WO2004099296A1 - Materiaux nanoporeux appropries a une utilisation dans les semiconducteurs - Google Patents

Materiaux nanoporeux appropries a une utilisation dans les semiconducteurs Download PDF

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Publication number
WO2004099296A1
WO2004099296A1 PCT/NL2004/000242 NL2004000242W WO2004099296A1 WO 2004099296 A1 WO2004099296 A1 WO 2004099296A1 NL 2004000242 W NL2004000242 W NL 2004000242W WO 2004099296 A1 WO2004099296 A1 WO 2004099296A1
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Prior art keywords
porogen
network system
network
resin
composition according
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PCT/NL2004/000242
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English (en)
Inventor
Shahab Jahromi
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Dsm Ip Assets B.V.
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Publication of WO2004099296A1 publication Critical patent/WO2004099296A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • H—ELECTRICITY
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—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
    • H01L21/02203—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 porous
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • 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
    • H01L21/02104—Forming layers
    • 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
    • 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
    • H01L21/76801—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/5329—Insulating materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—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
    • 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
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—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
    • 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
    • H01L21/02214—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 comprising silicon and oxygen
    • H01L21/02216—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 comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

Definitions

  • the present invention relates to nanoporous materials, which can for example be used as matrix for interlayer dielectrics, for example in semiconductors.
  • the nanoporous materials according to the present invention can have a low dielectric constant (k), for example even lower than 2.
  • the invention also relates to a composition on which the nanoporous materials according the invention can be based, a method of making the nanoporous materials according to the invention, and the products in which the nanoporous materials according to the invention can be used.
  • Macroscopic phase separation is here and hereafter defined as a stage in which two different phases are present, of which the porogen phase comprises structures larger than the wavelength of visible light, i.e. higher than approximately 400 nm.
  • the macroscopic phase separation large pores or even interconnected structures are formed, decreasing the mechanical properties of the interlayer once the porogen is burned out.
  • the composition according to the invention comprises a porogen network system (a) capable of forming a network.
  • the porogen network system comprises at least a functionalised porogen (i).
  • the functionalised porogen is capable of forming a network either by itself or with another compound (ii).
  • the presence of at least one other compound (ii) having functional groups capable of reacting with functional groups present on the porogen is required to make the porogen network system capable of forming a network.
  • Suitable porogens (i) for the composition according to the invention are either organic or inorganic compounds.
  • inorganic porogens are compounds which are labile at higher temperatures.
  • the used porogens are organic compounds. These organic compounds have to be decomposable, due to the fact that they have to be burned out the matrix structure during the production of the porous dielectric material.
  • Suitable organic porogens are for example linear, branched and crosslinked polymers and copolymers, but also crosslinked polymeric nanoparticles with reactive surface functionality.
  • the porogen may be a polymer comprised of aliphatic polycarbonates, polyester, polysulfones, polylactides, polylactones.
  • the porogen may be a polymer comprised of monomer units as for example styrene, halogenated styrene, hydroxy-substituted styrene, lower alkyl- substituted styrene, acrylic acid, acrylamide, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, ethylene oxide, propylene oxide, and combinations of any of them.
  • the porogen may be a homopolymer or a copolymer, for example based on the foregoing monomer units.
  • suitable polymers include but are not limited to poly(methylmethacrylate), polystyrene, poly( ⁇ -methylstyrene) aliphatic polycarbonates, polyesters, polyesteramides, polysulfones, polylactides or polylactones.
  • Branched polymers are suitable for the porogen, for example dendrimers, hyperbranched polymers, star shaped polymers.
  • dendrimers, polyesteramides or star shaped poly ( ⁇ -caprolactone) are used.
  • dendrimers to be used as porogen (i) in the present invention are for example described in WO93/14147 and WO95/02008 which dendrimers are incorporated by reference herein.
  • dendrimers used as porogens preferably at least generation 3 dendrimers are used. More preferably generation 3 or 4 dendrimers are used.
  • polyesteramides to be used as porogen (i) in the present invention are for example described in WO 99/16810, which describes linear or branched condensation polymers containing ester groups and at least one amide group in the backbone, having at least one hydroxy alkyl amide endgroup or modified hydroxyl amide endgroup, and having a weight average molecular mass of > 800 g/mol.
  • the polyesteramides described in WO 99/16810 are hereby incorporated by reference.
  • a preferred polyesteramide is a branched polyesteramide having at least two groups according to formula II:
  • Y C— C— O— H , H, (C C 24 )(cyclo)alkyl or (C ⁇ -C 10 ) aryl, R 5 ,
  • R B (C 2 -C 24 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may, independently of one another, be the same or different, H, (C 6 -C 10 ) aryl or (C C 8 )(cyclo)alkyl radical. Also mixtures of porogens may be used.
  • the porogen has to be capable of forming a network either by itself or with another compound. Therefore the porogen has to be equipped with functional groups.
  • the amount of functional groups is not limiting to the composition according to the invention, however, In all cases the average functionality of the porogen network system must be higher than 2.
  • the porogen should have a functionality of at least 2 per molecule.
  • Introduction of functional groups to the porogen can be carried out using conventional methods, known to those skilled in the art.
  • possible functional groups are for example oxazolines, nitriles, acryaltes, epoxy's, vinyl ethers.
  • porogen In a system where the porogen is not capable of reacting with itself, possible functional groups are hydroxy or amine groups, preferably hydroxy groups. In one embodiment of the invention, wherein the porogen is not capable of reacting with itself, the porogen has at least 2 functional groups per molecule.
  • compound (ii) is required to make the porogen network system of the present invention capable of forming a network.
  • Such compound (ii) has to be capable of reacting with the functional groups of the porogen.
  • suitable compounds (ii) are isocyanates, ketenes, cyano compounds, imino ethers, cardobiimides, aldehydes, ketons or the like.
  • compound (ii) is a porogen containing another functionality than the other porogen.
  • compound (ii) is an isocyanate.
  • suitable isocyanates are trifunctional isocyanates or bifunctional isocyanates.
  • trifunctional isocyanates are used.
  • a preferred embodiments of the invention is a composition comprising a bifunctional porogen (i) and a trifunctional compound (ii)
  • the amount of compound (ii) used may be determined by the person skilled in the art.
  • the ratio between the amount of functional groups of the porogen (i) and the amount of functional groups of the compound (ii) is at least 0.1 , more preferably at least 0,5, still more preferably at least 1.2 and most preferably about 1.
  • the ratio between the amount of functional groups of the porogen (i) and the amount of compatible functional groups of the compound (ii) is at most 10, more preferably at most 5 and still more preferably at most 1.2.
  • the functional groups of the porogen (i) and the functional groups of compound (ii) are present in stoichiometric amounts.
  • the network reaction of the functional groups of the porogen network system may involve all types of reactions, either forming physical networks or chemical networks. Examples of possible reactions resulting in physical networks are hydrogen- bridges, VanderWaals bonding, ionic bonding or coordination bonding. Examples of reactions resulting in chemical networks are nucleophilic substitution, electrophilic substitution, free radical substitution, Diels Alder reaction.
  • the functional groups forming a network in the porogen network system are capable of reacting fast with each other, so that phase separation due to evaporation of solvent or due to the curing reaction of the resin does not take place any more, as the porogen is part of the nettechnik already. It is believed that network formation of the porogen network system during the spin coating itself is most effective for preventing the macroscopic phase separation.
  • Examples of fast combinations of functional groups are the combination of alcohols and isocyanates, or amines and isocayanates, free radical polymerisation of acrylates.
  • the functional groups in the porogen network system are combinations of alcohols and isocyanates.
  • any resin (b) can be used in the composition according to the invention as long as it is not susceptible to thermal degradation at the same temperature the porogen network will degrade.
  • the resin should have, after curing, a glass transition temperature of at least about 400°C, more preferably at least about 440 °C, most preferably about 500 °C. Also mixtures of resins may be used.
  • the molecular weight (Mw) of the resin (b) is larger than 750. However, also high molecular weight resins are also suitable.
  • the molecular weight (Mw) of the resin (b) is preferably lower than 100,000.
  • the resin is not capable of reacting with the porogen itself. More preferably the resin is not capable of reacting with any components of the porogen network system. This has the advantage that the efficiency of the porogen network system is not influenced by any side reactions.
  • suitable resins are silicon-containing polymers, such as organosilicates, polyarylenes, polyimides and polybenzocyclobutene (eg. Sumitomo Bakelite).
  • suitable organosilicates are silsesquioxanes, alkoxy silanes, organic silicates, orthosilicates and organically modified silicates.
  • Suitable silsesquioxanes are for example, hydrogen silsesquioxanes, alkyl silsesquioxanes, preferably lower alkyl silsesquioxanes, aryl or alkyl/aryl silsequioxanes, such as phenyl silsesquioxanes, and copolymers of silsesquioxanes with for example polyimides.
  • suitable polyarylenes are polyphenylenes, poly(phenylquinoxalines) and poly(arylene ethers).
  • An example of a commercially available polyarylene is SiLKTM (Dow Chem Inc.).
  • organosilicates are used.
  • suitable commercially available organosilicates are Zirkon Lk (Shiply), HOSP (Honeywell), Fox (Dow Corning), MezoELK (Chemicals affiliate Schumacher), polysilazane (AZ Electronics/Clariant), and polymethylphenylsiloxane resin, such as GR150F (Techneglas).
  • HSQ hydrogen sisesquioxane
  • MSQ methyl silsesquioxane
  • the amount of porogen network system (a) with respect to the amount of resin (b) determines the amount of pores in the matrix material to be produced. The more pores in the matrix material, the lower the dielectric constant (k).
  • the composition according to the invention makes it possible that even an amount of 80 wt% porogen can be reached, without any sign of macroscopic phase separation.
  • the composition according to the invention comprises at least an amount of 0.1 wt% porogen, more preferably at least an amount of 1 wt% porogen and most preferably an amount of 5 wt% porogen.
  • the amount of porogen network system (a) is at most 80 wt% with respect to the total weight of the porogen network system (a) and the resin (b).
  • the amount of porogen network system (a) is at most 70 wt %, more preferably at most 60 wt % and even more preferably at most 50 wt%.
  • the composition according to the invention also comprises a catalyst (c) in order to speed up the network formation of the porogen network system.
  • a catalyst c
  • suitable catalysts depend on the porogen network system used. The person skilled in the art can determine which catalyst is suitable for the porogen network system used. Also mixtures of catalysts may be used.
  • Suitable catalysts for the composition according to the present invention are the present invention are acids and bases.
  • suitable acid catalyst are Sb 2 O 3 , As 2 O 3 , dibutyltinlaurate LiX, BX 3 , MgX 2 , AIX 3 , BiX 3 , SnX 4 , SbX 5 , FeX 3 , GeX 4 , GaX 3 , HgX 2 , ZnX 2 , AIX 3 , TiX 4 , MnX 2 , ZrX 4 , R 4 NX, R 4 PX, or HX where X is H, R, I, Br, Cl, F, acetylacetonate (acas), OR, O(O)CR or combinations of these and R is alkyl or aryl.
  • DABCO diazobicyclo[2,2,2]octane
  • DMAP dimethylaminopyridine
  • tin-based catalysts are preferred, for example dibutyltin acetate.
  • the amount of catalyst (c) used may be determined by the person skilled in the art. Generally the amount of catalyst is at least 0.01 wt % with respect to the porogen network system. Preferably the amount of catalyst is at least 0.1 wt%, more preferably at least 1 wt% and even more preferably at least 10 wt%. Generally the amount of catalyst is at most 100% with respect to the porogen network system.
  • the composition according to the invention may comprise an inert solvent (d).
  • the solvent should be inert as to not react with any of the other components of the composition. The components of the composition should however dissolve in the solvent. The person skilled in the art can easily determine which type of solvent is most suitable for the specific components as used in the composition of the present invention. Suitable solvents include but are not limited to ketones, esters, ethers, alcohols, and/or hydrocarbons. Also mixtures of different solvents can be used.
  • the amount of solvent used for spin coating preferably may range between 50 and 98% (based on the total weight of the composition according to the invention).
  • the solvent is chosen from the group including hydrocarbons, especially aromatic hydrocarbons; ethers, especially glycoethers and other equivalent ethers; and various esters, well-known to the person skilled in the art.
  • suitable solvents are for example aromatic hydrocarbon compounds (for example the 'Solvesso' types), N-methylpyrolidone, xylene, dichlorobenzene, propylene glycol monomethylether, methylpropylene glycol acetate, butyl acetate, dibasic ester, isophoron, ethyl ethoxypropionate, ethylene-propylene glycol acetate and/or butyl glycol.
  • aromatic hydrocarbon compounds for example the 'Solvesso' types
  • N-methylpyrolidone for example the 'Solvesso' types
  • xylene for example the 'Solvesso' types
  • dichlorobenzene propylene glycol monomethylether
  • methylpropylene glycol acetate butyl acetate
  • dibasic ester dibasic ester
  • isophoron ethyl ethoxypropionate
  • ethylene-propylene glycol acetate and/or butyl glycol
  • the present invention also relates to the use of a porogen network system (a) comprising at least a functionalised porogen for in the production of a porous material.
  • the porogen network system is used during a spin coating process, or a similarly fast coating process, for example spray coating.
  • Preferences for the porogen network system are as described above.
  • the porogen network system (a) is used in combination with a catalyst (c).
  • Preferences for the catalyst (c) are as described above.
  • the composition according to the invention is suitable for use in a method for making porous material using a fast coating process. Examples of suitable fast coating processes are spin coating or spray coating.
  • the coating of the substrate need not be performed at higher temperatures. Preferably, the coating takes place without additional heating, i.e. at room temperature.
  • An example of a suitable method to produce porous material comprises the steps of:
  • Td is higher than Tc, but less than Tg.
  • the porogen network system (a), the resin (b), the catalyst (c) and the inert solvent (d) being the same as already specified above, including the same preferences as to chemical consistence and amounts.
  • the completion of porogen network formation takes place after the application of the composition to the substrate, so that the composition can flow to form the coating.
  • the coating process preferably takes place at room temperature, thus the network formation preferably can take place at room temperature.
  • room temperature depends on the circumstances. It is here and hereafter defined as approximately 20 °C +/- 5 °C.
  • the nanoporous material can be used for several applications, for example in micro-electronics or anti-reflective coatings.
  • the pore size of the nanoporous material in micro-electronic applications is about 10% of the size of the individual metallic circuit lines or less.
  • the averabe pore size preferably is about 13 nm or less.
  • Pore sizes depend on the type of porogen used.
  • the average pore sizes of can be for example at least about 5 nm.
  • the pore size may be heterogeneously or homogeneously distributed.
  • the pore size is more homogeneously distributed, since this may be of benefit to the material properties of the nanoporous material, as well as the dielectric constant.
  • Nanoporous material prepared according to the invention can reach a dielectic constant of lower than 3, preferably lower than 2,5, and even more preferably lower than 2.
  • the substrate is generally an inert substrate, for example glass, silicon or ceramic.
  • Suitable inert substrates also include epoxy composites, polyimides, phenolic polymers, high temperature polymers, and the like.
  • the substrate can optionally have integrated circuits disposed therein.
  • the substrate may be provided with electrical conductor means such as input/output pins (I/O pins) for electrically connecting the packaging device to the circuit board.
  • I/O pins input/output pins
  • a plurality of electrically insulating and electrically conducting layers may be alternatively stacked up on the substrate. The layers are then generally formed on the substrate in a layer-by-layer process wherein each layer is formed in a separate process step.
  • a metallic film may be deposited on the substrate, where after the metallic film is lithographically patterned to provide a pattern of individual metallic circuit lines on the substrate followed by the method of making a layer of a nanoporous material on the substrate as described above.
  • nanoporous material made from the composition according to the invention can be used in a semiconductor.
  • a semiconductor may comprise a layer of the nanoporous material according to the invention.
  • Triisocyanate (DesmodurTM RFE, Bayer) was re-crystallised from dichloromethane to give white crystals having an isocyanate functionality of 3.
  • Samples were cured in an oven under nitrogen for 2 hours at 200°C and 2 hours at 530°C respectively, yielding coated substrates having a spin-coated film with a layer thickness below 2 ⁇ m.
  • a comparative example was prepared in the same manner as indicated above with the difference that no Desmodur RFE was added to the formulation.
  • Photograph 1 shows the light microscopy image of the spin coated film of Example I.
  • Photograph 2 shows the light microscopy image of the spin coated film of the comparative example.
  • Comparative Experiment A appeared white milky indicative of macroscopic phase separation. This is also reflected in the light microscopy image of Comparative Experiment A showing a clear two-phase structure. In fact, investigations at lower loadings have indicated that the macroscopic phase separation already occurs above 10 wt% dendrimer in formulations without Desmodur RFE. In contrast, samples containing Desmodur RFE all appeared transparent even at a dendrimer loading of 70 wt%. This is also evident from the microscopy image of Example I, which shows no structure at least on microscopic scale.
  • SAXS Small angle X-ray scattering
  • the Kratky setup is equipped with an entrance slit of 40 ⁇ m and features a sample-to-detector distance of 288mm.
  • the scattering patterns from the samples and the background scattering were recorded with a position sensitive detector (MBRAUN 50M) for about 2-3 days.
  • MBRAUN 50M position sensitive detector
  • the signal recorded from a PE reference sample was used for intensity calibration, whereas sample transmissions were derived from its attenuation.
  • q 2 ⁇ s - (4 ⁇ / ⁇ )*sm ' 3 , the position of the (attenuated) primary beam was recorded without beamstop.
  • SAXS data processing including subtraction of the transmission- weighted background signal were performed with subroutines of the FFSAXS software, developed by Vonk.
  • the overall background signal including parasitic scattering from the SAXS camera and contributions from the glass substrate was subtracted from the scattering pattern in order to minimize statistical errors at high s.

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Abstract

L'invention concerne une composition qui comprend: (a) un système à réseau porogène capable de former un réseau renfermant au moins un porogène fonctionnalisé (i); (b) une résine; (c) un catalyseur; et (d) un solvant inerte. On a constaté avec surprise que ladite composition se prêtait à une utilisation en application par centrifugation, mais sans risque de séparation de phase macroscopique. On peut ainsi élaborer un matériau nanoporeux à faible constante diélectrique.
PCT/NL2004/000242 2003-05-05 2004-04-09 Materiaux nanoporeux appropries a une utilisation dans les semiconducteurs WO2004099296A1 (fr)

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US60/467573 2003-05-05
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008049577A1 (fr) * 2006-10-25 2008-05-02 Dsm Ip Assets B.V. Dispositifs optoélectroniques organiques

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6391932B1 (en) * 2000-08-08 2002-05-21 Shipley Company, L.L.C. Porous materials
US6495479B1 (en) * 2000-05-05 2002-12-17 Honeywell International, Inc. Simplified method to produce nanoporous silicon-based films
US20030012942A1 (en) * 2001-05-03 2003-01-16 The Board Of Regents Of The University Of Nebraska Sol-gel preparation of porous solids using dendrimers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495479B1 (en) * 2000-05-05 2002-12-17 Honeywell International, Inc. Simplified method to produce nanoporous silicon-based films
US6391932B1 (en) * 2000-08-08 2002-05-21 Shipley Company, L.L.C. Porous materials
US20030012942A1 (en) * 2001-05-03 2003-01-16 The Board Of Regents Of The University Of Nebraska Sol-gel preparation of porous solids using dendrimers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008049577A1 (fr) * 2006-10-25 2008-05-02 Dsm Ip Assets B.V. Dispositifs optoélectroniques organiques

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