects disposed with the interlayer dielectric film sandwiched therebetween are never electrically connected to each other through the first sites of siloxane. Accordingly, copper ions drifting from the copper interconnects into the interlayer dielectric film are easily trapped by the first sites of siloxane, and hence the copper ions are minimally diffused into the interlayer dielectric film. As a result, the breakdown voltage of the fifth interlayer dielectric film is minimally lowered even when used for a long period of time. [0020]
  • In the fifth interlayer dielectric film, a largest distance between the plurality of first sites is preferably smaller than a distance between a pair of copper interconnects disposed with the organic polymer film sandwiched therebetween. [0021]
  • Thus, the copper interconnects adjacent to each other with the interlayer dielectric film sandwiched therebetween can be definitely prevented from being electrically connected through the first sites of siloxane. Therefore, copper ions drifting from one of the adjacent copper interconnects into the interlayer dielectric film minimally pass by the vicinity of the first sites of siloxane to reach the other copper interconnect. Accordingly, the copper ions drifting from one copper interconnect can be prevented from reaching the other copper interconnect, and hence, the copper interconnects can be prevented from being electrically connected to each other through the copper ions. [0022]
  • In the fifth interlayer dielectric film, pores are preferably dispersed in the organic polymer film. [0023]
  • Thus, the dielectric constant of the fifth interlayer dielectric film can be lowered. [0024]
  • In any of the first through fifth interlayer dielectric films, the first site is preferably represented by the following general formula (1): [0025]
    Figure US20030008998A1-20030109-C00001
  • wherein R[0026] 1, R2 and R3 are an oxygen atom or an organic group.
  • Thus, the copper ions can be definitely prevented from passing by the vicinity of the first sites of siloxane to diffuse into the interlayer dielectric film. [0027]
  • Alternatively, in any of the first through fifth interlayer dielectric films, the first site is preferably represented by the following general formula (2): [0028]
    Figure US20030008998A1-20030109-C00002
  • wherein R is an organic group; and R[0029] 1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
  • Thus, the copper ions can be definitely prevented from passing by the vicinity of the first sites of siloxane to diffuise into the interlayer dielectric film. [0030]
  • In any of the first through fifth interlayer dielectric films, the second site is preferably polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers. [0031]
  • The sixth interlayer dielectric film of the invention comprises a multi-layer film, in which a first layer of siloxane and a second layer of an organic molecule are alternately stacked on each other. [0032]
  • In the sixth interlayer dielectric film, a lower copper interconnect and an upper copper interconnect disposed below and on the interlayer dielectric film are never connected to each other through the first layer of siloxane or the second layer of the organic molecule. Therefore, copper ions drifting from the lower or upper copper interconnect into the interlayer dielectric film are easily trapped by siloxane included in the first layer. Accordingly, the copper ions are minimally diffused into the interlayer dielectric film, and hence, the lower copper interconnect and the upper copper interconnect can be prevented from being electrically connected to each other through the copper ions.[0033]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a diagram for showing the molecular structure of an organic/inorganic hybrid film corresponding to an interlayer dielectric film according to [0034] Embodiment 1 of the invention;
  • FIG. 2 is a conceptual diagram for showing the molecular structure of the organic/inorganic hybrid film corresponding to the interlayer dielectric film of [0035] Embodiment 1;
  • FIG. 3 is a diagram for roughly showing the molecular structure of a region A of FIG. 2; [0036]
  • FIG. 4 is a schematic diagram for showing the molecular structure of the region A of FIG. 2; [0037]
  • FIG. 5 is a diagram for three-dimensionally showing a bond between a first site composed of siloxane and a second site composed of an organic molecule in the organic/inorganic hybrid film of [0038] Embodiment 1;
  • FIG. 6 is a diagram for two-dimensionally showing the bond between the first site composed of siloxane and the second site composed of the organic molecule in the organic/inorganic hybrid film of [0039] Embodiment 1;
  • FIG. 7([0040] a) is a characteristic diagram for showing the relationship between a coordinate axis corresponding to a distance from the center of the main chain of a polymer included in the organic/inorganic hybrid film of Embodiment 1 and the potential energy required for movement of a copper ion and FIG. 7(b) is a schematic diagram of the main chain of the polymer of the organic/inorganic hybrid film of Embodiment 1;
  • FIG. 8([0041] a) is a characteristic diagram for showing the relationship between a coordinate axis corresponding to a distance from the center of the main chain of a polymer included in a conventional organic polymer film and the potential energy required for movement of a copper ion and FIG. 8(b) is a schematic diagram of the main chain of the polymer of the conventional organic polymer film;
  • FIG. 9([0042] a) is a characteristic diagram for showing the relationship between a coordinate axis corresponding to a distance from the center of the main chain of a polymer included in a conventional ladder type siloxane film and the potential energy required for movement of a copper ion and FIG. 9(b) is a schematic diagram of the main chain of the polymer of the conventional ladder type siloxane film;
  • FIG. 10 is a characteristic diagram for showing the height of a barrier and the drift rate of copper ions in the organic/inorganic hybrid film of [0043] Embodiment 1, the conventional organic polymer film and the conventional siloxane film;
  • FIGS. [0044] 11(a), 11(b) and 11(c) are diagrams for showing chemical reactions occurring in forming the organic/inorganic hybrid film of Embodiment 1;
  • FIG. 12 is a cross-sectional view of an interlayer dielectric film according to [0045] Embodiment 2 of the invention;
  • FIG. 13 is a cross-sectional view of an interlayer dielectric film according to [0046] Embodiment 3 of the invention; and
  • FIG. 14 is a diagram of general formula representing the chemical structure of conventional organic siloxane.[0047]
    • DETAILED DESCRIPTION OF THE INVENTION
  • [0048] Embodiment 1
  • An interlayer dielectric film and a method for forming the same according to [0049] Embodiment 1 of the invention will now be described with reference to the accompanying drawings.
  • FIG. 1 shows the molecular structure of an organic/inorganic hybrid film corresponding to the interlayer dielectric film of [0050] Embodiment 1. In FIG. 1, a indicates a first site composed of siloxane, b indicates a second site composed of an organic molecule and c indicates a free volume.
  • FIG. 2 is a conceptual diagram for showing the molecular structure of the organic/inorganic hybrid film corresponding to the interlayer dielectric film of [0051] Embodiment 1.
  • FIG. 3 roughly shows the molecular structure of a region A of FIG. 2, wherein a indicates the first site composed of siloxane, b indicates the second site composed of the organic molecule and c indicates the free volume. [0052]
  • FIG. 4 schematically shows the molecular structure of the region A of FIG. 2. [0053]
  • FIG. 5 three-dimensionally shows a bond between the first site a composed of siloxane and the second site b composed of the organic molecule in the organic/inorganic hybrid film of [0054] Embodiment 1.
  • FIG. 6 two-dimensionally shows the bond between the first site a composed of siloxane and the second site b composed of the organic molecule in the organic/inorganic hybrid film of [0055] Embodiment 1.
  • As shown in FIGS. 1, 3, [0056] 5 and 6, the organic/inorganic hybrid film of Embodiment 1 includes a plurality of first site a each composed of siloxane, a plurality of second sites b each composed of the organic molecule and a plurality of third sites c disposed dispersedly.
  • As a first characteristic of the organic/inorganic hybrid film of [0057] Embodiment 1, the first sites a each composed of siloxane and the second sites b each composed of the organic molecule together forming a main chain are alternately bonded to each other. As a second characteristic, the first site a is bonded to the second site b alone and the second site b is bonded to the first site a alone. As a third characteristic, each of the first sites a is surrounded with the plural second sites b. As a fourth characteristic, each of the second sites b is surrounded with the plural first sites a.
  • Although the first sites a and the second sites b are alternately bonded to each other in FIGS. 1, 3, [0058] 5 and 6, the first sites a and the second sites b may not be bonded to each other. In other words, the organic/inorganic hybrid film of Embodiment 1 may have the third or fourth characteristic without having the first and second characteristics.
  • FIG. 7([0059] a) shows the relationship between the coordinate axis (x-axis) corresponding to a distance from the center of the main chain of a polymer included in the organic/inorganic hybrid film of Embodiment 1 and the potential energy required for a copper ion to move along the main chain. FIG. 7(b) is a schematic diagram of the main chain of the polymer included in the organic/inorganic hybrid film of Embodiment 1. As is understood from FIGS. 7(a) and 7(b), the potential energy required for a copper ion to move from the vicinity of an oxygen atom (O) of siloxane (i.e., the first site a) to the vicinity of a carbon atom (C) of the organic molecule (i.e., the second site b) is very high and is specifically approximately 3 kcal/mol. In other words, a barrier to be cleared by the copper ion in moving from the first site a to the second site b is very high. Therefore, the copper ion drifting in the organic/inorganic hybrid film is easily trapped by the first site a.
  • FIG. 8([0060] a) shows the relationship between the coordinate axis (x-axis) corresponding to a distance from the center of the main chain of a polymer included in a conventional organic polymer film and the potential energy required for a copper ion to move along the main chain. FIG. 8(b) is a schematic diagram of the main chain of the polymer included in the organic polymer film. As is understood from FIGS. 8(a) and 8(b), the potential energy required for a copper ion to move from the vicinity of one carbon atom (C) included in the organic polymer to the vicinity of another carbon atom (C) is low and is specifically approximately 1.3 kcal/mol. Therefore, the copper ion drifting in the organic polymer film is minimally trapped.
  • FIG. 9([0061] a) shows the relationship between the coordinate axis (x-axis) corresponding to a distance from the center of the main chain of a polymer included in a conventional ladder type siloxane film and the potential energy required for a copper ion to move along the main chain. FIG. 9(b) is a schematic diagram of the main chain of the polymer included in the ladder type siloxane film. As is understood from FIGS. 9(a) and 9(b), the potential energy required for a copper ion to move from the vicinity of an oxygen atom (O) of siloxane to the vicinity of silicon (Si) is low and is specifically approximately 0.5 kcal/mol. Therefore, the copper ion drifting in the ladder type siloxane film is minimally trapped.
  • In FIG. 9([0062] b), when a hydrogen atom bonded to a Si atom is replaced with an organic group, the film is an organic siloxane film. Also in the organic siloxane film, the potential energy required for a copper ion to move from the vicinity of an oxygen atom (O) of siloxane to the vicinity of silicon (Si) is the same as that shown in FIG. 9(b). Therefore, the copper ion drifting in the organic siloxane film is minimally trapped.
  • FIG. 10 shows the barrier height and the drift rate of copper ions in the organic/inorganic hybrid film of [0063] Embodiment 1 shown in FIG. 7(b), the conventional organic polymer film shown in FIG. 8(b) and the conventional siloxane film shown in FIG. 9(b). In the organic polymer film, the data obtained in the experiment are varied. As is understood from FIG. 10, the barrier height for copper ions is large and the drift rate is low in the organic/inorganic hybrid film of Embodiment 1.
  • As is understood from the above description, the potential energy required for, namely, the barrier height to be cleared by, a copper ion moving along the main chain of the polymer included in the organic/inorganic hybrid film of [0064] Embodiment 1 is much higher than the potential energy required for, namely, the barrier height to be cleared by, a copper ion moving along the main chain of the organic polymer or the ladder type siloxane. Therefore, the copper ions are easily trapped and difficult to drift in the organic/inorganic hybrid film of Embodiment 1. Accordingly, copper (copper ions) used as the material for interconnects is minimally diffused into the interlayer dielectric film of Embodiment 1. As a result, the breakdown voltage of the interlayer dielectric film is minimally lowered even when used for a long period of time.
  • Now, a method for forming the organic/inorganic hybrid film of [0065] Embodiment 1 will be described with reference to FIGS. 11(a) through 11(c).
  • First, 1,6-(bistrichlorosilyl)hexane (a trichlorosilane derivative; a first silane derivative) shown on the left hand side of FIG. 11([0066] a) and methyltrichlorosilane (a second silane derivate) shown on the right hand side of FIG. 11(a) are hydrolyzed in a ratio of 1:1 in an alcohol solution, so as to obtain two silanols as shown in FIG. 11(b).
  • Next, the two silanols are polymerized through a dehydration condensation reaction, so as to give a silanol condensate as shown in FIG. 11([0067] c).
  • Then, a solution including the silanol condensate of FIG. 11([0068] c) is applied on a semiconductor substrate by spin coating and the resultant substrate is annealed. In this manner, the interlayer dielectric film of the organic/inorganic hybrid film having the structure as shown in FIG. 1 in which methylsilsesquioxanes in a cage structure (i.e., the first sites a) are bonded via methylene of hexane (i.e., the second site b) in a network structure is formed.
  • Although the trichlorosilane derivative is used as the first silane derivative in the above-described method for forming the interlayer dielectric film of [0069] Embodiment 1, a trialkoxysilane derivative may be used instead.
  • Also, although the silane derivative in which silicon atoms are crosslinked via hexane including six methylene groups is used as the second silane derivative, the number of methylene groups is not specified. Also, an organic molecule other than the methylene groups, such as phenylene, may be used as the crosslinking molecule. [0070]
  • Furthermore, any siloxane represented by the following general formula (1) may be widely used as the first site a included in the organic/inorganic hybrid film of Embodiment 1: [0071]
    Figure US20030008998A1-20030109-C00003
  • wherein R[0072] 1, R2 and R3 are an oxygen atom or an organic group.
  • Alternatively, any siloxane represented by the following general formula (2) may be widely used as the first site a included in the organic/inorganic hybrid film of Embodiment 1: [0073]
    Figure US20030008998A1-20030109-C00004
  • wherein R is an organic group; and R[0074] 1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
  • Moreover, polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers may be widely used as the second site b included in the organic/inorganic hybrid film of [0075] Embodiment 1.
  • [0076] Embodiment 2
  • An interlayer dielectric film and a method for forming the same according to [0077] Embodiment 2 of the invention will now be described with reference to the accompanying drawing.
  • The interlayer dielectric film of [0078] Embodiment 2 includes a plurality of first sites a each composed of siloxane and a plurality of second sites b each composed of an organic molecule. The plural second sites b together form an organic polymer film, in which the plural first sites a and a plurality of holes c are dispersed. In this case, the first site a composed of siloxane may be or may not be bonded to the second site b composed of the organic molecule.
  • FIG. 12 shows the cross-sectional structure of the interlayer dielectric film of [0079] Embodiment 2. As shown in FIG. 12, in the interlayer dielectric film formed on a semiconductor substrate 10, a plurality of silica fine particles 12 each corresponding to the first site a and a plurality of holes 13 are dispersed in an organic polymer film 11 formed from the plural second sites b.
  • Since the silica [0080] fine particles 12 of siloxane are dispersed in the organic polymer film 11 of the organic molecules in the interlayer dielectric film of Embodiment 2, copper interconnects 14 adjacent to each other are never connected through the silica fine particles 12 of siloxane. Therefore, copper ions drifting in the organic polymer film 11 from the copper interconnect 14 are trapped by the first sites a of siloxane and hence are minimally diffused into the organic polymer film 11. Accordingly, the copper interconnects 14 adjacent to each other can be prevented from being electrically connected through the copper ions.
  • In this case, the largest distance between the first sites a of siloxane forming the silica [0081] fine particles 12 is preferably smaller than the distance between the copper interconnects 14 adjacent to each other. Thus, the copper interconnects 14 adjacent to each other can be definitely prevented from being electrically connected through the first sites a of siloxane, and therefore, copper ions drifting in the organic polymer film 11 from one copper interconnect 14 can never pass by the vicinity of the first sites a of siloxane to reach the other adjacent copper interconnect 14. Accordingly, the copper ions drifting from one copper interconnect 14 can be prevented from reaching the other copper interconnect 14, and hence, the dielectric property of the interlayer dielectric film is never degraded.
  • Now, the method for forming the interlayer dielectric film of [0082] Embodiment 2 will be described.
  • Silica fine particles with an average particle size of 10 nm are dispersed in, for example, a polymer solution of the polyalyl ether family. Then, the solution in which the silica fine particles are dispersed is applied on a semiconductor substrate by spin coating, and the resultant semiconductor substrate is annealed. In this manner, the interlayer dielectric film as shown in FIG. 12 in which the plural silica [0083] fine particles 12 and the plural holes 13 are dispersed in the organic polymer film 11 formed from the plural second sites b can be obtained.
  • Although the polymer solution of the polyalyl ether family in which the silica fine particles are dispersed is used for forming the interlayer dielectric film in [0084] Embodiment 2, the interlayer dielectric film may be formed by using a solution including a silanol condensate obtained through hydrolysis and dehydration condensation of 1,6-(bistrichlorosily)hexane (first silane derivative) and methyltrichlorosilane as in Embodiment 1.
  • As the first site a included in the organic/inorganic hybrid film of [0085] Embodiment 2, any siloxane represented by the above-described general formula (1) or (2) may be widely used. As the second site b, polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers may be widely used.
  • [0086] Embodiment 3
  • An interlayer dielectric film according to [0087] Embodiment 3 of the invention will now be described with reference to the accompanying drawing.
  • FIG. 13 shows the cross-sectional structure of the interlayer dielectric film of [0088] Embodiment 3. As shown in FIG. 13, a lower interlayer dielectric film 21 and an upper interlayer dielectric film 22 are successively formed on a semiconductor substrate 20. A lower copper interconnect 23 is buried in the lower interlayer dielectric film 21, and an upper copper interconnect 24 is buried in the upper interlayer dielectric film 22.
  • As shown in FIG. 13, each of the lower and upper interlayer [0089] dielectric films 21 and 22 is made from a multi-layer film composed of a first layer d of siloxane and a second layer e of an organic molecule alternately stacked.
  • Since the first layer d of siloxane and the second layer e of the organic molecule are alternately stacked in the interlayer dielectric film of [0090] Embodiment 3, the lower copper interconnect 23 and the upper copper interconnect 24 are never electrically connected to each other through the first layer d of siloxane and the second layer e of the organic molecule. Therefore, copper ions drifting from the lower or upper copper interconnect 23 or 24 into the upper interlayer dielectric film 22 are trapped by siloxane included in the first layer d and hence are minimally diffused into the upper interlayer dielectric film 22. Accordingly, the lower copper interconnect 23 and the upper copper interconnect 24 can be prevented from being electrically connected to each other through the copper ions.

Claims (27)

What is claimed is:
1. An interlayer dielectric film comprising an organic/inorganic hybrid film having a main chain in which a first site of siloxane and a second site of an organic molecule are alternately bonded to each other.
2. The interlayer dielectric film of claim 1,
wherein pores are dispersed in said organic/inorganic hybrid film.
3. The interlayer dielectric film of claim 1,
wherein said first site is represented by the following general formula (1):
Figure US20030008998A1-20030109-C00005
wherein R1, R2 and R3 are an oxygen atom or an organic group.
4. The interlayer dielectric film of claim 1,
wherein said first site is represented by the following general formula (2):
Figure US20030008998A1-20030109-C00006
wherein R is an organic group; and R1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group
5. The interlayer dielectric film of claim 1,
wherein said second site is polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers.
6. An interlayer dielectric film comprising an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule,
wherein said first sites are bonded to said second sites alone and said second sites are bonded to said first sites alone.
7. The interlayer dielectric film of claim 6,
wherein pores are dispersed in said organic/inorganic hybrid film.
8. The interlayer dielectric film of claim 6,
wherein each of said plurality of first sites is represented by the following general formula (1):
Figure US20030008998A1-20030109-C00007
wherein R1, R2 and R3 are an oxygen atom or an organic group.
9. The interlayer dielectric film of claim 6,
wherein each of said plurality of first sites is represented by the following general formula (2):
Figure US20030008998A1-20030109-C00008
wherein R is an organic group; and R1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
10. The interlayer dielectric film of claim 6,
wherein each of said plurality of second sites is polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers.
11. An interlayer dielectric film comprising an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule,
wherein each of said plurality of first sites is surrounded with said plurality of second sites.
12. The interlayer dielectric film of claim 11,
wherein pores are dispersed in said organic/inorganic hybrid film.
13. The interlayer dielectric film of claim 11,
wherein each of said plurality of first sites is represented by the following general formula (1):
Figure US20030008998A1-20030109-C00009
wherein R1, R2 and R3 are an oxygen atom or an organic group.
14. The interlayer dielectric film of claim 11,
wherein each of said plurality of first sites is represented by the following general formula (2):
Figure US20030008998A1-20030109-C00010
wherein R is an organic group; and R1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
15. The interlayer dielectric film of claim 11,
wherein each of said plurality of second sites is polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers.
16. An interlayer dielectric film comprising an organic/inorganic hybrid film composed of a plurality of first sites of siloxane and a plurality of second sites of an organic molecule,
wherein each of said plurality of second sites is surrounded with said plurality of first sites.
17. The interlayer dielectric film of claim 16,
wherein pores are dispersed in said organic/inorganic hybrid film.
18. The interlayer dielectric film of claim 16,
wherein each of said plurality of first sites is represented by the following general formula (1):
Figure US20030008998A1-20030109-C00011
wherein R1, R2 and R3 are an oxygen atom or an organic group.
19. The interlayer dielectric film of claim 16,
wherein each of said plurality of first sites is represented by the following general formula (2):
Figure US20030008998A1-20030109-C00012
wherein R is an organic group; and R1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
20. The interlayer dielectric film of claim 16,
wherein each of said plurality of second sites is polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers.
21. An interlayer dielectric film comprising a plurality of first sites of siloxane and a plurality of second sites of an organic molecule,
wherein said plurality of second sites together form an organic polymer film, and
said plurality of first sites are dispersed in said organic polymer film.
22. The interlayer dielectric film of claim 21,
wherein a largest distance between said plurality of first sites is smaller than a distance between a pair of copper interconnects disposed with said organic polymer film sandwiched therebetween.
23. The interlayer dielectric film of claim 21,
wherein pores are dispersed in said organic polymer film.
24. The interlayer dielectric film of claim 21,
wherein each of said plurality of first sites is represented by the following general formula (1):
Figure US20030008998A1-20030109-C00013
wherein R1, R2 and R3 are an oxygen atom or an organic group.
25. The interlayer dielectric film of claim 21,
wherein each of said plurality of first sites is represented by the following general formula (2):
Figure US20030008998A1-20030109-C00014
wherein R is an organic group; and R1 and R2 are an oxygen atom or an organic group, which is selected from the group consisting of an alkyl group, an aryl group and an aryl group.
26. The interlayer dielectric film of claim 21,
wherein each of said plurality of second sites is polyimide, polyamide, polyimidazole, polyoxazole, polyphenylene, polyarylene, polyaryl ether, polyalkane or a fluorinated polymer of any of these polymers.
27. An interlayer dielectric film comprising a multi-layer film in which a first layer of siloxane and a second layer of an organic molecule are alternately stacked on each other.
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