WO2012087750A1 - Cyclic carbosilane dielectric films - Google Patents

Cyclic carbosilane dielectric films Download PDF

Info

Publication number
WO2012087750A1
WO2012087750A1 PCT/US2011/065196 US2011065196W WO2012087750A1 WO 2012087750 A1 WO2012087750 A1 WO 2012087750A1 US 2011065196 W US2011065196 W US 2011065196W WO 2012087750 A1 WO2012087750 A1 WO 2012087750A1
Authority
WO
WIPO (PCT)
Prior art keywords
dielectric film
substrate
cyclic
film
carbosilane
Prior art date
Application number
PCT/US2011/065196
Other languages
French (fr)
Inventor
David J. Michalak
James M. Blackwell
James S. Clarke
Original Assignee
Intel Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Intel Corporation filed Critical Intel Corporation
Publication of WO2012087750A1 publication Critical patent/WO2012087750A1/en

Links

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
    • H01L21/02104—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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • 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
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
    • H01L29/0603—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by particular constructional design considerations, e.g. for preventing surface leakage, for controlling electric field concentration or for internal isolations regions
    • H01L29/0642—Isolation within the component, i.e. internal isolation
    • H01L29/0649—Dielectric regions, e.g. SiO2 regions, air gaps
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene

Definitions

  • the embodiments of the invention relate generally to semiconductor processing and manufacture, integrated circuits, dielectric materials, interlayer dielectric materials, spin-on dielectric materials, and materials comprising cyclic carbosilanes.
  • an integrated circuit chip is also known as a microchip, a silicon chip, or a chip.
  • IC chips are found in a variety of common devices, such as the microprocessors in computers, cars, televisions, CD players, and cellular phones.
  • a plurality of IC chips are typically built on a silicon wafer (a thin silicon disk, having a diameter, for example, of 300 mm) and after processing the wafer is diced apart to create individual chips.
  • a 1 cm 2 IC chip having feature sizes around of about 90 nm can comprise hundreds of millions of components. Current technologies are pushing feature sizes even smaller than 45 nm.
  • FIGURE 1 shows cyclic carbosilane precursors useful for making dielectric films and low-k dielectric films.
  • FIGURE 2 illustrates a method for the synthesis of cyclic carbosilane precursors useful for making dielectric films and low-k dielectric films.
  • FIGURE 3 shows an additional cyclic carbosilane precursor useful for making dielectric films and low-k dielectric films.
  • FIGURE 4 illustrates a method for the synthesis of additional cyclic carbosilane precursors useful for making dielectric films and low-k dielectric films.
  • FIGURES 5A-C illustrate cyclic carbosilane precursor molecules useful for making dielectric films and low-k dielectric films.
  • FIGURES 6A-C show additional cyclic carbosilane precursor molecules useful for making dielectric films and low-k dielectric films.
  • FIGURE 7 provides a cyclic carbosilane-attached porogen molecule.
  • FIGURE 8 shows the acid or base catalyzed polymerization of cyclic carbosilane molecules.
  • FIGURE 9 illustrates a synthesis scheme for making dielectric films and low-k dielectric films.
  • FIGURE 10 describes a method for making a dielectric films and low-k dielectric films.
  • Embodiments of the invention provide dielectric films for integrated circuits.
  • Cyclic carbosilane precursors are capable of providing films with small dielectric constants and the cyclic carbosilane precursors are useful in semiconductor processing applications.
  • Dielectric films according to embodiments of the invention are useful in a variety of applications for integrated circuit devices.
  • the films described herein are useful as dielectric films, and low-k dielectric films, spin-on dielectric films, interlayer dielectric films (ILDs, intermetal dielectric films, or IMDs), and etch-selective layers.
  • Figure 1 illustrates linear oligomers of cyclic carbosilane molecules that are useful as precursors for making dielectric films and low-k dielectric films.
  • R is a functional group, such as, for example, an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms.
  • R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms.
  • the functional group R is a group such as, for example, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 ,
  • the R group is less than 50 % larger than the size of the porogen molecule chosen.
  • m is a number from 1 to 10.
  • m is a number from 3 to 10.
  • Other values for m are also possible, such as larger numbers.
  • one or two of the carbon atoms (i.e., -CH 2 - groups) in the cyclic carbosilane molecules is optionally replaced with an oxygen atom.
  • the carbosilane oligomer composition that is used to create a dielectric film is typically a mixture of different oligomers having different lengths (different numbers of cyclic carbosilane units), so that m represents an average oligomer length for the molecules present in the mixture.
  • Figure 2 provides a synthesis scheme for oligomers of cyclic carbosilane molecules that are useful as precursors for making dielectric films and low-k dielectric films.
  • the cyclic carbosilane monomer is functionalized with crosslinking groups and then crosslinked with carbosilane monomers.
  • ethyl (-Et) functional groups are shown, other alkyl groups are also possible, such as, for example, an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms.
  • R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms.
  • the functional group R is a group such as, for example, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 ,
  • the R group is less than 50 % larger than the size of the porogen molecule chosen.
  • one or two of the carbon atoms of the cyclic carbosilanes is optionally replaced with an oxygen atom.
  • scheme (1) molecule I (in this case, l,3,5-triethoxy-l,3,5-trimethyl-
  • 1,3,5-trisilacyclohexane is reacted with t-butyl lithium and then subsequently Me 2 SiHCl to form molecule II, in which one of the cyclic carbosilane ring carbons has been silanated.
  • the cyclic carbosilane oligomer composition produced by the method of Figure 2 is often a mixture of different oligomers having different lengths, so that m represents an average oligomer length for the molecules present in the mixture.
  • Figure 3 provides an additional oligomeric cyclic carbosilane precursor useful for making dielectric and low-k dielectric films.
  • the molecule of Figure 3 is a branched oligomer.
  • R is a functional group, such as, for example, an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms.
  • R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and fluorine atoms.
  • the functional group R is a group such as, for example, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 CH(CH 2 CH 3 ) 2 , -CH 2 OCH 3 ,
  • the R group is less than 50 % larger than the size of the porogen molecule chosen.
  • one or two of the carbon atoms of the cyclic carbosilanes is optionally replaced with an oxygen atom.
  • Figure 4 illustrates methods for synthesizing a branched oligomeric cyclic carbosilane precursor.
  • ethyl (-Et) functional groups are shown, other alkyl groups are also possible, such as, for example, an alkyl group comprising hydrogen atoms, and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms.
  • R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms.
  • the functional group R is a group such as, for example, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 CH(CH 2 CH 3 ) 2 , -CH 2 OCH 3 ,
  • the R group is less than 50 % larger than the size of the porogen molecule chosen.
  • one or two of the carbon atoms of the cyclic carbosilanes is optionally replaced with an oxygen atom.
  • Figure 4 two different methods of dendrimeric cyclic carbosilane precursor synthesis are shown.
  • molecule la is reacted with t-butyl lithium to form molecule Ila.
  • Molecule lb is reacted with three equivalents of Ila to condense the molecules into molecule III.
  • molecule lb is reacted with three equivalents of molecule lib in the presence of SiMe 2 HCl and B(C 6 F5) 3 in toluene to make molecule III.
  • Figures 5 A-C provide additional useful dielectric film precursor molecules that have attached porogens (pore-creating functional groups).
  • a cyclic carbosilane ring comprises a porogen functional group, X, linked to a silicon of the carbosilane ring through a linker group, L.
  • the cyclic carbosilane ring comprises two porogen functional groups, X, linked to silicon atoms of the carbosilane ring through a linker group, L.
  • the cyclic carbosilane ring comprises three porogen functional groups, X, linked to silicon atoms of the carbosilane ring through a linker group, L.
  • porogen functional groups have dimensions (widths, lengths, and heights or radii) that are from 0.25 nm to 2 nm. In alternate embodiments, the porogen functional groups have dimensions that are from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm.
  • Pore sizes in the resulting films have dimensions (widths, lengths, and heights or radii, depending on the shape of the pore) that are from 0.25 nm to 2 nm (or from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm), depending on the porogen group chosen.
  • porogen groups decompose (upon heating, UV curing, or electron beam curing, for example) with approximately 100 % volatile yield (approximately indicating 80 % ⁇ 20 %).
  • Porogen functional groups are, for example, cyclodextrins, polyethylene oxides, polystyrenes, polyacrylates, or poly-alpha-methylstyrenes.
  • Linker groups are carbon- containing groups containing hydrogen and carbon atoms. Linker groups also optionally contain oxygen atoms. Linkers include groups, such as for example, -CH 2 -, -OCH 2 -, -CH 2 O-, -CH 2 CH 2 -, -CH 2 OCH 2 -, -CH 2 (CH 3 )CH 2 -.
  • the functional group labeled R in Figures 5A-C is an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms.
  • R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms.
  • the functional group R is a group such as, for example, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CFI 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 CH(CH 3 ) 2 ,
  • the R group is less than 50 % larger than the size of the porogen molecule chosen.
  • Figures 6A-C provide further additional useful dielectric film precursor molecules that have attached porogens (pore-creating functional groups).
  • a cyclic carbosilane ring comprises a porogen functional group, X, linked to a carbon of the carbosilane ring through a linker group, L.
  • one or two of the carbon atoms (-CH 2 - groups) of the cyclic carbosilane ring is replaced with an oxygen atom.
  • the cyclic carbosilane ring comprises two porogen functional groups, X, linked to carbon atoms of the carbosilane ring through a linker group, L.
  • one of the carbon atoms (-CH 2 - groups) of the cyclic carbosilane ring is replaced with an oxygen atom.
  • the cyclic carbosilane ring comprises three porogen functional groups, X, linked to carbon atoms of the carbosilane ring through a linker group, L.
  • porogen functional groups have dimensions (widths, lengths, and heights or radii) that are from 0.25 nm to 2 nm.
  • the porogen functional groups have dimensions that are from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm.
  • Pore sizes in the resulting films have dimensions (widths, lengths, and heights or radii, depending on the shape of the pore) that are from 0.25 nm to 2 nm (or from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm), depending on the porogen group chosen.
  • porogen groups decompose (upon heating, UV curing, or electron beam curing, for example) with approximately 100 % volatile yield (approximately indicating 80 % ⁇ 20 %).
  • Porogen functional groups are, for example, cyclodextrins, polyethylene oxides, polystyrenes, polyacrylates, or poly-alpha-methylstyrenes.
  • Linker groups are carbon- containing groups containing hydrogen and carbon atoms. Linker groups also optionally contain oxygen atoms. Linkers include groups, such as for example, -CH 2 -, -OCH 2 -, -CH 2 O-, -CH 2 CH 2 -, -CH 2 OCH 2 -, -CH 2 (CH 3 )CH 2 -.
  • the functional group labeled R in Figures 5A-C is an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms.
  • R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms.
  • the functional group R is a group such as, for example, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , -CH 2 CH 2 CH(CH 3 ) 2 ,
  • the R group is less than 50 % larger than the size of the porogen molecule chosen.
  • Figure 7 provides a porogen molecule linked to a plurality of carbosilane rings.
  • the porogen molecule is an alpha cyclodextrin molecule comprises six attached cyclic carbosilanes. Each cyclic carbosilane is attached to one porogen molecule in this embodiment.
  • the carbosilane-linked porogen molecule of Figure 7 can be made, for example, by reacting the cyclodextrin with about 6 equivalents of molecule II of Figure 2 in the presence of B(CeF 5 ) 3 in toluene.
  • Figure 8 illustrates generally the acid or base catalyzed crosslinking of an exemplary cyclic carbosilane molecule. Through acid or base catalyzed reactions similar to the one illustrated in Figure 8, liquid-phase carbosilane film precursors of Figures 1-7 become solidified films.
  • R is an alkyl functional group such as one described with respect to any one of Figures 1-6.
  • Figure 9 shows the formation of a dielectric film on a substrate.
  • a cyclic carbosilane precursor that is an oligomer of cyclic carbosilane units (molecule III in Figure 9)
  • a photo acid generator (PAG) a photo base generator (PGB)
  • PGB photo base generator
  • TAG thermally-activated acid generator
  • TSG thermally-activated base generator
  • a photo acid generator or photo base generator is exposed to light to produce an acid or a base
  • porogen-comprising precursors and non-porogen containing precursors are used to generate films having desired porosities.
  • exemplary photo acid generators are diaryliodonium and
  • triarylsulfonium salts possessing weakly coordinating counter anions such as
  • neutral photoacid generators include those in the arylsulfonate family such as
  • phenyltrifluoromethanesulfonate and those in the N-sulfonated amine and imides family such as N-trifluoromethanesulfonatomaleimide.
  • Other classes of compounds common in the photolithographic and photopolymerization fields are also useful in embodiments of the invention.
  • Examples of photobase generators include amines protected with photodecomposable nitrobenzylcarbamate or other carbamate groups.
  • Other classes of compounds common in the photolithographic and photopolymerization fields and used as PAGs and PBGs are also useful in embodiments of the invention.
  • sulfonium salts possessing two aryl substituents and one alkyl substituent can behave as thermal acid generators.
  • common photobase generators can also serve as thermal base generators in films. Typical temperatures for carbamate- containing TAGs are temperatures between 200 and 400 °C.
  • Figure 10 describes a method for the formation of a spin-on-dielectric film.
  • a mixture of a polymerization initiator and oligomerized carbosilane precursors is deposited onto a substrate surface.
  • the mixture of the polymerization initiator and the oligomerized carbosilane precursors additionally comprises porogen-linked cyclic carbosilanes.
  • the mixture comprises a polymerization initiator and porogen-linked cyclic carbosilanes.
  • oligomers comprise between 3 and 10 cyclic carbosilane units
  • the polymerization initiator is a photo acid generator, a photo base generator, a thermally-activated acid, or a thermally-activated base.
  • the substrate is spun distributing the film precursor mixture across the substrate surface.
  • the polymerization initiator is then activated through exposing the substrate surface to light for photo-activated initiators or heating the substrate surface for heat-activated initiators.
  • Polymerization of the cyclic carbosilanes creates a solidified film.
  • the resulting film has a porosity that is between 5 % and 60 %. In additional embodiments the resulting film has a porosity that is between 25 % and 60 %, between 35 % and 50 %, or between 35 % and 45 %.
  • porosity is a measure of the space taken up by empty space (pores) in the material, and is described as a fraction of the volume of the empty space over the total volume of the material.
  • the pores in the resulting films have dimensions that are that are from 0.25 nm to 2 nm. In alternate embodiments, the pores have dimensions that are from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm
  • the resulting films are hydrophobic.
  • hydrophobic means that the films do not absorb or adsorb significant amounts of water from the atmosphere.
  • less than 5 % water uptake (as a volume of water taken up by the film to total volume of the film) is observed for the hydrophobic carbosilane films as measured by ellipsometric porosimetry in a saturated H 2 0 atmosphere at room temperature (20 to 23.5 °C).
  • less than 3 % water uptake or less than 1 % water uptake is observed for the hydrophobic carbosilane films as measured by ellipsometric porosimetry.
  • the dielectric constant (k) values for the carbosilane films range from 1.6 to 3.5. In additional embodiments, the dielectric constant (k) values for the carbosilane films are from 1.6 to 3.0, or from 1.6 to 2.5. Dielectric constant values are measured using a CV dot technique in which the film is deposited on a highly doped Si substrate and metallic dots are deposited on top of the film. The dielectric constant across the film is then measured.
  • films according to embodiments of the invention have percent compositions in the range of 45-60 % C, 25-35 %Si, and 10-20 % O (atomic percent).
  • Films according to embodiments of the invention are chemically stable.
  • chemical stability means that the film is significantly resistant to chemical degradation.
  • chemically stable films according to embodiments of the invention are resistant to degradation when a sample of the film is placed in a solution of 0.5 % HF (at 23 °C), 1.0 % KOH (at 50 °C), 15 % TMAH (tetramethylammonium hydroxide) (at 60 °C), or 30 % H 2 0 2 (at 50 °C) for 10 minutes.
  • Resistant to degradation means that 10 nm or less of film loss and 5 % or less change in refractive index is observed.
  • a porogen molecule or functional group is a molecule or functional group that is present in the precursor film that is capable of creating pores in the final film.
  • the porogen molecule is removed from the final film through heating, although other methods are possible.
  • Other methods for porogen removal include, for example, UV-curing or electron beam curing. After removal, the space occupied by the porogen molecule becomes a pore.
  • the substrate on which the devices that make up the IC circuit chip are built and dielectric films are used is, for example, a silicon wafer or a silicon-on-insulator substrate.
  • Silicon wafers are substrates that are typically used in the semiconductor processing industry, although embodiments of the invention are not dependent on the type of substrate used.
  • the substrate could also be comprised of, for example, germanium, indium antimonide, lead telluride, indium arsenide, indium phosphide, gallium arsenide, gallium antimonide, and or other Group III-V materials either alone or in combination with silicon or silicon dioxide or other insulating materials.
  • IC devices that make up the chip are built on the substrate surface. Devices are optionally distributed across the substrate surface and or stacked on top of each other.
  • a spin-on-dielectric film is a dielectric film created by spinning a solution to distribute it across a surface and then solidifying the solution on the surface.
  • a liquid form of the film is placed in the center of the substrate (such as a wafer).
  • the substrate is spun causing the liquid film material to distribute across the wafer surface.
  • the thickness of the resulting film depends in part on the viscosity of the liquid film. Excess liquid film material is spun off the substrate.
  • a low-k dielectric material is a dielectric material that has a lower dielectric constant that silicon dioxide (Si0 2 ). Silicon dioxide has a dielectric constant of 3.9.
  • Si0 2 silicon dioxide
  • the use of low-k dielectric materials in integrated circuit devices has enabled continued device size reduction. Although a variety of materials have lower dielectric constants that Si0 2 not all materials are suitable for integration into integrated circuits and integrated circuit manufacturing processes.
  • inter-layer dielectric (ILD) or inter-metal dielectric (IMD) film is the insulating material used between metal conductors and devices (such as transistors) in integrated circuit devices.

Abstract

Embodiments of the invention provide dielectric films and low k dielectric films and methods for making dielectric and low k dielectric films. Dielectric films are made from carbosilane-containing precursors. In embodiments of the invention, dielectric film precursors comprise attached porogen molecules. In further embodiments, dielectric films have nanometer-dimensioned pores.

Description

CYCLIC CARBOSILANE DIELECTRIC FILMS
BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
The embodiments of the invention relate generally to semiconductor processing and manufacture, integrated circuits, dielectric materials, interlayer dielectric materials, spin-on dielectric materials, and materials comprising cyclic carbosilanes.
BACKGROUND INFORMATION
The desire for ever-smaller integrated circuits (IC) devices places enormous performance demands on the techniques and materials used to construct IC devices. In general, an integrated circuit chip is also known as a microchip, a silicon chip, or a chip. IC chips are found in a variety of common devices, such as the microprocessors in computers, cars, televisions, CD players, and cellular phones. A plurality of IC chips are typically built on a silicon wafer (a thin silicon disk, having a diameter, for example, of 300 mm) and after processing the wafer is diced apart to create individual chips. A 1 cm2 IC chip having feature sizes around of about 90 nm can comprise hundreds of millions of components. Current technologies are pushing feature sizes even smaller than 45 nm.
BRIEF DESCRIPTION OF THE FIGURES FIGURE 1 shows cyclic carbosilane precursors useful for making dielectric films and low-k dielectric films.
FIGURE 2 illustrates a method for the synthesis of cyclic carbosilane precursors useful for making dielectric films and low-k dielectric films.
FIGURE 3 shows an additional cyclic carbosilane precursor useful for making dielectric films and low-k dielectric films.
FIGURE 4 illustrates a method for the synthesis of additional cyclic carbosilane precursors useful for making dielectric films and low-k dielectric films.
FIGURES 5A-C illustrate cyclic carbosilane precursor molecules useful for making dielectric films and low-k dielectric films.
FIGURES 6A-C show additional cyclic carbosilane precursor molecules useful for making dielectric films and low-k dielectric films.
FIGURE 7 provides a cyclic carbosilane-attached porogen molecule.
FIGURE 8 shows the acid or base catalyzed polymerization of cyclic carbosilane molecules. FIGURE 9 illustrates a synthesis scheme for making dielectric films and low-k dielectric films.
FIGURE 10 describes a method for making a dielectric films and low-k dielectric films.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the invention provide dielectric films for integrated circuits. Cyclic carbosilane precursors are capable of providing films with small dielectric constants and the cyclic carbosilane precursors are useful in semiconductor processing applications. Dielectric films according to embodiments of the invention are useful in a variety of applications for integrated circuit devices. For example, the films described herein are useful as dielectric films, and low-k dielectric films, spin-on dielectric films, interlayer dielectric films (ILDs, intermetal dielectric films, or IMDs), and etch-selective layers.
Figure 1 illustrates linear oligomers of cyclic carbosilane molecules that are useful as precursors for making dielectric films and low-k dielectric films. In Figure 1, R is a functional group, such as, for example, an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms. In addition, R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms. The functional group R is a group such as, for example, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3, -CH2CH(CH3)2,
-CH2CH2CH(CH3)2, -CH2CH2CH(CH2CH3)2, -CH2OCH3, -CH2CH2OCH3, and others. In embodiments of the invention, the R group is less than 50 % larger than the size of the porogen molecule chosen. In Figure 1, m is a number from 1 to 10. In embodiments of the invention m is a number from 3 to 10. Other values for m are also possible, such as larger numbers. Further, one or two of the carbon atoms (i.e., -CH2- groups) in the cyclic carbosilane molecules is optionally replaced with an oxygen atom. The carbosilane oligomer composition that is used to create a dielectric film is typically a mixture of different oligomers having different lengths (different numbers of cyclic carbosilane units), so that m represents an average oligomer length for the molecules present in the mixture.
Figure 2 provides a synthesis scheme for oligomers of cyclic carbosilane molecules that are useful as precursors for making dielectric films and low-k dielectric films. The cyclic carbosilane monomer is functionalized with crosslinking groups and then crosslinked with carbosilane monomers. Although, in Figure 2, ethyl (-Et) functional groups are shown, other alkyl groups are also possible, such as, for example, an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms. In addition, R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms. The functional group R is a group such as, for example, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3,
-CH2CH2CH2CH2CH3, -CH2CH(CH3)2, -CH2CH2CH(CH3)2, -CH2CH2CH(CH2CH3)2, -CH2OCH3, -CH2CH2OCH3, and others. In embodiments of the invention, the R group is less than 50 % larger than the size of the porogen molecule chosen. Further, one or two of the carbon atoms of the cyclic carbosilanes is optionally replaced with an oxygen atom. In Figure 2, scheme (1), molecule I (in this case, l,3,5-triethoxy-l,3,5-trimethyl-
1,3,5-trisilacyclohexane) is reacted with t-butyl lithium and then subsequently Me2SiHCl to form molecule II, in which one of the cyclic carbosilane ring carbons has been silanated. Molecule II is then reacted with molecule I in the presence of B(CsF5)3 to yield a mixture of oligomers in which m is a function of the number of equivalents of molecule II used, such that m = n - 1. The cyclic carbosilane oligomer composition produced by the method of Figure 2 is often a mixture of different oligomers having different lengths, so that m represents an average oligomer length for the molecules present in the mixture.
Figure 3 provides an additional oligomeric cyclic carbosilane precursor useful for making dielectric and low-k dielectric films. The molecule of Figure 3 is a branched oligomer. In Figure 3, R is a functional group, such as, for example, an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms. In addition, R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and fluorine atoms. The functional group R is a group such as, for example, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3, -CH2CH(CH3)2, -CH2CH2CH(CH3)2, -CH2CH2CH(CH2CH3)2, -CH2OCH3,
-CH2CH2OCH3, and others. In embodiments of the invention, the R group is less than 50 % larger than the size of the porogen molecule chosen. Further, one or two of the carbon atoms of the cyclic carbosilanes is optionally replaced with an oxygen atom. In additional embodiments, there are, for example, 1, 2, or 3 modified cyclic carbosilane groups around the central cyclic carbosilane group. Different oligomers comprising different numbers of cyclic carbosilane groups are possible.
Figure 4 illustrates methods for synthesizing a branched oligomeric cyclic carbosilane precursor. Although, in Figure 4, ethyl (-Et) functional groups are shown, other alkyl groups are also possible, such as, for example, an alkyl group comprising hydrogen atoms, and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms. In addition, R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms. The functional group R is a group such as, for example, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3, -CH2CH(CH3)2, -CH2CH2CH(CH3)2, -CH2CH2CH(CH2CH3)2, -CH2OCH3,
-CH2CH2OCH3, and others. In embodiments of the invention, the R group is less than 50 % larger than the size of the porogen molecule chosen. Further, one or two of the carbon atoms of the cyclic carbosilanes is optionally replaced with an oxygen atom. In Figure 4, two different methods of dendrimeric cyclic carbosilane precursor synthesis are shown. In Figure 4, molecule la is reacted with t-butyl lithium to form molecule Ila. Molecule lb is reacted with three equivalents of Ila to condense the molecules into molecule III. Alternately, in Figure 4, molecule lb is reacted with three equivalents of molecule lib in the presence of SiMe2HCl and B(C6F5)3 in toluene to make molecule III.
Figures 5 A-C provide additional useful dielectric film precursor molecules that have attached porogens (pore-creating functional groups). In Figure 5 A, a cyclic carbosilane ring comprises a porogen functional group, X, linked to a silicon of the carbosilane ring through a linker group, L. In Figure 5B the cyclic carbosilane ring comprises two porogen functional groups, X, linked to silicon atoms of the carbosilane ring through a linker group, L. In Figure 5C the cyclic carbosilane ring comprises three porogen functional groups, X, linked to silicon atoms of the carbosilane ring through a linker group, L. In alternate embodiments, one or two of the carbon atoms (i.e., -CH2- groups) of the cyclic carbosilane ring is replaced with an oxygen atom. In an embodiment of the invention, porogen functional groups have dimensions (widths, lengths, and heights or radii) that are from 0.25 nm to 2 nm. In alternate embodiments, the porogen functional groups have dimensions that are from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm. Pore sizes in the resulting films have dimensions (widths, lengths, and heights or radii, depending on the shape of the pore) that are from 0.25 nm to 2 nm (or from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm), depending on the porogen group chosen. Further, porogen groups decompose (upon heating, UV curing, or electron beam curing, for example) with approximately 100 % volatile yield (approximately indicating 80 % ± 20 %). Porogen functional groups are, for example, cyclodextrins, polyethylene oxides, polystyrenes, polyacrylates, or poly-alpha-methylstyrenes. Linker groups are carbon- containing groups containing hydrogen and carbon atoms. Linker groups also optionally contain oxygen atoms. Linkers include groups, such as for example, -CH2-, -OCH2-, -CH2O-, -CH2CH2-, -CH2OCH2-, -CH2(CH3)CH2-. The functional group labeled R in Figures 5A-C is an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms. In addition, R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms. The functional group R is a group such as, for example, -CH3, -CH2CH3, -CH2CH2CFI3, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3, -CH2CH(CH3)2, -CH2CH2CH(CH3)2,
-CH2CH2CH(CH2CH3)2, -CH2OCH3, -CH2CH2OCH3, and others. In embodiments of the invention, the R group is less than 50 % larger than the size of the porogen molecule chosen.
Figures 6A-C provide further additional useful dielectric film precursor molecules that have attached porogens (pore-creating functional groups). In Figure 6A, a cyclic carbosilane ring comprises a porogen functional group, X, linked to a carbon of the carbosilane ring through a linker group, L. In alternate embodiments of the invention, one or two of the carbon atoms (-CH2- groups) of the cyclic carbosilane ring is replaced with an oxygen atom. In Figure 6B the cyclic carbosilane ring comprises two porogen functional groups, X, linked to carbon atoms of the carbosilane ring through a linker group, L. In alternate embodiments of the invention, one of the carbon atoms (-CH2- groups) of the cyclic carbosilane ring is replaced with an oxygen atom. In Figure 6C the cyclic carbosilane ring comprises three porogen functional groups, X, linked to carbon atoms of the carbosilane ring through a linker group, L. In an embodiment of the invention, porogen functional groups have dimensions (widths, lengths, and heights or radii) that are from 0.25 nm to 2 nm. In alternate embodiments, the porogen functional groups have dimensions that are from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm. Pore sizes in the resulting films have dimensions (widths, lengths, and heights or radii, depending on the shape of the pore) that are from 0.25 nm to 2 nm (or from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm), depending on the porogen group chosen. Further, porogen groups decompose (upon heating, UV curing, or electron beam curing, for example) with approximately 100 % volatile yield (approximately indicating 80 % ± 20 %). Porogen functional groups are, for example, cyclodextrins, polyethylene oxides, polystyrenes, polyacrylates, or poly-alpha-methylstyrenes. Linker groups are carbon- containing groups containing hydrogen and carbon atoms. Linker groups also optionally contain oxygen atoms. Linkers include groups, such as for example, -CH2-, -OCH2-, -CH2O-, -CH2CH2-, -CH2OCH2-, -CH2(CH3)CH2-. The functional group labeled R in Figures 5A-C is an alkyl group comprising hydrogen atoms and from 1 to 10 carbon atoms or from 1 to a large number of carbon atoms. In addition, R also optionally comprises, oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and or fluorine atoms. The functional group R is a group such as, for example, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3, -CH2CH(CH3)2, -CH2CH2CH(CH3)2,
-CH2CH2CH(CH2CH3)2, -CH2OCH3, -CH2CH2OCH3, and others. In embodiments of the invention, the R group is less than 50 % larger than the size of the porogen molecule chosen.
Figure 7 provides a porogen molecule linked to a plurality of carbosilane rings. In Figure 7, the porogen molecule is an alpha cyclodextrin molecule comprises six attached cyclic carbosilanes. Each cyclic carbosilane is attached to one porogen molecule in this embodiment. The carbosilane-linked porogen molecule of Figure 7 can be made, for example, by reacting the cyclodextrin with about 6 equivalents of molecule II of Figure 2 in the presence of B(CeF5)3 in toluene.
Figure 8 illustrates generally the acid or base catalyzed crosslinking of an exemplary cyclic carbosilane molecule. Through acid or base catalyzed reactions similar to the one illustrated in Figure 8, liquid-phase carbosilane film precursors of Figures 1-7 become solidified films. In Figure 8, R is an alkyl functional group such as one described with respect to any one of Figures 1-6.
Figure 9 shows the formation of a dielectric film on a substrate. In Figure 9, a cyclic carbosilane precursor that is an oligomer of cyclic carbosilane units (molecule III in Figure 9), is mixed with a photo acid generator (PAG), a photo base generator (PGB), a thermally-activated acid generator (TAG) or a thermally-activated base generator (TBG), spun onto a substrate surface, such as a semiconductor wafer surface, and exposed to either heat or light to activate the acid- or base-producing compound. A photo acid generator or photo base generator is exposed to light to produce an acid or a base
(respectively) and a thermally-activated acid or a thermally-activated base is exposed to heat to produce an acid or a base (respectively). Once the acid or base species is produced, crosslinking of the carbosilane precursors occurs and the film solidifies. In this manner a dielectric and or a low-k dielectric film is produced. Cyclic carbosilane precursors according to Figures 1, 3, 5A-C, 6A-C, and 7 and mixtures thereof are useful for forming dielectric films in the method described in Figure 9. Mixtures of
porogen-comprising precursors and non-porogen containing precursors are used to generate films having desired porosities. In general, exemplary photo acid generators are diaryliodonium and
triarylsulfonium salts possessing weakly coordinating counter anions such as
trifluoromethanesulfonate, nonaflurorbutanesulfonate, hexafluorophosphate,
tetrafluoroborate, para-toluenesulfonate, and others. Examples of neutral photoacid generators include those in the arylsulfonate family such as
phenyltrifluoromethanesulfonate and those in the N-sulfonated amine and imides family such as N-trifluoromethanesulfonatomaleimide. Other classes of compounds common in the photolithographic and photopolymerization fields are also useful in embodiments of the invention. Examples of photobase generators include amines protected with photodecomposable nitrobenzylcarbamate or other carbamate groups. Other classes of compounds common in the photolithographic and photopolymerization fields and used as PAGs and PBGs are also useful in embodiments of the invention. Through the introduction of less stable substituents, the above described photoacid and photobase generators can be tuned to also behave as thermal acid and thermal base generators, respectively. For example, sulfonium salts possessing two aryl substituents and one alkyl substituent can behave as thermal acid generators. Additionally, due to the thermal instability of carbamate towards the release of C02, common photobase generators can also serve as thermal base generators in films. Typical temperatures for carbamate- containing TAGs are temperatures between 200 and 400 °C. Although, other photo and thermally-activated acid and photo and thermally-activated base generators are possible.
Figure 10 describes a method for the formation of a spin-on-dielectric film. In Figure 10, a mixture of a polymerization initiator and oligomerized carbosilane precursors is deposited onto a substrate surface. In an alternate embodiment the mixture of the polymerization initiator and the oligomerized carbosilane precursors additionally comprises porogen-linked cyclic carbosilanes. In further embodiments the mixture comprises a polymerization initiator and porogen-linked cyclic carbosilanes. In embodiments of the invention, oligomers comprise between 3 and 10 cyclic carbosilane units The polymerization initiator is a photo acid generator, a photo base generator, a thermally-activated acid, or a thermally-activated base. The substrate is spun distributing the film precursor mixture across the substrate surface. The polymerization initiator is then activated through exposing the substrate surface to light for photo-activated initiators or heating the substrate surface for heat-activated initiators. Polymerization of the cyclic carbosilanes creates a solidified film. Depending on the composition of the film precursors used, the resulting film has a porosity that is between 5 % and 60 %. In additional embodiments the resulting film has a porosity that is between 25 % and 60 %, between 35 % and 50 %, or between 35 % and 45 %. In general, porosity is a measure of the space taken up by empty space (pores) in the material, and is described as a fraction of the volume of the empty space over the total volume of the material. The pores in the resulting films have dimensions that are that are from 0.25 nm to 2 nm. In alternate embodiments, the pores have dimensions that are from 0.25 nm to 0.5 nm or from 0.5 nm to 5 nm
Additionally, the resulting films are hydrophobic. As used herein, hydrophobic means that the films do not absorb or adsorb significant amounts of water from the atmosphere. In embodiments of the invention, less than 5 % water uptake (as a volume of water taken up by the film to total volume of the film) is observed for the hydrophobic carbosilane films as measured by ellipsometric porosimetry in a saturated H20 atmosphere at room temperature (20 to 23.5 °C). In additional embodiments, less than 3 % water uptake or less than 1 % water uptake is observed for the hydrophobic carbosilane films as measured by ellipsometric porosimetry.
The dielectric constant (k) values for the carbosilane films range from 1.6 to 3.5. In additional embodiments, the dielectric constant (k) values for the carbosilane films are from 1.6 to 3.0, or from 1.6 to 2.5. Dielectric constant values are measured using a CV dot technique in which the film is deposited on a highly doped Si substrate and metallic dots are deposited on top of the film. The dielectric constant across the film is then measured.
Additionally, films according to embodiments of the invention have percent compositions in the range of 45-60 % C, 25-35 %Si, and 10-20 % O (atomic percent).
Films according to embodiments of the invention are chemically stable. In general, chemical stability means that the film is significantly resistant to chemical degradation. For example, chemically stable films according to embodiments of the invention are resistant to degradation when a sample of the film is placed in a solution of 0.5 % HF (at 23 °C), 1.0 % KOH (at 50 °C), 15 % TMAH (tetramethylammonium hydroxide) (at 60 °C), or 30 % H202 (at 50 °C) for 10 minutes. Resistant to degradation means that 10 nm or less of film loss and 5 % or less change in refractive index is observed.
In general, a porogen molecule or functional group is a molecule or functional group that is present in the precursor film that is capable of creating pores in the final film. Typically the porogen molecule is removed from the final film through heating, although other methods are possible. Other methods for porogen removal, include, for example, UV-curing or electron beam curing. After removal, the space occupied by the porogen molecule becomes a pore.
The substrate on which the devices that make up the IC circuit chip are built and dielectric films are used is, for example, a silicon wafer or a silicon-on-insulator substrate. Silicon wafers are substrates that are typically used in the semiconductor processing industry, although embodiments of the invention are not dependent on the type of substrate used. The substrate could also be comprised of, for example, germanium, indium antimonide, lead telluride, indium arsenide, indium phosphide, gallium arsenide, gallium antimonide, and or other Group III-V materials either alone or in combination with silicon or silicon dioxide or other insulating materials. IC devices that make up the chip are built on the substrate surface. Devices are optionally distributed across the substrate surface and or stacked on top of each other.
In general, a spin-on-dielectric film (SOD) is a dielectric film created by spinning a solution to distribute it across a surface and then solidifying the solution on the surface. A liquid form of the film is placed in the center of the substrate (such as a wafer). The substrate is spun causing the liquid film material to distribute across the wafer surface. The thickness of the resulting film depends in part on the viscosity of the liquid film. Excess liquid film material is spun off the substrate.
In general a low-k dielectric material is a dielectric material that has a lower dielectric constant that silicon dioxide (Si02). Silicon dioxide has a dielectric constant of 3.9. The use of low-k dielectric materials in integrated circuit devices has enabled continued device size reduction. Although a variety of materials have lower dielectric constants that Si02 not all materials are suitable for integration into integrated circuits and integrated circuit manufacturing processes.
An inter-layer dielectric (ILD) or inter-metal dielectric (IMD) film is the insulating material used between metal conductors and devices (such as transistors) in integrated circuit devices.
Persons skilled in the relevant art appreciate that modifications and variations are possible throughout the disclosure and combinations and substitutions for various components shown and described. Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention, but does not necessarily denote that they are present in every embodiment. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. Various additional layers and or structures may be included and or described features may be omitted in other embodiments.

Claims

CLAIMS We claim:
1. A device comprising,
a substrate,
a dielectric film disposed on the substrate, wherein the dielectric film is comprised of crosslinked cyclic carbosilanes wherein a cyclic carbosilane has a ring structure comprising carbon and silicon, and wherein the dielectric film is hydrophobic.
2. The device of claim 1 wherein the dielectric film has a k value of from 1.6 to 2.5.
3. The device of claim 1 wherein the dielectric film comprises between 45 and 60 atomic percent C, between 25 and 35 atomic percent Si, and between 10 and 20 atomic percent O.
4. The device of claim 1 wherein the substrate additionally comprises the components of an integrated circuit device and the dielectric film is between at least two components of the integrated circuit device.
5. The device of claim 1 wherein the dielectric film additionally comprises a reacted photo acid generator, a reacted photo base generator, a reacted thermally-activated acid generator, or a reacted thermally-activated base generator.
6. The device of claim 1 wherein the dielectric film is porous and the porosity of the film is in the range of 5 % and 60 %.
7. The device of claim 1 wherein the dielectric film is porous and the porosity of the film is in the range of 35 % and 50 %.
8. The device of claims 6 or 7 wherein the pores of the dielectric film have dimensions that are between 0.25 nm and 2 nm.
9. The device of claims 6 or 7 wherein the film is chemically stable.
10. A device comprising,
a substrate,
a dielectric film disposed on the substrate, wherein the dielectric film is comprised of crosslinked cyclic carbosilanes wherein a cyclic carbosilane has a ring structure comprising carbon and silicon, and wherein the dielectric film is porous and the porosity is in the range of 25 % to 60 %.
11. The device of claim 10 wherein the pores of the dielectric film have dimensions that are between 0.25 nm and 2 nm.
12. The device of claim 10 wherein the dielectric film has a k value of from 1.6 to 2.5.
13. The device of claim 10 wherein the dielectric film is porous and the porosity of the film is in the range of 35 % and 50 %.
14. The device of claim 10 wherein the dielectric film comprises between 45 and 60 atomic percent C, between 25 and 35 atomic percent Si, and between 10 and 20 atomic percent O.
15. The device of claim 10 wherein the substrate additionally comprises the components of an integrated circuit device and the dielectric film is between at least two components of the integrated circuit device.
16. The device of claim 10 wherein the film is chemically stable.
17. A method for making a dielectric film comprising,
providing a substrate having a surface,
depositing a mixture comprising oligomers of cyclic carbosilanes, wherein a cyclic carbosilane has a ring structure comprising carbon and silicon, and a polymerization initiator wherein the polymerization initiator is selected from the group consisting of photo acid generators, photo base generators,
thermally-activated acid generators, and thermally-activated base generators, onto the substrate surface, and
exposing the substrate to light or heat causing the photo acid generator, photo base generator, thermally-activated acid generator, or thermally-activated base generator to be activated producing and acid or a base and causing the mixture to solidify.
18. The method of claim 17 wherein the oligomers comprise between 3 and 10 cyclic carbosilane units.
19. The method of claim 17 wherein the oligomers of cyclic carbosilanes are linear oligomers.
20. The method of claim 17 wherein the oligomers of cyclic carbosilanes are branched oligomers.
21. The method of claim 17 wherein the mixture also comprises a porogen molecule that has attached carbosilanes.
22. The method of claim 17 wherein the method also includes spinning the substrate to distribute the mixture across the substrate surface before exposing the substrate to light or heat.
PCT/US2011/065196 2010-12-23 2011-12-15 Cyclic carbosilane dielectric films WO2012087750A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/978,385 US8441006B2 (en) 2010-12-23 2010-12-23 Cyclic carbosilane dielectric films
US12/978,385 2010-12-23

Publications (1)

Publication Number Publication Date
WO2012087750A1 true WO2012087750A1 (en) 2012-06-28

Family

ID=46314375

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/065196 WO2012087750A1 (en) 2010-12-23 2011-12-15 Cyclic carbosilane dielectric films

Country Status (3)

Country Link
US (2) US8441006B2 (en)
TW (1) TWI470695B (en)
WO (1) WO2012087750A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8441006B2 (en) 2010-12-23 2013-05-14 Intel Corporation Cyclic carbosilane dielectric films
US10714604B2 (en) 2018-06-25 2020-07-14 Intel Corporation Quantum dot devices with multiple dielectrics around fins

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201319299A (en) * 2011-09-13 2013-05-16 Applied Materials Inc Activated silicon precursors for low temperature plasma enhanced deposition
US8968864B2 (en) * 2011-09-23 2015-03-03 Imec Sealed porous materials, methods for making them, and semiconductor devices comprising them
US10155826B2 (en) 2014-12-12 2018-12-18 Exxonmobil Research And Engineering Company Olefin polymerization catalyst system comprising mesoporous organosilica support
WO2016094778A1 (en) 2014-12-12 2016-06-16 Exxonmobil Research And Engineering Company Organosilica materials and uses thereof
US10576453B2 (en) 2014-12-12 2020-03-03 Exxonmobil Research And Engineering Company Membrane fabrication methods using organosilica materials and uses thereof
WO2016094820A1 (en) 2014-12-12 2016-06-16 Exxonmobil Research And Engineering Company Adsorbent for heteroatom species removal and uses thereof
US10047304B2 (en) 2014-12-12 2018-08-14 Exxonmobil Research And Engineering Company Aromatic hydrogenation catalysts and uses thereof
WO2016094843A2 (en) 2014-12-12 2016-06-16 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system comprising mesoporous organosilica support
US10239967B2 (en) 2014-12-12 2019-03-26 Exxonmobil Research And Engineering Company Olefin polymerization catalyst system comprising mesoporous organosilica support
US10207249B2 (en) 2014-12-12 2019-02-19 Exxonmobil Research And Engineering Company Organosilica materials and uses thereof
US10351639B2 (en) 2014-12-12 2019-07-16 Exxonmobil Research And Engineering Company Organosilica materials for use as adsorbents for oxygenate removal
US10022701B2 (en) 2014-12-12 2018-07-17 Exxonmobil Research And Engineering Company Coating methods using organosilica materials and uses thereof
US9956541B2 (en) 2014-12-12 2018-05-01 Exxonmobil Research And Engineering Company Methods of separating aromatic compounds from lube base stocks
WO2017095397A1 (en) * 2015-12-02 2017-06-08 Intel Corporation Structures with fillable low-k materials based on cyclic carbosilane precursors
WO2017095433A1 (en) * 2015-12-04 2017-06-08 Intel Corporation Liquid precursor based dielectrics with control of carbon, oxygen and silicon composition
US11406972B2 (en) 2015-12-04 2022-08-09 Intel Corporation Activation of protected cross-linking catalysts during formation of dielectric materials
CN109311679A (en) 2016-06-10 2019-02-05 埃克森美孚研究工程公司 Organic silica material, its manufacturing method and application thereof
CN109311001B (en) 2016-06-10 2022-04-08 埃克森美孚研究工程公司 Organosilica polymer catalyst and method for producing same
US10179839B2 (en) 2016-11-18 2019-01-15 Exxonmobil Research And Engineering Company Sulfur terminated organosilica materials and uses thereof
WO2018125201A1 (en) * 2016-12-30 2018-07-05 Intel Corporation Synthesis of polycarbosilanes and derivitization to high density sic fill material
SG11202005456XA (en) 2017-12-21 2020-07-29 Exxonmobil Res & Eng Co Methods of producing organosilica materials and uses thereof
JP6980624B2 (en) * 2018-09-13 2021-12-15 株式会社Kokusai Electric Semiconductor device manufacturing method, substrate processing method, substrate processing device and program
US11499014B2 (en) 2019-12-31 2022-11-15 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Cureable formulations for forming low-k dielectric silicon-containing films using polycarbosilazane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080009141A1 (en) * 2006-07-05 2008-01-10 International Business Machines Corporation Methods to form SiCOH or SiCNH dielectrics and structures including the same
US20080150091A1 (en) * 2004-04-08 2008-06-26 International Business Machines Corporation MULTIPLE PATTERNING USING PATTERNABLE LOW-k DIELECTRIC MATERIALS
US20080271640A1 (en) * 2002-04-17 2008-11-06 Air Products And Chemicals, Inc. Porogens, Porogenated Precursors and Methods for Using the Same to Provide Porous Organosilica Glass Films with Low Dielectric Constants
US7479306B2 (en) * 2005-01-21 2009-01-20 International Business Machines Corporation SiCOH dielectric material with improved toughness and improved Si-C bonding, semiconductor device containing the same, and method to make the same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080268177A1 (en) * 2002-05-17 2008-10-30 Air Products And Chemicals, Inc. Porogens, Porogenated Precursors and Methods for Using the Same to Provide Porous Organosilica Glass Films with Low Dielectric Constants
US7041748B2 (en) * 2003-01-08 2006-05-09 International Business Machines Corporation Patternable low dielectric constant materials and their use in ULSI interconnection
US7071091B2 (en) 2004-04-20 2006-07-04 Intel Corporation Method of forming air gaps in a dielectric material using a sacrificial film
US20090130412A1 (en) * 2004-09-22 2009-05-21 Benjamin David Hatton Method of transformation of bridging organic groups in organosilica materials
US7947799B2 (en) * 2004-09-22 2011-05-24 Kai Manfred Martin Landskron High organic group content-periodic mesoporous organosilicas (HO-PMO's)
US7332445B2 (en) * 2004-09-28 2008-02-19 Air Products And Chemicals, Inc. Porous low dielectric constant compositions and methods for making and using same
US7135402B2 (en) * 2005-02-01 2006-11-14 Taiwan Semiconductor Manufacturing Company, Ltd. Sealing pores of low-k dielectrics using CxHy
JP2007045966A (en) * 2005-08-11 2007-02-22 Fujifilm Corp Composition for forming insulating film, insulating film and method for producing the same
US20100200991A1 (en) 2007-03-15 2010-08-12 Rohan Akolkar Dopant Enhanced Interconnect
US20080223287A1 (en) 2007-03-15 2008-09-18 Lavoie Adrien R Plasma enhanced ALD process for copper alloy seed layers
US7888220B2 (en) 2008-06-26 2011-02-15 Intel Corporation Self-aligned insulating etchstop layer on a metal contact
US8441006B2 (en) 2010-12-23 2013-05-14 Intel Corporation Cyclic carbosilane dielectric films

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080271640A1 (en) * 2002-04-17 2008-11-06 Air Products And Chemicals, Inc. Porogens, Porogenated Precursors and Methods for Using the Same to Provide Porous Organosilica Glass Films with Low Dielectric Constants
US20080150091A1 (en) * 2004-04-08 2008-06-26 International Business Machines Corporation MULTIPLE PATTERNING USING PATTERNABLE LOW-k DIELECTRIC MATERIALS
US7479306B2 (en) * 2005-01-21 2009-01-20 International Business Machines Corporation SiCOH dielectric material with improved toughness and improved Si-C bonding, semiconductor device containing the same, and method to make the same
US20080009141A1 (en) * 2006-07-05 2008-01-10 International Business Machines Corporation Methods to form SiCOH or SiCNH dielectrics and structures including the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8441006B2 (en) 2010-12-23 2013-05-14 Intel Corporation Cyclic carbosilane dielectric films
US9070553B2 (en) 2010-12-23 2015-06-30 Intel Corporation Cyclic carbosilane dielectric films
US10714604B2 (en) 2018-06-25 2020-07-14 Intel Corporation Quantum dot devices with multiple dielectrics around fins

Also Published As

Publication number Publication date
US20130249049A1 (en) 2013-09-26
TW201243947A (en) 2012-11-01
US8441006B2 (en) 2013-05-14
US9070553B2 (en) 2015-06-30
TWI470695B (en) 2015-01-21
US20120161295A1 (en) 2012-06-28

Similar Documents

Publication Publication Date Title
US9070553B2 (en) Cyclic carbosilane dielectric films
US20140004358A1 (en) Low k carbosilane films
US8399349B2 (en) Materials and methods of forming controlled void
KR101610978B1 (en) Low-k dielectrics obtainable by twin polymerization
TWI553038B (en) Polymer, organic layer composition, organic layer, and method of forming patterns
US20150093545A1 (en) Composition for a silica based layer, silica based layer, and method of manufacturing a silica based layer
US20230128779A1 (en) Filling openings by combining non-flowable and flowable processes
US9240443B2 (en) Process of preparing a gap filler agent, a gap filler agent prepared using same, and a method for manufacturing semiconductor capacitor using the gap filler agent
JP6923340B2 (en) Silica film forming composition and silica film
TWI575024B (en) Composition for forming silica layer, silica layer, and electronic device
KR20140012118A (en) Polysilanesiloxane copolymers and method of converting to silicon dioxide
KR101825546B1 (en) Composition for forming silica based layer, and method for manufacturing silica based layer
JP7007434B2 (en) Silica film forming composition and silica film
CN111051568A (en) Alkoxy silicon heterocyclic or acyloxy silicon heterocyclic compound and method for depositing film using the same
TWI719069B (en) Activation of protected cross-linking catalysts during formation of dielectric materials
CN112979408A (en) Compound and synthesis method thereof, hard mask composition and method for forming pattern
CN111944320B (en) Composition for forming silicon dioxide layer, silicon dioxide layer and electronic device
WO2017095397A1 (en) Structures with fillable low-k materials based on cyclic carbosilane precursors
KR102270138B1 (en) Composition for forming silica layer, method for manufacturing silica layer, and silica layer
JP5540784B2 (en) Container with film forming composition
KR101833801B1 (en) Composition for forming silica based layer, silica based layer, and electronic device
CN112731766A (en) Hardmask composition, hardmask layer and method of forming pattern

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11851636

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11851636

Country of ref document: EP

Kind code of ref document: A1