Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1675—Process conditions
  • C23C18/168—Control of temperature, e.g. temperature of bath, substrate
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1675—Process conditions
  • C23C18/1682—Control of atmosphere
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1689—After-treatment
  • C23C18/1692—Heat-treatment
  • C23C18/1696—Control of atmosphere
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1689—After-treatment
  • C23C18/1692—Heat-treatment
  • C23C18/1698—Control of temperature
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
  • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
  • C23C18/1886—Multistep pretreatment
  • C23C18/1889—Multistep pretreatment with use of metal first
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/208—Multistep pretreatment with use of metal first
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • 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
  • H01L21/76838—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 conductors
  • H01L21/76841—Barrier, adhesion or liner layers
  • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
  • H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • 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
  • H01L21/76838—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 conductors
  • H01L21/76841—Barrier, adhesion or liner layers
  • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
  • H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating

Definitions

• the present invention relates, in general, a metallization method of a substrate and, more particuliè ⁇ surely, a method of forming a primer layer permet- as the subsequent deposition of a metal.
• the components formed in integrated circuits are generally interconnected using metal tracks, for example copper, formed on the surface of a substrate.
• metal tracks for example copper
• One of them consists in producing a non-electrolytic deposition of copper on the substrate.
• non-electrolytic deposition or “electroless” is meant a deposit made electrolessly without the use of electrodes.
• a priming layer which allows a good grip on the substrate and which constitutes a primer to the autocatalytic reaction.
• Known methods for training this type of primer layer implement expensive operations, for example opera suites ⁇ physical deposition tions, e.g.
• phase physical deposition vapor (“physical vapor deposition", PVD), and etching, for example plasma etching.
• etching for example plasma etching.
• several steps are generally necessary to form, on the one hand, a layer of a material that provides adhesion on the substrate and, on the other hand, seeds of a material that allows the autocatalytic reaction of the metal.
• the material providing the adhesion to the substrate is a material based on tantalum nitride (TaN) or titanium nitride (TiN) and the material for the autocatalytic reaction of the metal is a palladium-based material (Pd ), tin (Sn) and / or ruthenium (Ru).
• the invention proposes to provide an adhesion and catalytic layer by immersing one or more substrates in a single bath comprising a mixture of a copper or nickel compound and a compound allowing adhesion to the substrate.
• an embodiment provides a method of forming, on a substrate, a priming layer for subsequent deposition of a layer of a metal, comprising immersing the substrate in a bath comprising a substrate material.
• a substrate material comprising a substrate material.
• the subsequent deposition is a non-electrolytic deposit.
• the bath is maintained at a temperature between 80 and 130 0 C, preferably 110 0 C, and a hydrogen atmosphere is maintained above the bath so as to have a total pressure between 2000 and 4000 hectopascals, preferably 3000 hectopascals, the substrate being immersed for several hours, preferably for about eight hours.
• said material is tetraethoxysilane (TEOS). According to one embodiment, the concentration of
• the copper or nickel amidinate in TEOS is between 15 grams per liter and the saturation concentration of the amidinate in TEOS.
• the substrate is made of a material, or is coated with a material, included in the group comprising silicon oxide, silicon, glass, benzobicyclobutene (BCB), and conductive materials. .
• the immersion step is followed by venting then an annealing step, at a temperature between 250 and 350 0 C, preferably about
• the substrate comprises trenches and / or vias.
• the bath comprises a photosensitive compound.
• Another embodiment provides a pretreatment agent applied to a substrate to be coated with a layer of a metal, consisting of a solvent of the family of ethoxysilanes or siloxanes and a nickel or copper amidinate .
• FIG. 1 illustrates a step of forming an electroless plating initiation layer according to one embodiment of the present invention
• Figure 2 shows a flowchart of a method according to an embodiment of the present invention
• FIGS. 3A to 3C are sectional views illustrating an example of application of an embodiment of the method to the formation of metal tracks on an integrated circuit
• Figs. 4A to 4D are sectional views illustrating an exemplary application of an embodiment of the method to formation of a track and a conductor via an interconnection stack of an integrated circuit.
• FIG. 1 illustrates a step of forming an electroless plating priming layer according to one embodiment of the present invention.
• a nacelle 3 in which are disposed several substrates 5 whose surfaces, or surface portions, must be metallized.
• the vessel 1 is filled with a bath 7 which comprises a mixture of a copper compound and a compound for adhesion to the substrate.
• the adhesion compound is a compound of the family of ethoxysilanes or siloxanes, for example tetraethoxysilane (TEOS) of the following semi-developed formula:
• Et denotes an ethyl group
• TEOS used as a solvent, forms a rough adhesion agent to the substrate.
• the copper compound is a copper amidinate.
• this copper amidinate may be copper (N, N'-diisopropylacetamidinate), of empirical formula [Cu ( 1 Pr-amd)] 2, and of the following semi-developed formula: iPr iPr
• amidinate used may be any known type of copper amidinate.
• Fig. 2 is a flowchart of a method of forming a non-electrolytic deposition priming layer according to an embodiment of the present invention.
• a bath containing a mixture of copper amidinate and TEOS is prepared.
• concentration of copper amidinate in TEOS will be between 15 and 150 grams per liter (up to the saturation concentration of the amidinate in the solvent).
• step 13 the substrates are prepared for their treatment (cleaning by plasma ).
• step 15 the substrates are arranged in a nacelle.
• step 17 the nacelle is immersed in the bath for several hours, for example from two to fifteen hours, and preferably for eight hours.
• a hydrogen atmosphere is maintained at a pressure of between 1000 and 3000 hectopascals (total pressure between 2000 and 4000 hectopascals), and preferably 2000 hectopascals (total pressure of 3000 hectopascals), as is illustrated in Figure 1 by arrows 9.
• the bath is maintained at a temperature between 80 and 130 0 C and, preferably, at a temperature of about 110 0 C to obtain good adhesion of the priming layer formed on the substrate.
• the nacelle (s) are removed from the tank and vented.
• step 21 the substrates, maintained or not in the nacelle, are annealed to densify the layer obtained.
• This annealing is carried out at a temperature of between 200 and 350 ° C., preferably 300 ° C., for a period of between two and four hours, for example three hours, under a flow of hydrogen and / or argon. .
• This step is optional in that the priming layer formed during the immersion also densifies in the open air. Annealing, however, has the advantage of accelerating this phenomenon.
• a priming layer having a thickness of approximately 0.3 ⁇ m.
• Figs. 3A-3C are sectional views illustrating an exemplary application of an embodiment of the priming layer deposition method to the formation of metal tracks on an integrated circuit.
• FIG. 3A illustrates a substrate 5 coated with a priming layer 23 formed by the method described in connection with FIGS. 1 and 2.
• a photolithography of the priming layer 23 is carried out so as to form openings 25 in this layer and leave portions 27 at the locations where the tracks are desired.
• the photolithography ⁇ graphy may conventionally be carried out using a mask and / or a suitable resin for obtaining slopes and / or portions 27 of desired dimensions.
• the etching may be a liquid etching with FeCl3 iron chloride.
• a photosensitive compound may be added to the bath 7 so as to render the priming layer 23 photosensitive and to eliminate certain steps of the photolithography.
• the non-electrolytic deposition is carried out.
• a non-electrolytic deposit of copper will be considered here.
• the substrates are immersed in a bath comprising, in a conventional manner, the following elements:
• a source of copper for example a sulfate salt CUSO 4, 5H 2 O;
• a reducing agent for example formaldehyde (HCOH);
• a pH stabilizer a hydroxide, for example
• - complexing agents for example EDTA (ethylenediaminetetraacetic acid, C] _OH] _6N2 ⁇ g) to prevent spontaneous deposition of copper in the bath; and
• additives which make it possible to improve the quality of the deposit, for example surfactants, stabilizers, wetting agents, accelerating agents and / or retarders.
• Figure 3C illustrates the result obtained after performing the electroless deposition of copper on the structure of Figure 3B.
• On each of the portions 27 is formed a portion of copper 29.
• the copper portions 29 are formed in a direction perpendicular to the surface of the substrate 5.
• the copper portions 29 may have a thickness of up to 5 microns.
• the substrate 5 may be a semiconductor wafer, for example made of silicon, but the invention is also applicable to the formation of copper portions on any other type of substrate, for example on substrates insulators such as glass plates, layers of silicon oxide (SiO 2) or benzocyclobutene (BCB), or on conductive substrates.
• substrates insulators such as glass plates, layers of silicon oxide (SiO 2) or benzocyclobutene (BCB), or on conductive substrates.
• FIG. 4A-4D are sectional views illustrating an example of application of the method according to one embodiment to the formation of a track and a conductive via in an interconnection stack of an integrated circuit.
• FIG. 4A starts from an interconnection stack in which an interconnection level N is formed, this level comprising an insulating layer 33, for example made of BCB or SiC> 2, on which a conducting track 35 is formed. , shown here in section along its length.
• an interconnection level N is formed on the interconnection level N is formed a layer of an insulating material 37 (interconnection level N + l), the surface is etched (opening 39) so as to define the ⁇ convenient location with the conductive material in the level of higher interconnection (tracks and vias of level N + 1).
• the structure was immersed in a bath such as that of FIG. 1 and the associated procedure presented above was followed.
• a priming layer 41 is obtained on the surface of the insulating material 37 and on the walls and bottom of the opening 39.
• a non-electrolytic deposit for example copper
• This deposit forms, in the opening 39 and on the layer 41, a copper layer 43.
• a chemical-mechanical polishing (CMP) of the structure of FIG. 4C was carried out so as to reveal the upper surface of the insulating layer 37. The level of interconnection N is then obtained. + l.
• this method also applies to the metallization of a substrate having any other shape, for example a substrate comprising vias and / or trenches.
• the method according to one embodiment may also allow the metallization of more complex forms on the surface of a substrate.
• the non-electrolytic deposition carried out on the copper or nickel based priming layer may be a deposit of any known metal that may be deposited on such a priming layer.
• a priming layer formed using copper amidinate copper, nickel or platinum may be deposited in particular.
• nickel amidinate On a priming layer formed using nickel amidinate, can be deposited in particular copper, nickel, platinum or gold.
• the copper or nickel based priming layer may be formed on any other type of known substrate, having any kind of more or less pronounced relief.
• the priming layer formed according to one embodiment may also be used as a priming layer for electrolytic deposits.

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• Chemical & Material Sciences (AREA)
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• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Manufacturing & Machinery (AREA)
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• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Chemically Coating (AREA)
• Electrodes Of Semiconductors (AREA)
• Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

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• 2008
  • 2008-03-28 FR FR0852045A patent/FR2929449A1/fr not_active Withdrawn
• 2009
  • 2009-03-30 WO PCT/FR2009/050524 patent/WO2009125143A2/fr active Application Filing
  • 2009-03-30 EP EP09729442A patent/EP2272085A2/fr not_active Withdrawn
  • 2009-03-30 US US12/935,186 patent/US9093381B2/en active Active
  • 2009-03-30 CN CN200980111161.5A patent/CN101981663B/zh active Active

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