EP1468446A1 - Procede de production de couches dielectriques avec utilisation de carbosilane multifonctionnel - Google Patents

Procede de production de couches dielectriques avec utilisation de carbosilane multifonctionnel

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Publication number
EP1468446A1
EP1468446A1 EP02804878A EP02804878A EP1468446A1 EP 1468446 A1 EP1468446 A1 EP 1468446A1 EP 02804878 A EP02804878 A EP 02804878A EP 02804878 A EP02804878 A EP 02804878A EP 1468446 A1 EP1468446 A1 EP 1468446A1
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EP
European Patent Office
Prior art keywords
dielectric layers
aryl
alkyl
layers according
multifunctional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02804878A
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German (de)
English (en)
Inventor
Stephan Kirchmeyer
Detlef Gaiser
Harald Kraus
Udo Merker
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HC Starck GmbH
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Bayer AG
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Publication date
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Publication of EP1468446A1 publication Critical patent/EP1468446A1/fr
Withdrawn legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming 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
    • H01L21/02123Forming 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
    • H01L21/02126Forming 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
    • HELECTRICITY
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • HELECTRICITY
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203Forming 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205Forming 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
    • H01L21/02208Forming 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
    • H01L21/02214Forming 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
    • H01L21/02216Forming 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
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    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282Forming 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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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/312Organic layers, e.g. photoresist
    • H01L21/3121Layers comprising organo-silicon compounds
    • H01L21/3122Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31695Deposition of porous oxides or porous glassy oxides or oxide based porous glass
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture 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
    • H01L21/71Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801Applying 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
    • H01L21/76829Applying 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 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894Materials of the insulating layers or coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/52Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522Arrangements 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
    • H01L23/532Arrangements 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
    • H01L23/5329Insulating materials
    • HELECTRICITY
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    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30Technical effects
    • H01L2924/301Electrical effects
    • H01L2924/3011Impedance
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/46Manufacturing multilayer circuits
    • H05K3/4644Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676Single layer compositions

Definitions

  • the present invention relates to a ner driving for the production of dielectric
  • Highly integrated microelectronic circuits consist of a large number of semiconducting elements, which are produced by selective doping and structuring of monocrystalline silicon. These individual semiconductor elements are connected to form a functioning unit by means of a layer structure consisting of conductor tracks and the intermediate layers required for insulation, the so-called interconnect.
  • the progressive miniaturization places extreme demands on the materials used.
  • the properties of the interconnect determine the performance characteristics of these highly integrated microelectronic circuits. These requirements are determined by the ever higher clock frequencies and the shorter signal delays required for this.
  • a high conductivity of the conductor track material and a low dielectric constant of the insulator material are desired.
  • the miniaturization of the semiconductor elements and the interconnect negatively influences the component properties.
  • Conductor resistance increased.
  • the interactions between the conductor tracks depend to a large extent on the relative dielectric constant ⁇ (the k value) of the insulator material. Attempts are made to counteract these technical difficulties by using conductor materials with a higher specific conductivity and insulator materials with a lower dielectric constant.
  • the aluminum that was previously used as a conductor material is gradually being replaced by copper, which has a higher specific conductivity.
  • silicon dioxide has proven itself as an insulator material in the manufacture of highly integrated circuits in both its electrical and process properties.
  • the dielectric constant of silicon dioxide is approx.
  • the value of the relative dielectric constant (k value) depends strongly on the temperature at which this value is determined.
  • the values given here are understood to mean the values which result from a determination at 22 ° C. and a pressure of 1 bar.
  • the dielectric constant (the k value)
  • the dielectric material must be able to withstand high process temperatures up to 400 ° C, which are achieved in subsequent metallization and tempering steps.
  • the layer materials or their precursors are available in sufficient purity, since impurities, in particular metals, can have a negative effect on the electrical properties of the layer materials.
  • the dielectric material should be as easy to process as possible and be applied as a thin layer in an industry-standard process such as the spin coating process.
  • silsesquioxanes and carbon-doped silicon dioxide have been described as dielectrics with a dielectric constant below 3.0.
  • Organic polymers as dielectrics with a low dielectric constant have found their way into technical production.
  • the properties of these polymers lead to considerable problems in process integration.
  • Their limited chemical and mechanical stability at elevated temperatures limits the subsequent process steps.
  • Necessary polishing steps are optimized, for example, on layers that are similar to silicon dioxide, and often lead to less than optimal results on organic polymer layers.
  • Silsesquioxanes are organosilicon polymers that are applied as oligomer solutions in the spin coating process and then thermally crosslinked.
  • WO 98/47944 AI teaches the use of organosilsesquioxanes for the production of layers with k values less than 2.7. However, these compounds can only be obtained from trialkoxysilanes via complex synthetic routes.
  • US-A-5,906,859 teaches the application of oligomeric hydridosilsequioxanes which are thermally crosslinked to form polymers. Dielectric constants of 2.7-2.9 are achieved with the compounds described in US Pat. No. 5,906,859.
  • Carbon-doped silicon dioxide is applied from organosilanes in a PE-CVD (Plasma Enhanced Chemical Vapor Deposition) process with reactive oxygen plasma.
  • PE-CVD Pullasma Enhanced Chemical Vapor Deposition
  • carbon-doped silicon dioxide Because of its silicon dioxide matrix, carbon-doped silicon dioxide has similar process properties to silicon dioxide and is therefore significantly lighter to integrate into the production process. The dielectric constant of these layers is reduced compared to silicon dioxide by the carbon content. US-A-6,054,206 teaches the application of such layers of gaseous organosilanes. However, the high vacuum plasma CND process is complex and involves high costs. With carbon-doped silicon dioxide layers, too
  • WO 99/55526 A1 also describes the production of dielectric layers by means of a CND process, preferably a plasma CND process.
  • a CND process preferably a plasma CND process.
  • layers are obtained which have a backbone structure made of Si-O-Si bonds, organic side groups being bound to this structure.
  • the CVD process is preferably carried out in such a way that the backbone has annular structures.
  • Cyclic organosiloxanes are particularly suitable as precursors.
  • the layers produced according to the examples have dielectric constants between 2.6 and 3.3.
  • WO 00/75975 A2 teaches the use of polycarbosilanes which are applied from a solution and converted into polyorganosilicon layers with k values of less than 2.5 by thermal treatment in discrete steps.
  • the polycarbosilanes used are hydridopolycarbosilanes which contain at least one
  • Silicon-bonded hydrogen atom and preferably contain allyl substituents.
  • Si-H bonds are sensitive to moisture and must therefore be handled accordingly.
  • the platinum compounds used to cross-link Si-H compounds with unsaturated groups are undesirable as metallic impurities.
  • the temperature treatment In order to achieve layers with low k values, the temperature treatment must be carried out under precisely controlled conditions, whereby various specified temperature steps must be observed.
  • the air contained in the pores has a k-value of almost 1. Bring it into a dense one If the material contains air-filled pores, the average k-value of the material is made up of the k-value of the dense material and a proportion of the k-value of air. The effective k-value is thus reduced.
  • the k value of pure silicon dioxide can thus be reduced from 4.0 to below 2.0, but this requires porosities> 90% (L. Hrubesch, Mat. Res. Soc. Symp. Proc, 381,
  • the principle can generally be applied to dense dielectric layers.
  • k values below 2.0 can be achieved with much lower porosities, which in turn benefits the mechanical stability of the layers.
  • German patent DE 196 03 241 Cl describes the production of multifunctional organosiloxanes which are used as crosslinkers in inorganic paints based on silica sol. After drying, these materials form soft
  • Cl are known to have dielectric layers with low k values produced by thermal treatment.
  • carbosilanes which have no Si-H bonds can be used. This is particularly surprising given the background of the teaching in WO 00/75975 A2, in which the last paragraph on page 8 explains that the manufacture of appropriate dielectric layers finally, polycarbosilanes are suitable which contain at least one hydrogen atom bonded to silicon.
  • the dielectric layers according to the invention are similar in their composition to carbon-doped silicon dioxide, and combine low k values with the advantage of simple temperature treatment.
  • the invention therefore relates to a method for producing dielectric layers, characterized in that sol-gel products of multifunctional carbosilanes are thermally treated.
  • the invention further relates to the dielectric layers which can be produced by this method.
  • the invention finally relates to the use of the dielectric
  • sol-gel products which can be used in the process according to the invention can be:
  • Reaction of a multifunctional carbosilane can be obtained with water in the presence of a catalyst.
  • Suitable carbosilanes are multifunctional carbosilanes which contain at least 2, preferably at least 3, silicon atoms, each having 1 to 3 alkoxy or
  • the silicon atoms being bonded to at least one Si — C bond to a structural unit linking the silicon atoms.
  • linking units within the meaning of the invention are linear or branched - to CIO-alkylene chains, C 5 - to CIO-cycloalkylene radicals, aromatic radicals, for example phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals called.
  • aromatic radicals for example phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals called.
  • the aliphatic and aromatic radicals can also contain hetero atoms, such as Si, N, O or F.
  • Multifunctional carbosilanes which do not have any Si-H bonds are preferably used.
  • Examples of suitable multifunctional carbosilanes are compounds of the general formula (I)
  • R 3 alkyl, aryl, preferably C ⁇ -C ⁇ o-alkyl, C 6 -C ⁇ 0 -aryl, particularly preferably methyl.
  • R can also mean hydrogen.
  • R 4 alkyl, aryl, preferably Ci-Cio-alkyl, C 6 -C ⁇ o-aryl, particularly preferably methyl, ethyl, isopropyl;
  • R can also mean hydrogen
  • R 5 alkyl, aryl, preferably Ci-Cio-alkyl, C ⁇ -Cio-aryl, particularly preferred
  • R 6 -C 6 alkyl or C 6 -C 4 aryl, preferably methyl, ethyl, particularly preferred
  • polyfunctional carbosilanes are compounds of the general formula (III)
  • R can also be hydrogen
  • R 9 alkyl, aryl, preferably Ci-Cio-alkyl, C ö -Ciö-aryl, particularly preferred
  • Oligomers or mixed oligomers of the compounds of the formulas (I) - (III) can also be used as multifunctional carbosilanes.
  • Examples of particularly suitable compounds are 1,3,5,7-tetramethyl-1,3,5,7-tetra (2- (diethoxymethylsilyl) ethylene) cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5, 7- tetra (2- (hydroxy-dimethylsilyl) ethylene) cyclotetrasiloxane or their oligomers.
  • the multifunctional can be used to manufacture the sol-gel product
  • EP 743 313 A2 EP 787 734 AI and WO 98/52992 AI described.
  • Suitable organic solvents are, for example, ketones, alcohols, diols, ethers and mixtures thereof. The addition of the solvent serves to give the solution the desired viscosity.
  • Preferred solvents are n-butanol, ethanol and i-propanol. Possible dilutions are 10-90% by weight, preferably 20-50% by weight, of multifunctional carbosilane in the solvent.
  • Catalysts i.e. Compounds which accelerate the reaction between the functional groups are added.
  • suitable catalysts are organic and inorganic acids such as aliphatic monocarboxylic acids with 1 to 10 carbon atoms such as e.g. Formic acid or acetic acid, aromatic carboxylic acids with 7 to 14 carbon atoms, e.g. Benzoic acid, dicarboxylic acids such as e.g. Oxalic acid, aliphatic and aromatic sulfonic acids such as e.g. p-toluenesulfonic acid, inorganic volatile acids such as hydrochloric acid or nitric acid. The use of p-toluenesulfonic acid is particularly preferred.
  • the catalysts can be used as aqueous or alcoholic solutions in concentrations of 0.05-5 n, preferably 0.1-1 n.
  • concentrations of 0.05-5 n, preferably 0.1-1 n For example, 1-50% by weight, preferably 5-20% by weight, of the catalyst solution can be added to the carbosilane solution.
  • Formulations of the multifunctional carbosilanes which have the following composition are particularly preferably used:
  • the sol-gel product is generally applied to a substrate.
  • all customary methods are available for applying the layers. These are e.g. Spin coating, dip coating, knife coating and spraying.
  • the sol-gel product of the multifunctional carbosilane or its formulation is thermally treated after being applied to a substrate.
  • the thermal treatment takes place, for example, at temperatures between 100 and 800 ° C., preferably between 200 and 600 ° C., particularly preferably between 200 and 400 ° C.
  • This thermal treatment serves to complete the crosslinking of the multifunctional carbosilanes and to remove the solvent, and furthermore the temperature treatment serves to create pores.
  • the temperature treatment can be carried out in a very simple manner in one step at a fixed temperature. However, it is also possible to carry out the treatment in several steps according to a suitable temperature and time profile. Suitable temperature and time profiles depend on the multifunctional carbosilanes, the
  • Catalyst and the solvent content can be determined by preliminary tests.
  • the layers are preferably crosslinked at temperatures of 100-150 ° C. for a period of 5-120 minutes.
  • the pore is generated by temperature treatment above a temperature at which parts of the carbosilane decompose and escape as gaseous components. This happens from temperatures above approx. 220 ° C, depending on the multifunctional carbosilanes used. It is also possible to add pore-forming substances such as high-boiling solvents or foaming agents to the sol-gel product before application. These remain in the layer during crosslinking and are only evaporated and / or decomposed into gaseous products during the subsequent temperature treatment.
  • the temperature treatment can be carried out using conventional furnaces, RTP (Rapid Thermal Processing) furnaces, hotplates etc. However, it is also possible to supply the energy required for crosslinking and pore formation with the aid of microwaves, LR light, lasers or other high-energy electromagnetic radiation.
  • the temperature treatment in an oven or on a is preferred
  • the temperature treatment can be carried out in air or other gases.
  • the temperature treatment is preferably carried out in air or in nitrogen.
  • thermally labile components of the layer are pyrolytically broken down, so that gas-filled pores remain.
  • a further processing step which serves to hydrophobize the pore surface.
  • the k value of an organosilicon material can be further reduced by the chemical conversion of Si-OH groups into Si-O-SiR 3 groups.
  • the surface is treated with suitable compounds, such as trichloromethylsilane or hexamethylene disilazane. Further information on the procedure and further examples are described, for example, in WO 99/36953 AI.
  • the invention also relates to dielectric layers which can be obtained by the process according to the invention.
  • the layers according to the invention are characterized by k values of less than 2.8, preferably less than 2.5, particularly preferably less than 2.0, the k value in particular depending on the choice of multifunctional carbosilane and the conditions of the thermal treatment of the sol gel Product depends.
  • the layers preferably have a layer thickness of 0.01 to 100 ⁇ m.
  • the layers according to the invention can be used, for example, as dielectric insulation layers in the production of microelectronic circuits, in chip packaging, for the construction of multichip modules, and for the production of laminated printed circuit boards and displays.
  • the substrate to be used, to which a dielectric layer according to the invention is applied depends on the application. All substrates are possible that deal with the aforementioned techniques such as spin and dip coating, knife coating or
  • Allow spray coating and which can withstand the temperatures that occur during the temperature treatment e.g. structured and unstructured silicon wafers, structured and unstructured wafers of other semiconductors such as gallium arsenide or silicon germanide, with structured layers provided, structured or unstructured glass plates or suitable structured and unstructured thermostable plastic substrates.
  • the layer thicknesses of the applied films were measured with a surface profiler (Alpha-Step 500, KLA-Tencor).
  • the dielectric constant k was determined by measuring the capacitance C of a model plate capacitor. The following applies:
  • Capacitor made.
  • the mating contact on the layer was made by means of a sputtered gold electrode (diameter approx. 5 mm).
  • the capacitance was measured with an impedance spectrometer (EG&G 398).
  • the impedance Z of the model plate capacitor was determined in the range from 10-100000 Hz without bias voltage.
  • the capacitance C of the model capacitor results from the impedance Z according to:
  • the film was then 0.61 ⁇ m, the k value 2.7.

Abstract

L'invention concerne un procédé de production de couches diélectriques de faible constante diélectrique par traitement thermique d'un produit sol-gel d'un carbosilane multifonctionnel. L'invention concerne en outre les couches correspondantes et leur utilisation pour la fabrication de composants électroniques.
EP02804878A 2001-12-19 2002-12-06 Procede de production de couches dielectriques avec utilisation de carbosilane multifonctionnel Withdrawn EP1468446A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10162443 2001-12-19
DE10162443A DE10162443A1 (de) 2001-12-19 2001-12-19 Verfahren zur Herstellung von dielektrischen Schichten unter Verwendung multifunktioneller Carbosilane
PCT/EP2002/013834 WO2003052809A1 (fr) 2001-12-19 2002-12-06 Procede de production de couches dielectriques avec utilisation de carbosilane multifonctionnel

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DE (1) DE10162443A1 (fr)
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040038048A1 (en) 2000-02-02 2004-02-26 Lg Chemical Ltd. Semiconductor interlayer dielectric material and a semiconductor device using the same
DE102004027857A1 (de) * 2004-06-08 2006-01-05 Siemens Ag Verfahren zum Herstellen eines keramischen Werkstoffs, keramischer Werkstoff und Keramikkörper mit dem keramischen Werkstoff
US7575979B2 (en) * 2004-06-22 2009-08-18 Hewlett-Packard Development Company, L.P. Method to form a film
US7892648B2 (en) * 2005-01-21 2011-02-22 International Business Machines Corporation SiCOH dielectric material with improved toughness and improved Si-C bonding
JP5324734B2 (ja) * 2005-01-21 2013-10-23 インターナショナル・ビジネス・マシーンズ・コーポレーション 誘電体材料とその製造方法
JP4935111B2 (ja) 2006-02-22 2012-05-23 富士通株式会社 絶縁膜形成用組成物、半導体装置用絶縁膜、その製造方法および半導体装置
US20080012074A1 (en) * 2006-07-14 2008-01-17 Air Products And Chemicals, Inc. Low Temperature Sol-Gel Silicates As Dielectrics or Planarization Layers For Thin Film Transistors
US20110076416A1 (en) * 2008-05-26 2011-03-31 Basf Se Method of making porous materials and porous materials prepared thereof
US10361137B2 (en) * 2017-07-31 2019-07-23 Taiwan Semiconductor Manufacturing Company, Ltd. Semiconductor device and method

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5677410A (en) * 1995-05-16 1997-10-14 Bayer Ag Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers
JPH09143420A (ja) * 1995-09-21 1997-06-03 Asahi Glass Co Ltd 低誘電率樹脂組成物
US6005131A (en) * 1996-01-30 1999-12-21 Bayer Aktiengesellschaft Multi-functional, cyclic organosiloxanes, process for the production thereof and use thereof
DE19603241C1 (de) * 1996-01-30 1997-07-10 Bayer Ag Multifunktionelle, cyclische Organosiloxane, Verfahren zu deren Herstellung und deren Verwendung
US6143855A (en) * 1997-04-21 2000-11-07 Alliedsignal Inc. Organohydridosiloxane resins with high organic content
US6043330A (en) * 1997-04-21 2000-03-28 Alliedsignal Inc. Synthesis of siloxane resins
WO1998052992A1 (fr) * 1997-05-23 1998-11-26 Bayer Aktiengesellschaft Oligomeres obtenus a partir d'organosilanes
US6042994A (en) * 1998-01-20 2000-03-28 Alliedsignal Inc. Nanoporous silica dielectric films modified by electron beam exposure and having low dielectric constant and low water content
US6068884A (en) * 1998-04-28 2000-05-30 Silcon Valley Group Thermal Systems, Llc Method of making low κ dielectric inorganic/organic hybrid films
US6054206A (en) * 1998-06-22 2000-04-25 Novellus Systems, Inc. Chemical vapor deposition of low density silicon dioxide films
US5906859A (en) * 1998-07-10 1999-05-25 Dow Corning Corporation Method for producing low dielectric coatings from hydrogen silsequioxane resin
US6225238B1 (en) * 1999-06-07 2001-05-01 Allied Signal Inc Low dielectric constant polyorganosilicon coatings generated from polycarbosilanes
JP3571004B2 (ja) * 2000-04-28 2004-09-29 エルジー ケム インベストメント エルティーディー. 半導体素子用超低誘電多孔性配線層間絶縁膜およびその製造方法ならびにそれを用いた半導体素子
EP1209036A3 (fr) * 2000-11-28 2003-11-19 Sumitomo Wiring Systems, Ltd. Boite de jonction électrique pour un véhicule
JP4246640B2 (ja) * 2002-03-04 2009-04-02 東京エレクトロン株式会社 ウェハ処理において低誘電率材料を不動態化する方法
JP4139710B2 (ja) * 2003-03-10 2008-08-27 信越化学工業株式会社 多孔質膜形成用組成物、多孔質膜の製造方法、多孔質膜、層間絶縁膜、及び半導体装置
KR100507967B1 (ko) * 2003-07-01 2005-08-10 삼성전자주식회사 실록산계 수지 및 이를 이용한 반도체 층간 절연막

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03052809A1 *

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TW200305618A (en) 2003-11-01
US20030181537A1 (en) 2003-09-25
JP2005513777A (ja) 2005-05-12
TWI265964B (en) 2006-11-11
AU2002366351A1 (en) 2003-06-30
DE10162443A1 (de) 2003-07-03
CN1605118A (zh) 2005-04-06
CN100336183C (zh) 2007-09-05
WO2003052809A1 (fr) 2003-06-26
US7090896B2 (en) 2006-08-15
KR20040068274A (ko) 2004-07-30
HK1076918A1 (en) 2006-01-27

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