US20020001973A1 - Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films - Google Patents

Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films Download PDF

Info

Publication number
US20020001973A1
US20020001973A1 US09841453 US84145301A US2002001973A1 US 20020001973 A1 US20020001973 A1 US 20020001973A1 US 09841453 US09841453 US 09841453 US 84145301 A US84145301 A US 84145301A US 2002001973 A1 US2002001973 A1 US 2002001973A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
film
surface modification
process
monomer
modification agent
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.)
Abandoned
Application number
US09841453
Inventor
Hui-Jung Wu
James Drage
Original Assignee
Hui-Jung Wu
Drage James S.
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

Links

Images

Classifications

    • GPHYSICS
    • G06COMPUTING; CALCULATING; COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/02Input arrangements using manually operated switches, e.g. using keyboards or dials
    • G06F3/023Arrangements for converting discrete items of information into a coded form, e.g. arrangements for interpreting keyboard generated codes as alphanumeric codes, operand codes or instruction codes
    • G06F3/0233Character input methods
    • G06F3/0237Character input methods using prediction or retrieval techniques
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • C09C1/30Silicic acid
    • C09C1/3081Treatment with organo-silicon compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • C09C1/3684Treatment with organo-silicon compounds
    • GPHYSICS
    • G06COMPUTING; CALCULATING; COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/02Input arrangements using manually operated switches, e.g. using keyboards or dials
    • G06F3/023Arrangements for converting discrete items of information into a coded form, e.g. arrangements for interpreting keyboard generated codes as alphanumeric codes, operand codes or instruction codes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H01L21/02225Forming 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H01L21/02296Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H01L21/02296Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02343Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a liquid
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H01L21/02296Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02359Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment to change the surface groups of the insulating layer
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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, 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, 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
    • H01L21/3105After-treatment
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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, 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, 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
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31608Deposition of SiO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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, 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, 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
    • 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter

Abstract

A process for treating a silica film on a substrate, which includes reacting a suitable silica film with an effective amount of a surface modification agent, wherein the silica film is present on a substrate. The reaction is conducted under suitable conditions and for a period of time sufficient for the surface modification agent to form a hydrophobic coating on the film. The surface modification agent includes at least one type of oligomer or polymer reactive with silanols on the silica film. Dielectric films and integrated circuits including such films are also disclosed.

Description

    CROSS REFERENCE TO RELATED APPLICATION
  • This patent application is a continuation-in-part of, and claims the benefit of provisional application serial No. 60/117,248, filed on Jan. 26, 1999, the disclosure of which is incorporated by reference herein in its entirety.[0001]
  • FIELD OF THE INVENTION
  • The present invention relates to low dielectric constant silica films and to improved processes for producing the same on substrates suitable for use in the production of semiconductor devices, such as integrated circuits (“ICs”). [0002]
  • BACKGROUND OF THE INVENTION
  • As feature sizes in integrated circuits (ICs) approach 0.18 microns and below, it is believed that electrical insulation layers having a dielectric constant ≦2.5 will be required for interlevel dielectric (ILD) and intermetal dielectric (IMD) applications. [0003]
  • Nanoporous Silica Films [0004]
  • One material with a low dielectric constant (“k”) is nanoporous silica, which can be prepared with relatively low dielectric constants, by the incorporation of air, with a k of 1, in the form of nanometer-scale pores. Nanoporous silica is attractive because it employs similar precursors, including organic-substituted silanes, e.g., tetramethoxysilane (“TMOS”) and/or tetraethoxysilane (“TEOS”), and/or methyltriethoxysilane, as are used for the currently employed spin-on-glasses (“SOG”) and chemical vapor deposition (“CVD”) of silica (SiO[0005] 2). Nanoporous silica is also attractive because it is possible to control the porosity, and hence the density, material strength and dielectric constant of the resulting film material. In addition to a low k, nanoporous silica offers other advantages including: 1) thermal stability to 500° C., 2) substantially small pore size, i.e., at least an order of magnitude smaller in scale than the microelectronic features of the integrated circuit), 3) as noted above, preparation from materials such as silica and TEOS that are widely used in semiconductors, 4) the ability to “tune” the dielectric constant of nanoporous silica over a wide range, and 5) deposition of a nanoporous film can be achieved using tools similar to those employed for conventional SOG processing.
  • One difficulty associated with nanoporous silica films is the presence of polarizable functional groups on internal pore surfaces. Functional groups present in previously available nanoporous films include silanol (SiOH), siloxane (SiOSi), alkoxy (SiOR), where R is an organic species such as, but not limited to, a methyl, ethyl, isopropyl, or phenyl groups, or an alkylsilane (SiR), where R is as defined previously. In particular, silanol groups are highly polarizable and hygroscopic. Since nanoporous silica has a relatively large (internal) surface area associated with its porous structure, the contribution of the highly polarizable silanol groups results in higher than desired dielectric constant values. Adsorption of environmental water by the silanol groups can potentially raise the dielectric constant of such materials even further. [0006]
  • Even if the dielectric film is out-gassed by heating before subsequent processing, the presence of the polar silanols can contribute negatively to the dielectric constant and dielectric loss. Previously employed methods for overcoming this limitation and rendering the internal pore surfaces of nanoporous silica less polarizable and less hydrophilic include reacting the internal surface silanols with surface modifying agents, also referred to in the art as silylation agents or capping agents. Such capping agents include, e.g., chlorosilanes or disilazanes. [0007]
  • In one previously employed method of capping silanol groups on pore surfaces, an organic reagent such as hexamethyldisilazane (HMDZ) is introduced into the pores of the film and allowed to react with the surface silanol groups to cap the silanols by forming trimethylsilyl groups. These silylated surface groups are significantly less polarizable than the original silanols, and render the pore surfaces of the film hydrophobic. One disadvantage in the use of trimethylsilyl groups is that they are not very thermally stable and may out-gas during processing of the IC and cause via poisoning. [0008]
  • Another critical parameter of a nanoporous silica film is its mechanical strength. Generally the mechanical strength of a material decreases in proportion to any decrease in density in that material. For a nanoporous film to be useful as a dielectric film in IC devices, it is important that the combination of mechanical strength and low dielectric constant be optimized. For a given dielectric constant (which is proportional to refractive index and density), the density is fixed, at least for a specific chemical composition. With fixed density, the strength of the nanoporous silica is maximized by having the greatest fraction of solid within the skeleton of the film rather than as appended chemical groups on the surfaces of the nanometer-scale pores. Thus, in another drawback, reagents such as HMDZ introduce a significant additional mass, in the form of trimethylsilyl groups, to the pore surfaces. The disproportionate mass of the trimethylsilyl groups is not available to contribute to mechanical strength, but it does raise the density of the film and therefore is an obstacle to achieving the lowest possible k. [0009]
  • For these reasons, and in view of the need for rapid competitive advances in the art of semiconductor, and/or microprocessor or IC fabrication, there remains a constant need in the art to improve upon previous methods and materials. In particular, there is a need to provide silica dielectric films with hydrophobic surfaces, and in particular to provide nanoporous silica films with hydrophobic pore surfaces, while desirably enhancing the mechanical strength of such treated hydrophobic films. The successful solution of this problem will provide greater material film strength for a given desired dielectric constant. [0010]
  • SUMMARY OF THE INVENTION
  • Surprisingly, the methods of the present invention are able to solve these and other problems in the art by providing surface modification agents that are able to render treated silica dielectric films hydrophobic while also enhancing the mechanical strength of the treated films, relative to previously employed methods and agents or reagents. [0011]
  • Accordingly, the invention provides novel processes for forming silica dielectric films or coatings on a desired substrate by the steps of reacting a suitable silica film with a surface modification agent. The silica film is present on a substrate, and the reaction is conducted under suitable conditions, and for a period of time sufficient for the surface modification agent to form a hydrophobic coating on the silica dielectric film. The surface modification agent comprises at least one type of oligomer or polymer reactive with silanols on the silica film. Compositions, including silica dielectric films and integrated circuits with at least one silica dielectric film treated by the processes of the invention are also provided. The processes of the invention are unexpectedly applied to silica dielectric films without significantly degrading the obtainable range of desirable dielectric values. [0012]
  • Optionally, the silica film is pretreated with a monomer-type surface modification agent that can cap or silylate silanols in the dielectric film surface. In a further option, the silica film is treated with a composition that includes both an oligomer or polymer surface modification agent and a monomer-type surface modification agent. [0013]
  • The silica dielectric film to be treated may be non-porous, but is preferably a nanoporous silica film prepared on the substrate immediately prior to the time of treatment, or may be previously prepared and stored or obtained from another source. It should also be mentioned that the silica dielectric films to be treated by the novel processes of the invention are optionally aged or gelled, although this is not required. If an aging step is employed, it can be conducted before or after application of the surface modification treatment as described herein, but preferably, the film is aged prior to surface modification. [0014]
  • The processes of the invention may be conducted in either a vapor phase or a liquid phase, as desired. Further, the processes are optionally conducted in the presence of a solvent or co-solvent, and it should be appreciated that when the surface modification is to be conducted in the liquid phase, the solvent or co-solvent is effective to dissolve and/or suspend the surface modification agent or agents without significantly dissolving the film to be treated. [0015]
  • Any suitable material may be employed as a solvent or co-solvent, including both ketones and non-ketones, but preferably, such solvent or co-solvent is selected from the group consisting of ethers, esters, ketoses, glycol ethers, chlorinated solvents, low viscosity siloxanes, and suitable combinations thereof. [0016]
  • While the silica film to be treated need not be porous, preferably, the film to be treated is a nanoporous dielectric film having a pore structure with a high surface area, and the surface modification process is conducted for a period of time sufficient for the surface modification agent to surface modification agent to effectively coat the surface of the film. and to produce a treated nanoporous silica film having a dielectric constant of about 3 or less. Preferably, the surface modification reaction is conducted for a time period ranging from about 10 seconds to about 1 hour and at a temperature ranging from about 10° C. to about 300° C. [0017]
  • Preferably the film to be treated is on a substrate, e.g., a wafer suitable for production of an integrated circuit. [0018]
  • The invention also provides for dielectric films and an integrated circuit or circuits that include at least one dielectric film produced by the processes of the invention. Preferably, dielectric silica-based films produced by the inventive processes reveal no significant silanol absorbance in the wavelengths ranging from about 3200 to about 3700 cm[0019] −1 under Fourier transform infrared spectroscopy.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
  • Accordingly, in contrast to previously reported methods for rendering silica dielectric films and materials hydrophobic, the present invention provides for polymer and/or oligomer-based reagents for surface modification treatment. This approach has a number of advantages over previous methods. In particular, surface modification using a polymer-based reagent will provide improved mechanical strength, relative to previously employed reagents. Without wishing to be bound by any hypothesis or theory as to how the inventive reagents might operate, it is believed that weakest part of the fine structure of a nanoporous silica film is the contact point between the particles or grains of the film. Thus, a polymer coating on the film surface, particularly a coating on the surfaces of the nanometer-scale pores, is believed to both eliminate the moisture absorbing problem, and to strengthen the mechanical properties of the film, by overcoating and binding together the fine particles or grains that make up the film. Whatever the underlying reasons for the positive effect on film mechanical strength, the examples provided hereinbelow confirm that the methods and reagents of the invention in fact provide enhanced film strength. [0020]
  • The processes and reagents of the invention are applied to silica dielectric films. A number of methods for the preparation of nanoporous silica films on substrates are known to the art, as summarized in the “Background of the Invention”, above. In addition, a number of variations and improvement to these generally known methods for the preparation of nanoporous films are taught by co-owned U.S. patent application Ser. Nos. 09/046,475 and 09/046,473, both filed on Mar. 25, 1998; U.S. patent application Ser. No. 09/054,262, filed on Apr. 3, 1998; and U.S. patent application Ser. Nos. 09/055,244 and 09/055,516, both filed on Apr. 6, 1998, as well as co-owned U.S. patent application Ser. Nos. 09/379,484, filed on Aug. 23, 1999, 09/392,413, filed on Sep. 9, 1999, the disclosures of which are incorporated by reference herein in their entireties. In any event, the artisan will appreciate that the methods and materials of the invention are readily applied to a wide variety of art-known dielectric materials, including organic-based dielectric materials, and preferably, to silica-based dielectric materials, and most preferably to nanoporous dielectric silica materials, to provide for enhanced strength and/or a protective hydrophobic coating. [0021]
  • In order to better appreciate the scope of the invention, it should be understood that unless the “SiO[0022] 2” functional group is specifically mentioned when the term “silica” is employed, the term “silica” as used herein, for example, with reference to dielectric films, is intended to refer to dielectric films prepared by the inventive methods from an organic or inorganic glass base material, e.g., any suitable silicon-based material. In addition, it should also be understood that the use of singular terms herein is not intended to be so limited, but, where appropriate, also encompasses the plural, e.g., exemplary processes of the invention may be described as applying to and producing a “film” but it is intended that multiple films can be produced by the described, exemplified and claimed processes, as desired.
  • Further, the use of the terms, “agent” or “agents” herein should be considered to be synonymous with the terms, “reagent” or “reagents,” unless otherwise indicated. Use of the term, “integrated circuit,” or “IC,” is intended to represent any semiconductor product for which the processes and compositions of the invention are employed, unless otherwise specified. [0023]
  • Further still, although the description provided herein generally describes processes employed for treating nanoporous dielectric materials, the artisan will readily appreciate that the instantly provided methods and compositions are readily applied to nonporous dielectric silica films as well. Thus, nonporous films applied to a suitable substrate, e.g., a semiconductor wafer suitable for producing an integrated circuit, as described below, will also benefit from the methods and materials provided by the present invention. For example, adsorption of environmental water vapor onto hydrophilic silica films employed as insulators and the like in fabricating integrated circuits will cause problems such as an excessively high dielectric constant, current leakage and via poisoning. These additional problems are solved by the methods and compositions of the invention. [0024]
  • Substrates [0025]
  • Broadly speaking, a “substrate” as described herein includes any suitable composition formed before a nanoporous silica film of the invention is applied to and/or formed on that composition. For example, a substrate is typically a silicon wafer suitable for producing an integrated circuit, and the base material from which the nanoporous silica film is formed is applied onto the substrate by any methods, e.g., including, but not limited to, the art-known methods of spin-coating, chemical vapor deposition or CVD, and dip-coating. Prior to application of the base materials to form the nanoporous silica film, the substrate surface is optionally prepared for coating by standard, art-known cleaning methods. [0026]
  • Suitable substrates for the present invention non-exclusively include semiconductor materials such as gallium arsenide (“GaAs”), silicon and compositions containing silicon such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, and silicon dioxide (“SiO[0027] 2”) and mixtures thereof. On the surface of the substrate is an optional pattern of raised lines, such as metal, oxide, nitride or oxynitride lines which are formed by well known lithographic techniques. Suitable materials for the lines include silica, silicon nitride, titanium nitride, tantalum nitride, aluminum, aluminum alloys, copper, copper alloys, tantalum, tungsten and silicon oxynitride. These lines form the conductors or insulators of an integrated circuit. Such are typically closely separated from one another at distances of about 20 microns or less, preferably 1 microns or less, and more preferably from about 0.05 to about 1 microns. Other optional features of the surface of a suitable substrate include previously formed nanoporous silica dielectric films
  • The starting materials for conducting the processes of the invention also include a nanoporous silica film formed on the substrate by applying a silica precursor, such as a spin-on glass composition onto the substrate and then optionally aging the film. If an aging step is applied, this is typically conducted, for example, by treating the coated substrate with, e.g., ammonia and water vapor, to promote gelation. [0028]
  • Generally, the processes of the invention are conducted on the nanoporous film while it is still wet film, directly after aging. In alternative embodiments, the processes of the invention are optionally conducted on nanoporous silica films not yet subjected to aging, to dried nanoporous films and to nanoporous silica films that have been stored for a time period after completing the aging process. [0029]
  • While a number of alternative aging methods are known to the art, preferably, in the processes of the invention, the film is aged by treatment with ammonium hydroxide. As exemplified hereinbelow, the film is aged statically by exposing the film-bearing substrate to 15M ammonium hydroxide and water vapor in a confined chamber for a time period and under conditions effective to allow the water and ammonia vapor to diffuse into the film. [0030]
  • Polymeric/Oligomeric Surface Modification Compositions [0031]
  • In order to optimize the density/dielectric constant parameters together with the need for sufficient mechanical strength, the invention provides a surface modification process using one or more polymer/oligomer surface modification compositions, able to form a hydrophobic surface film over the silanol-containing surfaces of the silica dielectric films. Thus, within these broad parameters, a surface modification composition includes one or more surface modification agents, prepared in a composition that allows for the formation of a hydrophobic coating upon contact with the surface of a silica dielectric film. [0032]
  • More particularly, it is contemplated that the surface modification agent is prepared from a monomer i.e., a monomer precursor, that can be induced to polymerize and cross-link with itself and/or other types of monomers present in the reaction mixture to form a surface modification reagent. The formed surface modification reagent is, for example, a mixture that includes oligomers, e.g., multimers of 100 or fewer repeat units, and/or polymers, e.g., multimers of 100 or more repeat units. This surface modification reagent is then applied to a silica dielectric film in need of such treatment where it will react with, i.e., cap, a substantial proportion of silanol groups thereon to form a desired hydrophobic coating. This surface modification reagent can be prepared from polymerization of suitable monomer(s), including organosilicon monomers able to form polymers that can react with silanols, e.g., methyltriacetoxysilane, tris(dimethlyaimino)-methylsilane, and tris(diethylamino)methylsilane. [0033]
  • More typically, the surface modification reagent is prepared from silicon-based monomers, e.g., siloxanes, silazanes, silanes, carbosilanes, and the like, and combinations thereof, e.g,, by hydrolysis/condensation or other type of polymerization/reactions. Simply by way of example, and without limitation, one such reaction will proceed as follows. [0034]
  • CH3Si(OCOCH3)+H2O→[—O—Si(CH3)(OCOCH3)—]n+CH3COOH
  • wherein “→” symbolizesthe proceeding of the polymerization, in the case, hydrolysis/condensation, and “n” is an integer ranging in value from 2 to about 10,000, or greater. [0035]
  • The molar ratio of water to monomer in the reaction mixture is readily adjusted according to the particular products. In preferred embodiments, the water is present during the reaction in proportion to the monomer in a ratio ranging from about 0.50:1.5 to about 1.5:0.5, mole/mole. [0036]
  • While not wishing to be bound by any theory of hypothesis as to how the reagents of the invention operate, based on this illustrative reaction scheme, the polymeric—OCOCH[0037] 3 moiety is the functional group that is believed to react with silanols (Si—OH) on the porous silica surface. While it is believed that such surface modification reagents will primarily link to the surface silanols, it is also contemplated that in certain optional embodiments, a significant amount of cross-linking within the resulting hydrophobic coating will take place during formation of that coating.
  • Thus, one exemplary class of siloxane polymer/oligomers that have multi-functional groups that can react with silanol (Si—OH) have the following general formula [0038]
  • (—SiXR—O—)n   Formula I
  • wherein R can be H, alkyl, or aryl group and X is, e.g., selected from one or more of the following moieties: H, acetoxy (OCOCH[0039] 3), enoxy (CH2═C(CH3)—O—Si), oxime (R2C═N—Os—Si), alkoxy(RO—Si), amine(R2N—Si) and/or silanol (Si—OH), and n is an integer ranging, for example, in value from 2 to about 10,000, or greater. In a further option, n is an integer ranging in value from about 2 to about 1000. It should also be understood that, in a given preparation, the sizes of the oligomers and/or polymer species formed, and therefore the value of n, will typically be distributed over a range of values.
  • Another general class of suitable surface modification reagents include silazane polymer/oligomers that have multi-functional group that can react with silanol (Si—OH) having the general formula: [0040]
  • (—SiXR1—NR2—)n   Formula II
  • wherein R[0041] 1 and R2 are independently H, alkyl, and/or aryl, and is, e.g., selected from one or more of the following moieties: acetoxy (OCOCH3), enoxy (CH2═C(CH3)—O—Si), oxime(R2C═N—Os—Si), alkoxy(RO—Si), and amine(R2N—Si), and n is defined as for formula I.
  • It will also be appreciated that since the backbone of silazane polymers is Si—N, this group can optionally provide additional functionality and options for derivitization and cross-linking. Suitable silazane reagents include, e.g., poly(1,2-dimethylsilazne), (1,2-dimethylsilazane)(1-methylsilazane) copolymer, and N-methylsilazane resin in toluene. These silazane polymers can be synthesized by the reaction of an appropriate amine or NH[0042] 3 with the desired silane reagents.
  • Yet another general class of suitable surface modification reagents include silane polymer/oligomers that have multi-functional group that can react with silanol (Si—OH) having the general formula: [0043]
  • (—SiXR—)n   Formula III
  • wherein R can be H, alkyl, or aryl group and X is, e.g., selected from one or more of the following moieties: H, acetoxy (OCOCH[0044] 3), enoxy (CH2═C(CH3)—O—Si), oxime(R2C═N—Os—Si), alkoxy(RO—Si), and amine(R2N—Si), and n is defined as for formula I. It will also be appreciated that since the backbone of silane polymers is Si—Si, this group can optionally provide additional functionality and options for derivatization and cross-linking. Typical silane reagents that can be used for this application include, e.g., polydimethylsilane, polyphenylmethylsilane, and the like, as well as combinations thereof.
  • Another general class of suitable surface modification reagents include carbosilanes polymer/oligomers that have multi-functional group that can react with silanol (Si—OH) having the general formula: [0045]
  • (—SiR1R2—R3—)n   Formula IV
  • Wherein R[0046] 1 and R2 can independently H, alkyl, aryl groups, acetoxy (OCOCH3), enoxy (CH2═C(CH3)—O—Si), oxime(R2C═N—Os—Si), alkoxy(RO—Si), or amine(R2N—Si), and R3 can be substituted or un-substituted alkylene or arylene,
  • Suitable siloxane polymers having multi-functional groups and silanol groups, are also commercially available. For example, the artisan will be familiar with the T-11 series of siloxane reagents available from the Advanced Microelectronic Materials division of Honeywell (formerly AlliedSignal) (Sunnyvale, Calif.). Many suitable silane and silazane polymers are also commercially available, e.g., from United Chemical Technology (Bristol, Pa.). [0047]
  • It is also contemplated that combinations of one or more of the above, e.g., of reagents represented by Formulas I, II, III and/or IV, in the form of polymer and/or copolymer combinations, are also usefully employed in the methods and compositions of the invention. [0048]
  • Preferably, the surface modification agent is the hydrolysis/condensation product of a spin-on-glass type silica reagent, e.g., methyltriacetoxysilane (“MTAS”). The hydrolysis/condensation product of MTAS has a siloxane backbone structure with acetoxy multi-functional groups, formed by mixing a suitable MTAS solution with a defined proportion of water under appropriate conditions. [0049]
  • Methods of Reacting Silica Dielectric Films with Surface Modification Agents [0050]
  • Although the exemplified methods for reacting silica films with surface modification agents are conducted in the liquid phase, the artisan will appreciate that surface modification agent or agents may be delivered into contact with the film to be treated in either a liquid phase, with or without an optional co-solvent, or in the vapor phase, with or without an optional co-solvent, as described, e.g., in co-owned Ser. No. 09/111,084, filed Jul. 7, 1998, incorporated herein by reference in its entirety, provided that the reaction is conducted with an amount or concentration of surface modification agent(s) effective to provide a treated dielectric film having the desired range of dielectric constant and mechanical strength to produce a suitable integrated circuit on the substrate. [0051]
  • In one embodiment of the invention, the silica film is exposed to a vapor phase material that includes a monomer for forming a polymer/oligomer surface modification agent as described herein, and optionally in combination with a carrier gas, in an amount and under conditions effective to cap silanol moieties on the film surface. [0052]
  • It will be appreciated that a suitable vapor phase monomer for producing a polymer/oligomer surface modification agent will exhibit a satisfactory boiling point/vapor pressure, reactivity, purity, and will yield an effective and heat stable hydrophobic surface on the treated film without causing significant undesirable effects. Monomers for forming surface modification agents desirably employed in the vapor phase will have suitable vapor pressures in the temperature range for conducting the surface modification treatment. Simply by way of example, and without limitation, the vapor pressure of a suitable monomer will range from about 1 to about 500 torr. Preferably, the vapor pressure of a suitable surface modification agent will range from about 5 to about 100 torr. More preferably, the vapor pressure of a monomer will range from about 5-100 torr. Most preferably, the vapor pressure of a monomer for forming a surface modification agent will range from about 10 to about 50 torr. [0053]
  • As exemplified herein, the monomer was mixed with a suitable solvent/co-solvent in liquid phase. Suitable co-solvents are those solvents in which the surface modification agent and any other optional materials are soluble, but which will not dissolve the dielectric material to be treated or interfere with the capping of the silanols on the treated surface and which can be readily removed by evaporation and/or heating after the surface modification reaction is complete. Simply by way of example, and without limitation, such co-solvents include ethers, esters, ketones, glycol ethers, chlorinated solvents, low viscosity siloxanes and suitable combinations of the members of these solvent classes. The artisan will appreciate that the term, “low viscosity” as applied to siloxanes is that which is generally understood in the art, and will preferably range from about 1 to about 100 centistokes and preferably have a molecular weight ranging from about 160 to about 3800 Daltons. Exemplary low viscosity siloxanes useful in the inventive processes are commercially available, e.g., from Dow Corning. [0054]
  • Suitable solvents/co-solvents can be employed in concentrations ranging generally from about 0.5 to about 99 percent, or greater, by weight of the total solution. Exemplary ethers useful in the inventive processes include diethyl ether, diisopropyl ether, dibutyl ether and combinations thereof. Exemplary ethers useful in the inventive processes include: ethyl acetate, isopropyl acetate, n-butyl acetate, and combinations thereof. Exemplary hydrocarbons useful in the inventive processes include: n-hexane, n-heptane, cyclohexanes, toluene, and combinations thereof. Exemplary ketones useful in the inventive processes include: acetone, 3-pentanone, methyl isobutyl ketone, and combinations thereof. Exemplary glycol ethers useful in the inventive processes include: tri(ethylene glycol) dimethyl ether, tetra(ethylene glycol) dimethyl ether, tri(propylene glycol) dimethyl ether, and combinations thereof. Exemplary chlorinated solvents useful in the inventive processes include: 1,2-dichloroethane, carbon tetrachloro, chloroform, and combinations thereof. As exemplified in the examples below, 3-pentanone is a preferred co-solvent. 3-pentanone is useful in amounts ranging from about 0.5 to about 99 percent, or greater, or more preferably, in amounts ranging from about 50 to 80 percent, by weight of the total solution. [0055]
  • In the exemplified embodiments of the invention, the monomer was mixed with a solvent or co-solvent containing water, and the surface modification agent is a hydrolysis/condensation product formed in the presence of water. The water content of the co-solvent ranges from about 0.05 percent or greater. Preferably, the water content of the solvent or co-solvent ranges from about 0.05 percent to about 10 percent, or greater. More preferably, the water content of the solvent or co-solvent ranges from about 0.5 percent to about 4 percent. [0056]
  • The solution was then mixed with various defined proportions of the co-solvent solution, and applied by art-standard methods to the dielectric film on the substrate, e.g., the solution or suspension containing the hydrolysis/condensation product was spun onto various test films. The monomer is mixed with the water containing solvent/co-solvent in a concentration (monomer to co-solvent) ranging from about 5 to about 90 percent, or greater. Preferably, the concentration of the monomer in the co-solvent ranges from about 5 to about 50 percent. More preferably, the concentration of the monomer in the co-solvent ranges from about 10 to about 30 percent. The proportion of monomer to water ranges from about 0.50:1 to about 1:0.50, mole/mole. More preferably, the proportion of monomer to water ranges from about 0.75:1 to about 1:0.75. In the examples below, the monomer was exemplified by MTAS. [0057]
  • Thereafter, the substrate and the treated film was heated to a temperature and for a time period sufficient to drive off remaining surface modification agent and solvent. In one preferred embodiment the film is then cured. Optionally, the heating steps can be conducted in a plurality of stages, each stage utilizing similar or differing times and temperatures, or combined into a single process step. For example, the heat treatment was conducted under air at 175 and 320° C., respectively. The treated film was thereafter cured, e.g., at 400° C. [0058]
  • Combinations with Other Methods and Reagents—Monomer-Type Surface Modification Agents [0059]
  • As noted above in the Background of the Invention, one previously employed method of capping silanol groups on dielectric film pore surfaces employed an organic reagent monomer, such as hexamethyldisilazane (HMDZ), that is introduced into the pores of the film and allowed to react with the surface silanol groups. This reaction caps the silanols by forming hydrophobic trimethylsilyl groups. As noted above, one disadvantage in the use of trimethylsilyl groups is that they are not very thermally stable and may out-gas during further processing of the IC, and cause via poisoning. [0060]
  • However, an optional embodiment of the present invention provides for a combination of this other method, i.e., capping silanor groups with monomers to produce a hydrophobic surface, with the methods and compositions of the present invention. Advantageously, a combined treatment provides additional capping of internal silanols, e.g., on film surfaces located inside the pore structure of a nanoporous film, which is believed to further reduce the film dielectric constant. Further, the oligomer or polymer surface modification agent according to the invention seals the film surface, provides added mechanical strength, improved hydrophobicity and is believed to inhibit out-gassing during IC processing. [0061]
  • The combined process may be conducted sequentially, by first reacting the film with a monomer-type surface modification agent, and then reacting the film with the oligomer or polymer surface modification agent of the invention. Preferably, the reactions are conducted simultaneously by (1) forming a solution of the oligomer or polymer surface modification agent and then (2) adding an additional quantity of a selected monomer agent to that solution. The combined solution is then applied to the dielectric film to be treated by the methods previously described supra. [0062]
  • A number of monomer-type surface modification agents and methods for producing hydrophobic, low dielectric nanoporous silica films have been described, for example, in co-owned U.S. application Ser. Nos.: 60/098,068 and 09/140,855, both filed on Aug. 27, 1998, 09/234,609 and 09/235,186, both filed on Jan. 21, 1999, the disclosures of which are incorporated by reference herein in their entirety. [0063]
  • One preferred monomer-type surface modification agent is a compound having a formula selected from the group consisting of Formulas V (1)-(6): (1) R[0064] 3SiNHSiR3, (2) RxCly, (3) RxSi(OH)y, (4) R3SiOSiR3, (5) RxSi(OR)y, and/or (6) RxSi(OCOCH3)y and combinations thereof, wherein x is an integer ranging from 1 to 3, y is an integer ranging from 1 to 3 such that y=4−x, p is an integer ranging from 2 to 3; each R is an independently selected from hydrogen and a hydrophobic organic moiety. The R groups are preferably independently selected from the group of organic moieties consisting of alkyl, aryl and combinations thereof. The alkyl moiety is substituted or unsubstituted and is selected from the group consisting of straight alkyl, branched alkyl, cyclic alkyl and combinations thereof, and wherein said alkyl moiety ranges in size from C1 to about C18. The aryl moiety is substituted or unsubstituted and ranges in size from C5 to about C18. Preferably the monomer-type surface modification agent is an acetoxysilane such as, acetoxytrimethylsilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane, and/or an alkoxysilane such as, trimethylethoxysilane, trimethylmethoxysilane, 2-trimethylsiloxypent-2-ene-4-one, n-(trimethylsilyl)acetamide, and/or one or more of the following: 2-(trimethylsilyl) acetic acid, n-(trimethylsilyl)imidazole, trimethylsilylpropiolate, trimethylsilyl(trimethylsiloxy)-acetate, nonamethyltrisilazane, hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol, diphenylsilanediol and combinations thereof.
  • The monomer-type surface modification agent may be mixed with a suitable solvent such as acetone, applied to the nanoporous silica surface in the form of a vapor or liquid, and then dried. [0065]
  • Additional monomer-type surface modification agents include multifunctional surface modification agents as described in detail in co-owned U.S. Ser. No. 09/235,186, incorporated by reference herein in its entirety, as described above. Such multifunctional surface modification agents can be applied in either vapor or liquid form, optionally with or without co-solvents. Suitable co-solvents include, e.g., ketones, such as acetone, 3-pentanone, diisolpropylketon, and others, as described in detail in co-owned U.S. application Ser. No. 09/111,084, filed on Jul. 7, 1998, the disclosure of which in incorporated by reference herein in its entirety. For example, as described in detail in U.S. Ser. No. 09/235,186, as incorporated by reference above, certain preferred surface modification agents will have two or more functional groups and react with surface silanol functional groups while minimizing mass present outside the structural framework of the film, and include, e.g., suitable silanols such as [0066]
  • R1Si(OR2)3   Formula VI
  • wherein R[0067] 1 and R2 are independently selected moieties, such as H and/or an organic moiety such as an alkyl, aryl or derivatives of these. When R1 or R2 is an alkyl, the alkyl moiety is optionally substituted or unsubstituted, and may be straight, branched or cyclic, and preferably ranges in size from C1 to about C18, or greater, and more preferably from C1 to about C8. When R1 or R2 is aryl, the aryl moiety preferably consists of a single aromatic ring that is optionally substituted or unsubstituted, and ranges in size from C5 to about C18, or greater, and more preferably from C5 to about C8. In a further option, the aryl moiety is not a heteroaryl.
  • Thus, R[0068] 1 or R2 are independently selected from H, methyl, ethyl, propyl, phenyl, and/or derivatives thereof, provided that at least one of R1 or R2 is organic. In one embodiment, both R1 and R2 are methyl, and a trifunctional surface modification agent according to Formula VI is methyltrimethoxysilane.
  • In another embodiment, a suitable silane according to the invention has the general formula of [0069]
  • R1Si(NR2R3)3   Formula VII
  • Wherein R[0070] 1, R2, R3 are independently H, alkyl and/or aryl. When any of R1, R2, R3 are alkyl and/or aryl, they are defined as for R1 and R2 of Formula VI, above. In preferred embodiments according to Formula VII, R1 is selected from H, CH3, C6H5, and R2 and R3 are both CH3. Thus trifunctional monomer-type surface modification agents according to Formula VI include, e.g., tris(dimethylamino)methylsilane, tris(dimethylamino)phenylsilane, and/or tris(dimethylamino)silane.
  • In yet another embodiment, a suitable silane according to the invention has the general formula of [0071]
  • R1Si(ON═CR2R3)3   Formula VIII
  • wherein R[0072] 1, R2, R3 are independently H, alkyl and/or aryl. When any of R1, R2, R3 are alkyl and/or aryl, they are defined as for R1 and R2 of Formula VI, above. In one preferred embodiment, R1 and R2 are both CH3, and R3 is CH2CH3. Thus trifunctional monomer-type surface modification agents according to Formula VII include, e.g., methyltris(methylethylkeoxime)silane.
  • In yet a further embodiment, a suitable silane according to the invention has the general formula of [0073]
  • R1SiCl3   Formula IX
  • wherein R[0074] 1 is H, alkyl or aryl. When R1 is alkyl and/or aryl, they are defined as for Formula IV, above. In one preferred embodiment, R1 is CH3. Thus trifunctional monomer-type surface modification agents according to Formula VIII include, e.g., methyltrichlorosilane.
  • In a more preferred embodiment, the capping reagent includes one or more organoacetoxysilanes which have the following general formula, [0075]
  • (R1)xSi(OCOR2)y   Formula X
  • Preferably, x is an integer ranging in value from 1 to 2, and x and y can be the same or different and y is an integer ranging from about 2 to about 3, or greater. [0076]
  • Useful organoacetoxysilanes, including multifunctional alkylacetoxysilane and/or arylacetoxysilane compounds, include, simply by way of example and without limitation, methyltriacetoxysilane (“MTAS”), dimethyldiacetoxysilane (DMDAS), phenyltriacetoxysilane and diphenyldiacetoxysilane and combinations thereof. [0077]
  • Properties of Produced Nanoporous Dielectric Films [0078]
  • Nanoporous silica films formed on a substrate for use according to the invention are generally formed with a porosity of about 20% or greater and with pore sizes that range from about 1 nm to about 100 nm, more preferably from about 2 nm to about 30 nm, and most preferably from about 3 nm to about 20 nm. The density of the silicon containing composition, including the pores, ranges from about 0.1 to about 1.9 g/cm[0079] 3, more preferably from about 0.25 to about 1.6 g/cm3, and most preferably from about 0.4 to about 1.2 g/cm2.
  • Thus, the nanoporous silica films produced by the processes of the invention preferably have a moisture stable dielectric constant that is less than about 3. More preferably, the nanoporous silica films of the invention have a dielectric constant ranging from about 1.1 to about 3.0, even more preferably from about 1.3 to about 2.5, and most preferably from about 1.7 to about 2. [0080]
  • Non-Porous Silica Dielectric Films [0081]
  • In a further beneficial result of the present invention, it will be appreciated that the above-described methods and compositions can be optionally applied to non-porous silica dielectric materials, in order to, e.g., stabilize such materials against the effects of environmental moisture and the like, for use as insulators and dielectrics in microelectronic and/or integrated circuit products, as may be desired, for utilities where a very low dielectric constant and/or porosity is not required. Such non-porous silica-based dielectric materials include, for example, films deposited by art-standard methods, e.g., chemical vapor deposition (“CVD”), dip coating, spray coating, or any other similar materials that have surface silanols which it is desirable to cap. [0082]
  • Preferably, such silica dielectric materials are formed by CVD. However, the produced film tends to have free silanols on the surface that will adsorb environmental moisture. Thus, application of the methods of the present invention will usefully cap these free silanols, even on non-porous dielectric silica materials. [0083]
  • The following non-limiting examples serve to further explain and illustrate the invention.[0084]
  • EXAMPLE 1
  • This example illustrates the preparation of dielectric films treated with a 25% solution of MTAS-derived siloxane polymer, that contained an average of 1.5 reactive functional group per repeating unit. [0085]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0086]
  • Methyltriacetoxysilane (“MTAS”; purchased from United Chemical Technologies, Bristol, Pa.) was purified by vacuum distillation prior to use. 3-pentanone(Pacific Pac) with a low water content (<250 PPM) was employed. 116 g of 3-pentanone was added to 1.78 g of water in a 500 mL flask with a magnetic stir bar. Then 29 g of MTAS was added to the above 3-pentanone/water mixture with proper stirring, which was continued overnight at room temperature to produce a clear, colorless solution. Gas chromatography-mass spectroscopy was used to analyze this product and found no sign of MTAS presence in the product, suggesting that all of the MTAS has reacted. This solution was then filtered through 0.2 micron Teflon® filter and used for the surface treatment described below. [0087]
  • Preparation of Nanoporous Film [0088]
  • A nanoporous silica precursor was synthesized by adding 208 mL of tetraethoxysilane, 94 mL of triethyleneglycol monomethyl ether(TIEGMME), 16.8 mL deionized water, and 0.68 mL of 1N nitric acid together in a round bottom flask. The solution was heated to about 80° C. with vigorous stirring (heating and stirring were begun at the same time) and refluxed for 1.5 hours, to form a clear solution. The resulting solution was allowed to cool down to room temperature and then it was diluted 25% by weight with ethanol, and filtered through a 0.1 micron Teflon® filter. [0089]
  • About 2 mL of the nanoporous silica precursor, was deposited onto a 4″ silicon wafer and then spun at 2500 rpm for 30 seconds. Then the resulting film was gelled/aged in a vacuum chamber as follows. [0090]
  • 1. The chamber was evacuated to 250 torr. [0091]
  • 2. 15M ammonium hydroxide was heated and equilibrated at 45° C. and introduced into the chamber to increase the pressure to 660 torr for 10 minutes [0092]
  • 3. The chamber was refilled with air and the film was removed from the chamber for next step surface treatment/solvent exchange. [0093]
  • Oligomer/Polymer Treatment of Film Surface [0094]
  • The surface treatment/solvent exchange of the film was carried out using the following conditions: [0095]
  • 1. The reagent used for the surface treatment was prepared as described above. [0096]
  • 2. The aged film was put on the spinning chuck and spun at 250 rpm. [0097]
  • 3. About 30 mL of the above MTAS solution was spun on the film without allowing the film to dry for 20 seconds. [0098]
  • 4. Then the film was spun dry at 2500 rpm for 10 seconds, and then the film was removed from the chuck and subjected to heat treatment. [0099]
  • Heat Treatment [0100]
  • The film obtained from the above process was then heated at 175 and 320° C., under air, for two 60 second steps, respectively. Then the film was cured in a furnace at 400° C. for 30 minutes under nitrogen. [0101]
  • The refractive index and thickness of the obtained films were measured by Woollam ellipsometer by standard methods. [0102]
  • Determination of Dielectric Constant [0103]
  • The dielectric constant was measured by the standard CV curve technique, using MOS capacitor (“MOSCAP”) structure as follows. The MOSCAP structure is formed by sputtering aluminum onto the film through a circular dot mask and an aluminum blanket film is also sputtered onto the back side of the wafer. An appropriately biased voltage was applied to the MOSCAP and the capacitance was then measured at 1 MHz. This method was employed for dielectric constant determinations in all subsequent examples. [0104]
  • Determination of Film Mechanical Strength [0105]
  • The force required to break the film was determined by an art-standard stud-pull test. The film to be tested was placed on substrate wafer, and an aluminum layer was placed on top of the film to prevent penetration of the pore structure by the subsequently applied epoxy. An epoxy test stud was then epoxied to the top of the aluminized film. Once the epoxy was cured, the stud was pulled away from the film, with a measured force, until some component broke. The measured pull force at the moment just prior to breakage was reported as the stud pull strength. As described below and in the following examples, the stud-pull is defined as the force exerted on the workpiece, at the moment of mechanical failure, measured in kilopounds per square inch (“KPSI”). [0106]
  • The measured film properties are summarized in the following table. [0107]
    TABLE 1
    Refractive
    Index Film Thickness (Å) Dielectric constant Stud pull (KPSI)
    1.221 7206 2.23 2.54
  • EXAMPLE 2
  • This example illustrates preparation of dielectric films treated with a 30% solution of MTAS-derived siloxane polymer that contained 1 reactive functional group per repeating unit. [0108]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0109]
  • MTAS and 3-pentanone were obtained and prepared as for Example 1, above. 76.3 g of 3-pentanone was added to 2.67 g of water in a 250 mL flask with magnetic stir bar. Then 32.7 g of MTAS was added to the above 3-pentanone/water mixture with proper stirring, which was continued overnight at room temperature to produce a clear, colorless solution. Gas chromatography-mass spectroscopy was used to analyze this product and found no sign of MTAS presence in the product. suggesting all of the MTAS has reacted. This solution was then filtered through a 0.2 micron Teflon® filter and used for surface treatment described below. [0110]
  • Preparation of Nanoporous Film [0111]
  • About 2 mL of a nanoporous silica precursor prepared as described in Example 1, above, was deposited onto a 4″ silicon wafer and then spun at 2500 rpm for 30 seconds. Then the film was gelled/aged in a vacuum chamber using the three-step method described above for Example 1. [0112]
  • The surface treatment/solvent exchange of the film was carried with the above-described surface modification reagent using the four-step process described by Example 1. [0113]
  • The film obtained from the above process was then heated in the two-step process, and cured under nitrogen gas, as described above for Example 1. The refractive index, dielectric constant and stud pull test were all conducted as for Example 1. The measured film properties are shown in the following table. [0114]
    TABLE 2
    Refractive
    Index Film Thickness (Å) Dielectric constant Stud pull (KPSI)
    1.3144 6115 3.13 3.96
  • EXAMPLE 3
  • This example illustrates preparation of dielectric films treated with a 20% solution of MTAS-derived siloxane polymer that contained 1 reactive functional group per repeating unit. [0115]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0116]
  • MTAS and 3-pentanone were obtained and prepared as for Example 1, above. 122 g of 3-pentanone was added to 2.5 g of water in a 500 mL flask with magnetic stir bar. Then 30.5 g of MTAS was added to the above 3-pentanone/water mixture with proper stirring, which was continued overnight at room temperature to produce a clear, colorless solution. Gas chromatography-mass spectroscopy was used to analyze this product and found no sign of MTAS presence in the product. suggesting all of the MTAS has reacted. This solution was then filtered through a 0.2 micron Teflon® filter and used for surface treatment described below. [0117]
  • Preparation of Nanoporous Film [0118]
  • About 2 mL of a nanoporous silica precursor prepared as described in Example 1, above, was deposited onto a 4″ silicon wafer and then spun at 2500 rpm for 30 seconds. Then the film was gelled/aged in a vacuum chamber using the three-step method described above for Example 1. [0119]
  • The surface treatment/solvent exchange of the film was carried with the above-described surface modification reagent using the four-step process described by Example 1. [0120]
  • The film obtained from the above process was then heated in the two-step process, and cured under nitrogen gas, as described above for Example 1. The refractive index, dielectric constant and stud pull test were all conducted as described for Example 1. The measured film properties are shown in the following table. [0121]
    TABLE 3
    Refractive
    Index Film Thickness (Å) Dielectric constant Stud pull (KPSI)
    1.2329 6390 2.18 2.21
  • EXAMPLE 4
  • This example illustrates preparation of dielectric films treated with a 10% solution of MTAS-derived siloxane polymer that contained 1 reactive functional group per repeating unit. [0122]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0123]
  • MTAS and 3-pentanone were obtained and prepared as for Example 1, above. 185.4 g of 3-pentanone was added to 1.68 g of water in a 500 mL flask with magnetic stir bar: Then 20:6 g of MTAS was added to the above 3-pentanone/water mixture with proper stirring, which was continued overnight at room temperature to produce a clear, colorless solution. Gas chromatography-mass spectroscopy was used to analyze this product and found no sign of MTAS presence in the product, suggesting all of the MTAS has reacted. This solution was then filtered through a 0.2 micron Teflon® filter and used for surface treatment described below. [0124]
  • Preparation of Nanoporous Film [0125]
  • About 2 mL of a nanoporous silica precursor prepared as described in Example 1, above, was deposited onto a 4″ silicon wafer and then spun at 2500 rpm for 30 seconds. Then the film was gelled/aged in a vacuum chamber using the three-step method described above for Example 1. [0126]
  • The surface treatment/solvent exchange of the film was carried with the above-described surface modification reagent using the four-step process described by Example 1. [0127]
  • The film obtained from the above process was then heated in the two-step process, and cured under nitrogen gas, as described above for Example 1. The refractive index, dielectric constant and stud pull test were all conducted as described for Example 1. The measured film properties are shown in the following table. [0128]
    TABLE 4
    Refractive
    Index Film Thickness (Å) Dielectric constant Stud pull (KPSI)
    1.1933 5871 2.49 1.70
  • EXAMPLE 5
  • This example illustrates preparation of dielectric films treated with a 10% solution of MTAS-derived siloxane polymer that contained 1.5 reactive functional group per repeating unit. [0129]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0130]
  • MTAS and 3-pentanone were obtained and prepared as for Example 1, above. 223.2 g of 3-pentanone was added to 1.52 g of water in a 500 mL flask with a magnetic stir bar. Then 24.8 g of MTAS was added to the above 3-pentanone/water mixture with proper stirring, which was continued overnight at room temperature to produce a clear, colorless solution. Gas chromatography-mass spectroscopy was used to analyze this product and found no sign of MTAS presence in the product, suggesting all of the MTAS has reacted. This solution was then filtered through a 0.2 micron Teflon® filter and used for surface treatment described below. [0131]
  • Preparation of Nanoporous Film [0132]
  • About 2 mL of a nanoporous silica precursor prepared as described in Example 1, above, was deposited onto a 4″ silicon wafer and then spun at 2500 rpm for 30 seconds. Then the film was gelled/aged in a vacuum chamber using the three-step method described above for Example 1. [0133]
  • The surface treatment/solvent exchange of the film was carried with the above-described surface modification reagent using the four-step process described by Example 1. [0134]
  • The film obtained from the above process was then heated in the two-step process, and cured under nitrogen gas, as described above for Example 1. The refractive index, dielectric constant and stud pull test were all conducted as described for Example 1. The measured film properties are shown in the following table. [0135]
    TABLE 5
    Refractive
    Index Film Thickness (Å) Dielectric constant Stud pull (KPSI)
    1.1766 6694 2.25 1.54
  • EXAMPLE 6
  • This example is provided for comparison purposes and illustrates preparation of dielectric films treated only with MTAS monomer. No polymer/oligomer was applied to these films. [0136]
  • Preparation of Nanoporous Film [0137]
  • About 2 mL of a nanoporous silica precursor prepared as described in Example 1, above, was deposited onto a 4″ silicon wafer and then spun at 2500 rpm for 30 seconds. Then the film was gelled/aged in a vacuum chamber using the three-step method described above for Example 1. [0138]
  • The surface treatment/solvent exchange of the film was conducted according to the method of Example 1, but the reagent used for the surface modification was prepared by mixing 5 grams of MTAS with 95 grams of 3-pentanone (each obtained as described by Example 1) to form a clear colorless solution. [0139]
  • The film obtained from the above process was then heated in the two-step process, and cured under nitrogen gas, as described above for Example 1. The refractive index, dielectric constant and stud pull test were all conducted as described for Example 1. The measured film properties are shown in the following table. [0140]
    TABLE 6
    Refractive
    Index Film Thickness (Å) Dielectric constant Stud pull (KPSI)
    1.1665 7518 1.98 1.5
  • EXAMPLE 7
  • This example illustrates preparation of dielectric films treated with a (monomer) silylation surface reagent followed by treatment with a 25% solution of MTAS-derived siloxane polymer that contained an average of 1.5 reactive functional group per repeating unit. [0141]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0142]
  • MTAS and 3-pentanone were obtained and prepared as for Example 1, above. 50 g of MTAS was dissolved in 150 g of 3-pentanone. 3.05 gram of water was then added to the above solution with proper stirring. The resulted clear colorless solution that included hydrolyzed MTAS was filtered through 0.2 micron filter prior to use for surface treatment. [0143]
  • Preparation of Nanoporous Film [0144]
  • About 4 mL of a nanoporous silica precursor prepared as described in Example 1, above, was deposited onto a 8″ silicon wafer and then spun at 2500 rpm for 30 seconds. The spun film was gelled/aged in a vacuum chamber using the following conditions: [0145]
  • 1. The chamber was evacuated to 250 torr. [0146]
  • 2. 15M ammonium hydroxide was heated and equilibrated at 45° C. and introduced into the chamber to increase the pressure to 660 torr for 5 minutes. [0147]
  • 3. The chamber was evacuated to 250 torr. [0148]
  • 4. 15M ammonium hydroxide was heated and equilibrated at 45° C. and introduced into the chamber to increase the pressure to 660 torr for 5 minutes. [0149]
  • 5. The chamber was refilled with air and the aged film was removed from the chamber. [0150]
  • Conventional Surface Modification for Silylating Pore Surfaces [0151]
  • The aged film was then subjected to surface treatment/solvent exchange. The solution used for surface treatment/solvent exchange was prepared by dissolving MTAS, prepared and distilled as described by Example 1, in 3-pentanone to make a 5 wt. % MTAS concentration in 3-pentanone. The surface treatment/solvent exchange of the film was carried out using the following conditions: [0152]
  • 1. The aged film was put on the spinning chuck and spun at 250 rpm. [0153]
  • 2. About 30 mL of the above MTAS solution was spun onto the film, without allowing the film to dry, for 20 seconds. [0154]
  • 3. Then the film was spun dry at 2500 rpm for 10 second, removed from the chuck, and subjected to heat treatment at 175 and 320° C., under air, for 60 seconds respectively, to produce a baked film. [0155]
  • Polymer/oligomer Surface Treatment [0156]
  • The baked film resulting from step 3 of the above procedure was then treated with the hydrolyzed MTAS solution described [0157]
  • The surface treatment/solvent exchange of the film was carried out using the following conditions: [0158]
  • 1. The baked film obtained from the above process was put on the spinning chuck and spun at 250 rpm. [0159]
  • 2. About 30 mL of the above described hydrolyzed MTAS solution was spun on the film without allowing the film to dry for 20 seconds. [0160]
  • 3. Then the film was spun dry at 2500 rpm for 10 second and then the film was removed from the chuck and subjected to heat treatment. [0161]
  • The film obtained from the above process was then heated at 175 and 320° C. under air for 60 seconds, respectively. Then it was cured in a furnace at 400° C. for 30 minute under nitrogen. Refractive index and thickness of the obtained film was measured by a Woollam ellipsometer. [0162]
  • Dielectric Constant Measurement [0163]
  • Dielectric constant was measured by the standard CV curve technique, as described by Example 1, supra. [0164]
  • Film Mechanical Strength Measurement [0165]
  • The cohesive strength of the film was measured by a stud pull test, as described by Example 1, supra. [0166]
  • The modulus of the prepared films was measured with Nano Indenter XP (MTS Systems Corp., Oak Ridge, Tenn. 37830). This measurement provides the modulus of the films in GPa (10[0167] 6 N/m2).
    TABLE 7
    Film Cohesive
    Refractive Thickness Dielectric Strength Modulus
    Index (Å) Constant (KPSI) (GPa)
    Ex. 7 Data
    Multi- 1.2565 7823 2.4 8.3 6.3
    function-
    Polymer
    Ex. 6 Data
    Treated by 1.1665 7518 1.98 1.5 N/A
    MTAS
    without
    H2O
    (mon-
    omer)
  • As can be appreciated from Table 7, above, the properties of the film treated by the exemplified multifunctional polymer/oligomer compares are improved relative to the properties of the film treated with just MTAS monomer. In particular, there is a greater than 5-fold increase in the cohesive strength, combined with a relatively modest increase in the dielectric constant. [0168]
  • EXAMPLE 8
  • This example illustrates preparation of dielectric films treated with a solution that contained both a 5% monomeric silylation reagent (MTAS monomer) and a 25% MTAS-derived siloxane polymer that contained an average of 1.5 reactive functional groups per repeating unit. [0169]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0170]
  • MTAS and 3-pentanone were obtained and prepared as for Example 1, above. 250 g MTAS was mixed with 750 g 3-pentanone and then 15.3 g water was added while the solution was properly stirred. The solution was then stirred overnight. 15.4 g of MTAS was added to 185 g of clear solution obtained from previous step. The resulting clear colorless solution was filtered through a 0.2 micron filter prior to use for surface treatment. [0171]
  • Preparation of Nanoporous Film [0172]
  • A nanoporous silica precursor was synthesized, spin-deposited onto a 8″ silicon wafer and then gelled/aged in a vacuum chamber as described by Example 7, supra. [0173]
  • Polymer/oligomer Surface Treatment [0174]
  • The resulting aged film was then treated with the hydrolyzed MTAS polymer solution, which also included monomer MTAS, as described above. [0175]
  • The surface treatment/solvent exchange of the film was carried out using the following conditions: [0176]
  • 1. The aged film obtained from the above process was put on the spinning chuck and spun at 250 rpm. [0177]
  • 2. About 30 mL of the above hydrolyzed MTAS solution was spun on the film without allowing the film to dry for 20 seconds. [0178]
  • 3. Then the film was spun dry at 2500 rpm for 10 second and then the film was removed from the chuck and subjected to heat treatment. [0179]
  • The film obtained from the above process was then heated at 175 and 320° C. under air for 60 seconds respectively. Then it was cured in a furnace at 400° C. for 30 minute under nitrogen. Refractive index and thickness of the obtained film was measured by Woollam ellipsometer. [0180]
    TABLE 8
    Refractive Film Thickness Dielectric Cohesive
    Index (Angstrom) Constant Strength (KPSI)
    1.3054 6898 2.38 8.27
  • This process demonstrated a simplified co-treatment process (compared to Example 7) with both silylation of surface silanols by MTAS monomer and by the hydrolyzed MTAS polymer composition. The result is a film with physical properties (dielectric constant, cohesive strength) similar to those obtained by the process of Example 8. [0181]
  • EXAMPLE 9
  • This example illustrates preparation of dielectric films treated with a silylation reagent (MTAS monomer) followed by treatment with a 25% solution of MTAS-derived siloxane polymer that contained an average of 1.5 reactive functional group per repeating unit. [0182]
  • Preparation of Hydrolyzed MTAS for Surface Modification [0183]
  • 250 g MTAS was mixed with 750 g 3-pentanone and then 15.3 g water was added while the solution was properly stirred. The solution was then stirred overnight. The resulting clear colorless solution was filtered through 0.2 micron filter prior to use for surface treatment. [0184]
  • Preparation of Nanoporous Film [0185]
  • A nanoporous silica precursor was synthesized, spin-deposited onto a 8″ silicon wafer and then gelled/aged in a vacuum chamber as described by Example 7, supra. [0186]
  • Polymer/oligomer Surface Treatment [0187]
  • The surface treatment/solvent exchange of the film was carried out using the hydrolyzed MTAS polymer composition of this example applied using the process as described above for Example 8. [0188]
  • The film obtained from the above process was then heated at 175 and 320 C. under air for 60 seconds respectively. Then it was cured in a furnace at 400 C. for 30 minute under nitrogen. Refractive index and thickness of the obtained film was measured by Woollam ellipsometer, as described above in Example 1. [0189]
    TABLE 9
    Refractive Film Thickness Dielectric Cohesive
    Index (Angstrom) Constant Strength (KPSI)
    1.2826 6439 2.15 8.29
  • This process demonstrated a simplified process (compared to example 8) and provide films with similar physical properties (dielectric constant, cohesive strength). [0190]
  • While there have been described what are presently believed to be the preferred embodiments of the invention, those skilled in the art will realize that changes and modifications may be made thereto without departing from the spirit of the invention. It is intended to claim all such changes and modifications that fall within the true scope of the invention. Numerous references are cited in the specification, the disclosures of which are incorporated by reference in their entireties. [0191]

Claims (30)

    What is claimed is:
  1. 1. A process for treating a silica film on a substrate, which comprises reacting a suitable silica film with a composition comprising a surface modification agent, wherein said silica film is present on a substrate and wherein said reaction is conducted under conditions and for a period of time sufficient for said surface modification agent to form a hydrophobic coating on said film and said surface modification agent comprises at least one type of oligomer or polymer reactive with silanols on said silica film.
  2. 2. The process of claim 1 wherein said reaction is conducted in the presence of at least one solvent or co-solvent.
  3. 3. The process of claim 1 wherein said silica film is a nanoporous dielectric film having a pore structure that comprises silanols, and wherein said reaction is conducted for a period of time sufficient for said surface modification agent to produce a treated nanoporous silica film having a dielectric constant of about 3 or less.
  4. 4. The process of claim 3 that produces a nanoporous silica film having a dielectric constant ranging from about 1.1 to about 3.0.
  5. 5. The process of claim 1 wherein said reaction is conducted at a temperature ranging from about 10° C. to about 300° C.
  6. 6. The process of claim 1 wherein said reaction is conducted for a time period ranging from about 10 seconds to about 1 hour.
  7. 7. The process of claim 1 wherein said surface modification agent is a polymer or oligomer that comprises functional groups that will react with silanols.
  8. 8. The process of claim 7 wherein said surface modification agent is prepared by reacting a suitable monomer with water in a solvent to form said surface modification agent.
  9. 9. The process of claim 2 wherein said solvent or co-solvent is selected from the group consisting of ethers, esters, ketones, glycol ethers, hydrocarbons, chlorinated solvents, low viscosity siloxanes and combinations thereof.
  10. 10. The process of claim 2 wherein said co-solvent is selected from the group consisting of ethers, esters, ketones, glycol ethers, hydrocarbons, chlorinated solvents, low viscosity siloxanes and combinations thereof.
  11. 11. The process of claim 8 wherein said monomer is selected from the group consisting of a siloxane, a silazane, a silane, a carbosilane, and combinations thereof.
  12. 12. The process of claim 8 wherein said water is present in said co-solvent in a concentration ranging from about 0.05 to about 10 percent, by weight, relative to the co-solvent.
  13. 13. The process of claim 8 wherein said water is present during said reaction in proportion to said monomer in a ratio ranging from about 0.50:1.5 to about 1.5:0.5, mole/mole.
  14. 14. The process of claim 8 wherein said monomer compound is selected from the group consisting of said monomer compound is selected from the group consisting of methyltriacetoxysilane, phenyltriacetoxysilane, tris(dimethlyaimino)methylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)methylsilane and combinations thereof.
  15. 15. The process of claim 1 wherein the composition comprises an oligomer or polymer surface modification agent and a monomer surface modification agent, wherein said monomer is reactive with silanol groups on said silica film.
  16. 16. The process of claim 1 wherein said silica film is pre-treated with a monomer surface modification agent, wherein said monomer is reactive with silanol groups on said silica film.
  17. 17. The process of claim 8 further comprising adding at least one additional monomer to said solution after the water is fully reacted, wherein said monomer is reactive with silanol groups on said silica film.
  18. 18. The process of claim 15 wherein the monomer surface modification agent is an selected from the group consisting of siloxanes, silazanes, silanes, carbosilanes and combinations thereof.
  19. 19. The process of claim 15 wherein the monomer surface modification agent is selected from the group consisting of acetoxytrimethylsilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane, trimethylethoxysilane, trimethylmethoxysilane, 2-trimethylsiloxypent-2-ene-4-one, n-(trimethylsilyl)acetamide, 2-(trimethylsilyl) acetic acid, n-(trimethylsilyl)imidazole, trimethylsilylpropiolate, trimethylsilyl(trimethylsiloxy)-acetate, nonamethyltrisilazane, hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol, diphenylsilanediol, tris(dimethylamino)methylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)silanemethyltrimethoxysilane, methyltris(methylethylkeoxime)silane. methyltrichlorosilane, and combinations thereof.
  20. 20. A dielectric film produced by a process comprising the steps of reacting a suitable silica film with a composition comprising a surface modification agent, wherein said silica film is present on a substrate and wherein said reaction is conducted under conditions and for a period of time sufficient for said surface modification agent to form a hydrophobic coating on said film and said surface modification agent comprises at least one type of oligomer or polymer reactive with silanol groups on said silica film.
  21. 21. The dielectric film of claim 20 wherein a stud-test conducted on said film exhibits a film break strength of greater than 2 KPSI and a dielectric constant ranging from about 1.1 to about 3.0.
  22. 22. An integrated circuit comprising at least one dielectric silica film treated by reacting said silica film with a surface modification agent, wherein said reaction is conducted under conditions and for a period of time sufficient for said surface modification agent to form a hydrophobic coating on said film, and said surface modification agent comprises at least one type of oligomer or polymer reactive with silanol groups on said silica film.
  23. 23. The integrated circuit of claim 22 wherein said surface modification agent is prepared by reacting a suitable monomer with water in a solvent to form said surface modification agent.
  24. 24. The integrated circuit of claim 22 wherein said solvent or co-solvent is selected from the group consisting of ethers, esters, ketones, glycol ethers, chlorinated solvents, low viscosity siloxanes and combinations thereof.
  25. 25. The integrated circuit of claim 24 wherein said co-solvent is selected from the group consisting of ethers, esters, ketones, glycol ethers, chlorinated solvents, low viscosity siloxanes and combinations thereof.
  26. 25. The integrated circuit of claim 23 wherein said monomer is selected from the group consisting of a siloxane, a silazane, a silane, a carbosilane, and combinations thereof.
  27. 26. The integrated circuit of claim 23 wherein said water is present in said co-solvent in a concentration ranging from about 0.05 to about 10 percent, by weight, relative to the co-solvent.
  28. 27. The integrated circuit of claim 26 wherein said water is present during said reaction in proportion to said monomer in a ratio ranging from about 0.50:1.5 to about 1.5:0.5, mole/mole.
  29. 28. The integrated circuit of claim 24 wherein said monomer compound is selected from the group consisting of methyltriacetoxysilane, phenyltriacetoxysilane, tris(dimethlyaimino)methylsilane, tris(dimethylamino)phenylsilane, tris(diethylamino)methylsilane and combinations thereof.
  30. 29. A polymer or oligomer surface modification reagent prepared by reacting a suitable monomer with water in a solvent to form said surface modification agent.
US09841453 1999-01-26 2001-04-24 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films Abandoned US20020001973A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US11724899 true 1999-01-26 1999-01-26
US09488075 US6770572B1 (en) 1999-01-26 2000-01-19 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films
US09841453 US20020001973A1 (en) 1999-01-26 2001-04-24 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US09841453 US20020001973A1 (en) 1999-01-26 2001-04-24 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09488075 Division US6770572B1 (en) 1999-01-26 2000-01-19 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films

Publications (1)

Publication Number Publication Date
US20020001973A1 true true US20020001973A1 (en) 2002-01-03

Family

ID=22371772

Family Applications (3)

Application Number Title Priority Date Filing Date
US09488075 Expired - Fee Related US6770572B1 (en) 1999-01-26 2000-01-19 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films
US09841453 Abandoned US20020001973A1 (en) 1999-01-26 2001-04-24 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films
US09912509 Active 2020-06-08 US6799303B2 (en) 1999-01-26 2001-07-26 Speed typing apparatus and method

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09488075 Expired - Fee Related US6770572B1 (en) 1999-01-26 2000-01-19 Use of multifunctional si-based oligomer/polymer for the surface modification of nanoporous silica films

Family Applications After (1)

Application Number Title Priority Date Filing Date
US09912509 Active 2020-06-08 US6799303B2 (en) 1999-01-26 2001-07-26 Speed typing apparatus and method

Country Status (6)

Country Link
US (3) US6770572B1 (en)
EP (1) EP1153426A1 (en)
JP (1) JP4947836B2 (en)
KR (1) KR100716022B1 (en)
CN (1) CN1236480C (en)
WO (1) WO2000044036A1 (en)

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6531344B1 (en) * 2000-07-06 2003-03-11 Motorola, Inc. High frequency gallium arsenide MMIC die coating method
US20040013858A1 (en) * 2000-06-23 2004-01-22 Hacker Nigel P. Method to restore hydrophobicity in dielectric films and materials
US20040021224A1 (en) * 2002-08-02 2004-02-05 Fujitsu Limited Semiconductor device using low-k material as interlayer insulating film and its manufacture method
WO2004068555A3 (en) * 2003-01-25 2005-02-03 Honeywell Int Inc Repair and restoration of damaged dielectric materials and films
US20050095840A1 (en) * 2003-01-25 2005-05-05 Bhanap Anil S. Repairing damage to low-k dielectric materials using silylating agents
US20060057855A1 (en) * 2004-09-15 2006-03-16 Ramos Teresa A Method for making toughening agent materials
US20060156934A1 (en) * 2003-09-19 2006-07-20 Gallus Druckmaschinen Ag Rotary printing press
US7094713B1 (en) 2004-03-11 2006-08-22 Novellus Systems, Inc. Methods for improving the cracking resistance of low-k dielectric materials
US20060216952A1 (en) * 2005-03-22 2006-09-28 Bhanap Anil S Vapor phase treatment of dielectric materials
US20060281010A1 (en) * 2005-06-14 2006-12-14 Seok-Soo Lee Organic electrolytic solution and lithium battery employing the same
US7166531B1 (en) 2005-01-31 2007-01-23 Novellus Systems, Inc. VLSI fabrication processes for introducing pores into dielectric materials
US7176144B1 (en) 2003-03-31 2007-02-13 Novellus Systems, Inc. Plasma detemplating and silanol capping of porous dielectric films
WO2007025114A2 (en) * 2005-08-26 2007-03-01 The Regents Of The University Of California Stepwise growth of oligomeric redox-active molecules on a surface without the use of protecting groups
US7208389B1 (en) 2003-03-31 2007-04-24 Novellus Systems, Inc. Method of porogen removal from porous low-k films using UV radiation
US7241704B1 (en) 2003-03-31 2007-07-10 Novellus Systems, Inc. Methods for producing low stress porous low-k dielectric materials using precursors with organic functional groups
US7253125B1 (en) 2004-04-16 2007-08-07 Novellus Systems, Inc. Method to improve mechanical strength of low-k dielectric film using modulated UV exposure
US7265061B1 (en) 2003-05-09 2007-09-04 Novellus Systems, Inc. Method and apparatus for UV exposure of low dielectric constant materials for porogen removal and improved mechanical properties
US7326444B1 (en) 2004-09-14 2008-02-05 Novellus Systems, Inc. Methods for improving integration performance of low stress CDO films
US7341761B1 (en) 2004-03-11 2008-03-11 Novellus Systems, Inc. Methods for producing low-k CDO films
US7381644B1 (en) 2005-12-23 2008-06-03 Novellus Systems, Inc. Pulsed PECVD method for modulating hydrogen content in hard mask
US7381662B1 (en) 2004-03-11 2008-06-03 Novellus Systems, Inc. Methods for improving the cracking resistance of low-k dielectric materials
US7390537B1 (en) 2003-11-20 2008-06-24 Novellus Systems, Inc. Methods for producing low-k CDO films with low residual stress
US20080199977A1 (en) * 2007-02-15 2008-08-21 Air Products And Chemicals, Inc. Activated Chemical Process for Enhancing Material Properties of Dielectric Films
US20080280047A1 (en) * 2004-03-11 2008-11-13 The Regents Of The University Of California Procedure for preparing redox-active polymers on surfaces
US20090026924A1 (en) * 2007-07-23 2009-01-29 Leung Roger Y Methods of making low-refractive index and/or low-k organosilicate coatings
US7510982B1 (en) 2005-01-31 2009-03-31 Novellus Systems, Inc. Creation of porosity in low-k films by photo-disassociation of imbedded nanoparticles
US7622400B1 (en) 2004-05-18 2009-11-24 Novellus Systems, Inc. Method for improving mechanical properties of low dielectric constant materials
US7622162B1 (en) 2007-06-07 2009-11-24 Novellus Systems, Inc. UV treatment of STI films for increasing tensile stress
US7695765B1 (en) 2004-11-12 2010-04-13 Novellus Systems, Inc. Methods for producing low-stress carbon-doped oxide films with improved integration properties
US7781351B1 (en) 2004-04-07 2010-08-24 Novellus Systems, Inc. Methods for producing low-k carbon doped oxide films with low residual stress
US7790633B1 (en) 2004-10-26 2010-09-07 Novellus Systems, Inc. Sequential deposition/anneal film densification method
US7851232B2 (en) 2006-10-30 2010-12-14 Novellus Systems, Inc. UV treatment for carbon-containing low-k dielectric repair in semiconductor processing
US7892985B1 (en) 2005-11-15 2011-02-22 Novellus Systems, Inc. Method for porogen removal and mechanical strength enhancement of low-k carbon doped silicon oxide using low thermal budget microwave curing
US7906174B1 (en) 2006-12-07 2011-03-15 Novellus Systems, Inc. PECVD methods for producing ultra low-k dielectric films using UV treatment
US7923376B1 (en) 2006-03-30 2011-04-12 Novellus Systems, Inc. Method of reducing defects in PECVD TEOS films
US20110117678A1 (en) * 2006-10-30 2011-05-19 Varadarajan Bhadri N Carbon containing low-k dielectric constant recovery using uv treatment
US8110493B1 (en) 2005-12-23 2012-02-07 Novellus Systems, Inc. Pulsed PECVD method for modulating hydrogen content in hard mask
US8137465B1 (en) 2005-04-26 2012-03-20 Novellus Systems, Inc. Single-chamber sequential curing of semiconductor wafers
US8211510B1 (en) 2007-08-31 2012-07-03 Novellus Systems, Inc. Cascaded cure approach to fabricate highly tensile silicon nitride films
US8242028B1 (en) 2007-04-03 2012-08-14 Novellus Systems, Inc. UV treatment of etch stop and hard mask films for selectivity and hermeticity enhancement
US8282768B1 (en) 2005-04-26 2012-10-09 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US8454750B1 (en) 2005-04-26 2013-06-04 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US8889233B1 (en) 2005-04-26 2014-11-18 Novellus Systems, Inc. Method for reducing stress in porous dielectric films
US8980769B1 (en) 2005-04-26 2015-03-17 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US9050623B1 (en) 2008-09-12 2015-06-09 Novellus Systems, Inc. Progressive UV cure
US9659769B1 (en) 2004-10-22 2017-05-23 Novellus Systems, Inc. Tensile dielectric films using UV curing
US9847221B1 (en) 2016-09-29 2017-12-19 Lam Research Corporation Low temperature formation of high quality silicon oxide films in semiconductor device manufacturing
US10037905B2 (en) 2009-11-12 2018-07-31 Novellus Systems, Inc. UV and reducing treatment for K recovery and surface clean in semiconductor processing

Families Citing this family (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6922810B1 (en) * 2000-03-07 2005-07-26 Microsoft Corporation Grammar-based automatic data completion and suggestion for user input
US6548892B1 (en) * 2000-08-31 2003-04-15 Agere Systems Inc. Low k dielectric insulator and method of forming semiconductor circuit structures
EP1388178A2 (en) * 2001-05-14 2004-02-11 CDT Oxford Limited A method of providing a layer including a metal or silicon or germanium and oxygen on a surface
US7083342B2 (en) 2001-12-21 2006-08-01 Griffin Jason T Keyboard arrangement
US7934236B1 (en) * 2002-01-30 2011-04-26 Lee Capital Llc Advanced navigation method for music players and video players
US6864809B2 (en) * 2002-02-28 2005-03-08 Zi Technology Corporation Ltd Korean language predictive mechanism for text entry by a user
US20040078189A1 (en) * 2002-10-18 2004-04-22 Say-Ling Wen Phonetic identification assisted Chinese input system and method thereof
JP2004246603A (en) * 2003-02-13 2004-09-02 Sony Corp Information processing apparatus
US7129932B1 (en) * 2003-03-26 2006-10-31 At&T Corp. Keyboard for interacting on small devices
JP2004292636A (en) * 2003-03-27 2004-10-21 Matsushita Electric Ind Co Ltd Porous film, composition and method for forming the same, interlayer insulating film and semiconductor device
WO2004095414A1 (en) * 2003-04-18 2004-11-04 Keyless Systems Ltd Systems to enhance data entry in mobile and fixed environment
US7179758B2 (en) 2003-09-03 2007-02-20 International Business Machines Corporation Recovery of hydrophobicity of low-k and ultra low-k organosilicate films used as inter metal dielectrics
US7345000B2 (en) * 2003-10-10 2008-03-18 Tokyo Electron Limited Method and system for treating a dielectric film
US20050091604A1 (en) * 2003-10-22 2005-04-28 Scott Davis Systems and methods that track a user-identified point of focus
US8200866B2 (en) * 2004-04-27 2012-06-12 Varia Holdings Llc Reduced keypad for a mobile communication device for predictive input
US20050283724A1 (en) * 2004-06-18 2005-12-22 Research In Motion Limited Predictive text dictionary population
US7439959B2 (en) 2004-07-30 2008-10-21 Research In Motion Limited Key arrangement for a keyboard
US7387973B2 (en) * 2004-09-30 2008-06-17 Taiwan Semiconductor Manufacturing Co., Ltd. Method for improving low-K dielectrics by supercritical fluid treatments
KR100935620B1 (en) * 2004-10-27 2010-01-07 인터내셔널 비지네스 머신즈 코포레이션 Recovery of hydrophobicity of low-k and ultra low-k organosilicate films used as inter metal dielectrics
KR101063591B1 (en) * 2004-10-27 2011-09-07 인터내셔널 비지네스 머신즈 코포레이션 A low k and a method for restoring the extreme hydrophobicity of the organosilicate film having a low k, and in the article of manufacture from which is used as the dielectric between the metal
US20060095842A1 (en) * 2004-11-01 2006-05-04 Nokia Corporation Word completion dictionary
US20060128163A1 (en) * 2004-12-14 2006-06-15 International Business Machines Corporation Surface treatment of post-rie-damaged p-osg and other damaged materials
JP4894153B2 (en) 2005-03-23 2012-03-14 三井化学株式会社 Precursor composition and preparation method thereof of the porous membrane, a porous membrane and a manufacturing method thereof, and a semiconductor device
EP1726609A1 (en) 2005-05-25 2006-11-29 DSM IP Assets B.V. Hydrophobic coating
US20070076862A1 (en) * 2005-09-30 2007-04-05 Chatterjee Manjirnath A System and method for abbreviated text messaging
US8467530B2 (en) * 2005-10-05 2013-06-18 Kabushiki Kaisha Toshiba System and method for encrypting and decrypting document reproductions
US9842143B2 (en) * 2005-11-21 2017-12-12 Zi Corporation Of Canada, Inc. Information delivery system and method for mobile appliances
GB0604583D0 (en) 2006-03-08 2006-04-19 Dow Corning Impregnated flexible sheet material
US20070219954A1 (en) * 2006-03-15 2007-09-20 Microsoft Corporation Refined Search User Interface
JP5372323B2 (en) 2006-03-29 2013-12-18 富士通株式会社 Manufacturing method of interfacial roughness reducing film, a wiring layer and a semiconductor device and a semiconductor device using the same
US8296484B2 (en) * 2006-03-30 2012-10-23 Harris Corporation Alphanumeric data entry apparatus and method using multicharacter keys of a keypad
JP5030478B2 (en) 2006-06-02 2012-09-19 三井化学株式会社 Precursor composition and preparation method thereof of the porous membrane, a porous membrane and a manufacturing method thereof, and a semiconductor device
US8395586B2 (en) * 2006-06-30 2013-03-12 Research In Motion Limited Method of learning a context of a segment of text, and associated handheld electronic device
US7565624B2 (en) 2006-06-30 2009-07-21 Research In Motion Limited Method of learning character segments during text input, and associated handheld electronic device
KR100690961B1 (en) * 2006-06-30 2007-02-27 삼성전자주식회사 Method and apparatus for inputting character of mobile communication terminal
US7675435B2 (en) * 2006-08-31 2010-03-09 Microsoft Corporation Smart filtering with multiple simultaneous keyboard inputs
US20080133222A1 (en) * 2006-11-30 2008-06-05 Yehuda Kogan Spell checker for input of reduced keypad devices
US20080154576A1 (en) * 2006-12-21 2008-06-26 Jianchao Wu Processing of reduced-set user input text with selected one of multiple vocabularies and resolution modalities
US8126699B2 (en) * 2007-02-26 2012-02-28 Jeremy Thorne Process for translating machine shorthand into text
JP5131267B2 (en) * 2007-03-15 2013-01-30 富士通株式会社 Surface-hydrophobicized film-forming material, a method for manufacturing a multilayer wiring structure, a semiconductor device and a semiconductor device
US20080242353A1 (en) * 2007-04-02 2008-10-02 William Daniel Willey Input Shortcuts for a Communications Device
JP5154907B2 (en) * 2007-06-29 2013-02-27 富士通株式会社 A method of manufacturing a semiconductor device
US8702919B2 (en) * 2007-08-13 2014-04-22 Honeywell International Inc. Target designs and related methods for coupled target assemblies, methods of production and uses thereof
JP5119832B2 (en) * 2007-09-27 2013-01-16 富士通株式会社 Interfacial roughness reducing film, a wiring layer, a semiconductor device and a method of manufacturing a semiconductor device
CN101907930A (en) * 2009-06-04 2010-12-08 鸿富锦精密工业(深圳)有限公司;鸿海精密工业股份有限公司 Electronic device with key promoting and key promoting method
JP5396288B2 (en) * 2010-01-19 2014-01-22 菊水化学工業株式会社 Organic polysilazane paint
CN102191040B (en) * 2010-03-13 2013-06-12 中国科学院合肥物质科学研究院 Silica film doped with 9-fluorenylmethyl chloroformate and preparation method and application thereof
US8487877B2 (en) 2010-06-10 2013-07-16 Michael William Murphy Character specification system and method that uses a limited number of selection keys
EP2447777A3 (en) 2010-10-27 2015-05-27 ASML Netherlands BV Lithographic apparatus for transferring pattern from patterning device onto substrate, and damping method
RU2484517C1 (en) * 2011-11-01 2013-06-10 Межрегиональное общественное учреждение "Институт инженерной физики" Method for inputting letters and symbols for mobile telephones
US9589477B2 (en) * 2011-12-19 2017-03-07 Ellsworth Publishing Company, Inc. Method of keyboard training using keystroke time-out period
US9933857B2 (en) * 2012-12-03 2018-04-03 Paul Francis Streitz Data entry keyboard
US9182830B2 (en) 2012-12-12 2015-11-10 Marvin Blumberg Speed typing apparatus
US9098198B2 (en) 2012-12-12 2015-08-04 Marvin Blumberg Speed typing apparatus
US8996355B2 (en) 2013-02-08 2015-03-31 Machine Zone, Inc. Systems and methods for reviewing histories of text messages from multi-user multi-lingual communications
US9231898B2 (en) 2013-02-08 2016-01-05 Machine Zone, Inc. Systems and methods for multi-user multi-lingual communications
US8996353B2 (en) * 2013-02-08 2015-03-31 Machine Zone, Inc. Systems and methods for multi-user multi-lingual communications
US8990068B2 (en) 2013-02-08 2015-03-24 Machine Zone, Inc. Systems and methods for multi-user multi-lingual communications
US9600473B2 (en) 2013-02-08 2017-03-21 Machine Zone, Inc. Systems and methods for multi-user multi-lingual communications
US9298703B2 (en) 2013-02-08 2016-03-29 Machine Zone, Inc. Systems and methods for incentivizing user feedback for translation processing
US9031829B2 (en) 2013-02-08 2015-05-12 Machine Zone, Inc. Systems and methods for multi-user multi-lingual communications
US8996352B2 (en) 2013-02-08 2015-03-31 Machine Zone, Inc. Systems and methods for correcting translations in multi-user multi-lingual communications
KR101645793B1 (en) 2014-06-19 2016-08-08 (주)가온테크 Roll to roll processing apparatus and method of surface modification of thin film
US9372848B2 (en) 2014-10-17 2016-06-21 Machine Zone, Inc. Systems and methods for language detection
JP2016103531A (en) * 2014-11-27 2016-06-02 Jsr株式会社 Thin film transistor, manufacturing method and insulation film thereof
US20170103057A1 (en) * 2015-10-12 2017-04-13 Sugarcrm Inc. Context sensitive user dictionary utilization in text input field spell checking
CN105773458B (en) * 2016-05-16 2017-08-29 衢州学院 A high-solids content of the spherical silica nano polishing film and preparation method
CN106977982A (en) * 2017-03-31 2017-07-25 中国科学院地球化学研究所 Surface protection coating of nano-pore heat insulating material and preparation method of surface protection coating

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5661344A (en) * 1994-08-05 1997-08-26 Texas Instruments Incorporated Porous dielectric material with a passivation layer for electronics applications
US5723368A (en) * 1994-06-23 1998-03-03 Cho; Chi-Chen Porous dielectric material with improved pore surface properties for electronics applications
US5789819A (en) * 1994-05-20 1998-08-04 Texas Instruments Incorporated Low dielectric constant material for electronics applications
US5801092A (en) * 1997-09-04 1998-09-01 Ayers; Michael R. Method of making two-component nanospheres and their use as a low dielectric constant material for semiconductor devices
US5807607A (en) * 1995-11-16 1998-09-15 Texas Instruments Incorporated Polyol-based method for forming thin film aerogels on semiconductor substrates
US5936295A (en) * 1994-05-27 1999-08-10 Texas Instruments Incorporated Multilevel interconnect structure with air gaps formed between metal leads
US5955140A (en) * 1995-11-16 1999-09-21 Texas Instruments Incorporated Low volatility solvent-based method for forming thin film nanoporous aerogels on semiconductor substrates

Family Cites Families (104)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647973A (en) 1967-12-04 1972-03-07 Peter James Computer system utilizing a telephone as an input device
US3967273A (en) 1974-03-29 1976-06-29 Bell Telephone Laboratories, Incorporated Method and apparatus for using pushbutton telephone keys for generation of alpha-numeric information
DE2435860B2 (en) 1974-07-25 1977-10-20 silicas or silicates process for the preparation of finely divided hydrophobic
US4191854A (en) 1978-01-06 1980-03-04 Coles George A Telephone-coupled visual alphanumeric communication device for deaf persons
JPS6239467Y2 (en) 1978-11-20 1987-10-08
US4360892A (en) 1979-02-22 1982-11-23 Microwriter Limited Portable word-processor
US4442506A (en) 1980-09-18 1984-04-10 Microwriter Limited Portable word-processor
US4464070A (en) 1979-12-26 1984-08-07 International Business Machines Corporation Multi-character display controller for text recorder
JPS6357810B2 (en) 1980-04-08 1988-11-14 Sony Corp
JPS6122808B2 (en) 1980-12-26 1986-06-03 Sharp Kk
US4427848B1 (en) 1981-12-29 1994-03-29 Telephone Lottery Company Inc Telephonic alphanumeric data transmission system
US4426555A (en) 1982-01-18 1984-01-17 General Electric Company Telephone communications device for hearing-impaired person
US4459049A (en) 1982-03-24 1984-07-10 International Business Machines Corporation Abbreviated typing with special form display
US5062070A (en) 1983-01-21 1991-10-29 The Laitram Corporation Comprehensive computer data and control entries from very few keys operable in a fast touch typing mode
US4549279A (en) 1983-01-21 1985-10-22 The Laitram Corporation Single hand, single finger stroke alphameric data processing keyboard system
US4924431A (en) 1983-01-21 1990-05-08 The Laitram Corporation Keyboard located indicia for instructing a multi-mode programmable computer having alphanumeric capabilities from a few keyboard keys
US4680725A (en) 1983-01-21 1987-07-14 The Laitram Corporation Dual function decimal key
US5067103A (en) 1983-01-21 1991-11-19 The Laitram Corporation Hand held computers with alpha keystroke
USRE32773E (en) 1983-02-22 1988-10-25 Method of creating text using a computer
US4891786A (en) 1983-02-22 1990-01-02 Goldwasser Eric P Stroke typing system
JPH0571983B2 (en) * 1983-04-06 1993-10-08 Canon Kk
US4566065A (en) 1983-04-22 1986-01-21 Kalman Toth Computer aided stenographic system
US5289394A (en) 1983-05-11 1994-02-22 The Laitram Corporation Pocket computer for word processing
US4891777A (en) 1983-05-11 1990-01-02 The Laitram Corporation Single hand keyboard arrays providing alphanumeric capabilities from twelve keys
US4633227A (en) 1983-12-07 1986-12-30 Itt Corporation Programmable keyboard for a typewriter or similar article
US4650349A (en) 1984-02-17 1987-03-17 Cpt Corporation Speed typing apparatus and method
US4649563A (en) 1984-04-02 1987-03-10 R L Associates Method of and means for accessing computerized data bases utilizing a touch-tone telephone instrument
US4661916A (en) 1984-10-15 1987-04-28 Baker Bruce R System for method for producing synthetic plural word messages
JPS6195472A (en) 1984-10-16 1986-05-14 Brother Ind Ltd Electronic typewriter
USRE34304E (en) 1985-04-02 1993-07-06 Quasi-steno keyboard for text entry into a computer
FR2585487B1 (en) 1985-07-29 1990-09-07 Guyot Sionnest Laurent Computer keyboards, <70 cm2 and less than 13 contacts operated combinedly by the fingers of one hand
US4849732A (en) 1985-08-23 1989-07-18 Dolenc Heinz C One hand key shell
US4677659A (en) 1985-09-03 1987-06-30 John Dargan Telephonic data access and transmission system
US4674112A (en) 1985-09-06 1987-06-16 Board Of Regents, The University Of Texas System Character pattern recognition and communications apparatus
US4969097A (en) 1985-09-18 1990-11-06 Levin Leonid D Method of rapid entering of text into computer equipment
US4760528A (en) 1985-09-18 1988-07-26 Levin Leonid D Method for entering text using abbreviated word forms
US4754474A (en) 1985-10-21 1988-06-28 Feinson Roy W Interpretive tone telecommunication method and apparatus
US4807181A (en) 1986-06-02 1989-02-21 Smith Corona Corporation Dictionary memory with visual scanning from a selectable starting point
US4823294A (en) 1986-08-28 1989-04-18 Rouhani S Zia Single-hand computer keyboard
NL8700410A (en) 1987-02-19 1988-09-16 Philips Nv A text processing device for shorthand typing.
US4817129A (en) 1987-03-05 1989-03-28 Telac Corp. Method of and means for accessing computerized data bases utilizing a touch-tone telephone instrument
US4789564A (en) * 1987-03-31 1988-12-06 Union Carbide Corporation Hydridoaminosilane treatment for rendering surfaces water-repellent
US4791408A (en) 1987-05-14 1988-12-13 Ted Scudder Keyboard for one-hand operation
US4866759A (en) 1987-11-30 1989-09-12 Riskin Bernard N Packet network telecommunication system having access nodes with word guessing capability
US5031206A (en) 1987-11-30 1991-07-09 Fon-Ex, Inc. Method and apparatus for identifying words entered on DTMF pushbuttons
GB8729466D0 (en) 1987-12-17 1988-02-03 Automotive Prod Plc Vehicle brake systems
US4846598A (en) 1987-12-21 1989-07-11 Livits Eric A One-handed keyboard
US5069816A (en) * 1988-01-11 1991-12-03 Mmii Incorporated Zirconium silica hydrogel compositions and methods of preparation
US4872196A (en) 1988-07-18 1989-10-03 Motorola, Inc. Telephone keypad input technique
US5013585A (en) * 1989-06-13 1991-05-07 Shin-Etsu Chemical Co., Ltd. Method for the preparation of surface-modified silica particles
US5007008A (en) 1988-12-15 1991-04-09 Hewlett-Packard Company Method and apparatus for selecting key action
US5621641A (en) * 1988-12-21 1997-04-15 Freeman; Alfred B. Computer assisted text system
CA2006163A1 (en) 1988-12-21 1990-06-21 Alfred B. Freeman Keyboard express typing system
US5214689A (en) 1989-02-11 1993-05-25 Next Generaton Info, Inc. Interactive transit information system
US4885262A (en) 1989-03-08 1989-12-05 Intel Corporation Chemical modification of spin-on glass for improved performance in IC fabrication
US5063376A (en) 1989-05-05 1991-11-05 Chang Ronald G Numeric mouse one hand controllable computer peripheral pointing device
US5255310A (en) 1989-08-11 1993-10-19 Korea Telecommunication Authority Method of approximately matching an input character string with a key word and vocally outputting data
US5163084A (en) 1989-08-11 1992-11-10 Korea Telecommunication Authority Voice information service system and method utilizing approximately matched input character string and key word
DE3930344A1 (en) * 1989-09-12 1991-03-14 Merck Patent Gmbh silane derivatives
US5065661A (en) 1989-11-27 1991-11-19 Hacker Robert G Hand held electronic keyboard instrument
US5392338A (en) 1990-03-28 1995-02-21 Danish International, Inc. Entry of alphabetical characters into a telephone system using a conventional telephone keypad
US5339358A (en) 1990-03-28 1994-08-16 Danish International, Inc. Telephone keypad matrix
US5131045A (en) 1990-05-10 1992-07-14 Roth Richard G Audio-augmented data keying
CA2045906A1 (en) 1990-06-29 1991-12-30 Wei Zhang High efficiency input processing apparatus for alphabetic writings
US5305205A (en) 1990-10-23 1994-04-19 Weber Maria L Computer-assisted transcription apparatus
US5156475A (en) 1990-12-06 1992-10-20 Arkady Zilberman Keyboard divided by central inverted T-shaped entry-space key
US5229936A (en) 1991-01-04 1993-07-20 Franklin Electronic Publishers, Incorporated Device and method for the storage and retrieval of inflection information for electronic reference products
US5200988A (en) 1991-03-11 1993-04-06 Fon-Ex, Inc. Method and means for telecommunications by deaf persons utilizing a small hand held communications device
US5258748A (en) 1991-08-28 1993-11-02 Hewlett-Packard Company Accessing and selecting multiple key functions with minimum keystrokes
US5528235A (en) 1991-09-03 1996-06-18 Edward D. Lin Multi-status multi-function data processing key and key array
US5281966A (en) 1992-01-31 1994-01-25 Walsh A Peter Method of encoding alphabetic characters for a chord keyboard
US5317647A (en) 1992-04-07 1994-05-31 Apple Computer, Inc. Constrained attribute grammars for syntactic pattern recognition
US5410305A (en) 1992-07-10 1995-04-25 Intelligent Peripheral Devices, Inc. Portable computer keyboard
US5404321A (en) 1993-05-21 1995-04-04 Mattox; Jeffrey Computer system and method for modifying and enhancing the built-in programs of a computer
US5388061A (en) 1993-09-08 1995-02-07 Hankes; Elmer J. Portable computer for one-handed operation
JP2664876B2 (en) 1993-11-01 1997-10-22 インターナショナル・ビジネス・マシーンズ・コーポレイション Method and apparatus for improving user interaction
GB2283598A (en) 1993-11-03 1995-05-10 Ibm Data entry workstation
US5734749A (en) * 1993-12-27 1998-03-31 Nec Corporation Character string input system for completing an input character string with an incomplete input indicative sign
WO1995020187A1 (en) 1994-01-24 1995-07-27 Matsushita Electric Industrial Co., Ltd. Data input processor
US5488015A (en) 1994-05-20 1996-01-30 Texas Instruments Incorporated Method of making an interconnect structure with an integrated low density dielectric
US5577188A (en) 1994-05-31 1996-11-19 Future Labs, Inc. Method to provide for virtual screen overlay
US5938990A (en) 1994-07-01 1999-08-17 Roche Vitamins Inc. Encapsulation of oleophilic substances and compositions produced thereby
US5805911A (en) * 1995-02-01 1998-09-08 Microsoft Corporation Word prediction system
US5786776A (en) * 1995-03-13 1998-07-28 Kabushiki Kaisha Toshiba Character input terminal device and recording apparatus
US5818437A (en) 1995-07-26 1998-10-06 Tegic Communications, Inc. Reduced keyboard disambiguating computer
DK0842463T3 (en) 1995-07-26 2000-07-17 Tegic Communications Inc Reduced keyboard disambiguating system
US5790103A (en) 1995-10-04 1998-08-04 Willner; Michael A. Ergonomic keyboard entry system
US6037277A (en) * 1995-11-16 2000-03-14 Texas Instruments Incorporated Limited-volume apparatus and method for forming thin film aerogels on semiconductor substrates
US5748008A (en) 1995-12-06 1998-05-05 Landreth; Keith W. Electrical integrity test system for boats
US5781891A (en) * 1996-01-29 1998-07-14 Epic Systems Corporation Medical transcription system with text expansion
ES2163753T3 (en) * 1996-04-02 2002-02-01 Johnson & Son Inc S C Method for imparting hydrophobicity to a surface of a substrate with low concentration organofunctional silanes.
GB2313939B (en) * 1996-06-03 2000-09-13 Ibm Word processing
US5664896A (en) 1996-08-29 1997-09-09 Blumberg; Marvin R. Speed typing apparatus and method
JP3282976B2 (en) 1996-11-15 2002-05-20 セイコーエプソン株式会社 Character information processing apparatus and method
JP3889466B2 (en) * 1996-11-25 2007-03-07 ソニー株式会社 Text input device and method
EP0849796A3 (en) 1996-12-17 1999-09-01 Texas Instruments Incorporated Improvements in or relating to integrated circuits
US5953541A (en) 1997-01-24 1999-09-14 Tegic Communications, Inc. Disambiguating system for disambiguating ambiguous input sequences by displaying objects associated with the generated input sequences in the order of decreasing frequency of use
JPH1185362A (en) * 1997-09-01 1999-03-30 Nec Corp Keyboard control method and keyboard controller
DK1018069T3 (en) * 1997-09-25 2002-11-18 Tegic Communications Inc Reduced keyboard disambiguating system
US6377965B1 (en) * 1997-11-07 2002-04-23 Microsoft Corporation Automatic word completion system for partially entered data
US6114978A (en) * 1998-01-14 2000-09-05 Lucent Technologies Inc. Method and apparatus for assignment of shortcut key combinations in a computer software application
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
US5945928A (en) * 1998-01-20 1999-08-31 Tegic Communication, Inc. Reduced keyboard disambiguating system for the Korean language
US6395651B1 (en) * 1998-07-07 2002-05-28 Alliedsignal Simplified process for producing nanoporous silica

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5789819A (en) * 1994-05-20 1998-08-04 Texas Instruments Incorporated Low dielectric constant material for electronics applications
US5804508A (en) * 1994-05-20 1998-09-08 Texas Instruments Incorporated Method of making a low dielectric constant material for electronics
US5936295A (en) * 1994-05-27 1999-08-10 Texas Instruments Incorporated Multilevel interconnect structure with air gaps formed between metal leads
US5723368A (en) * 1994-06-23 1998-03-03 Cho; Chi-Chen Porous dielectric material with improved pore surface properties for electronics applications
US5661344A (en) * 1994-08-05 1997-08-26 Texas Instruments Incorporated Porous dielectric material with a passivation layer for electronics applications
US5807607A (en) * 1995-11-16 1998-09-15 Texas Instruments Incorporated Polyol-based method for forming thin film aerogels on semiconductor substrates
US5955140A (en) * 1995-11-16 1999-09-21 Texas Instruments Incorporated Low volatility solvent-based method for forming thin film nanoporous aerogels on semiconductor substrates
US5801092A (en) * 1997-09-04 1998-09-01 Ayers; Michael R. Method of making two-component nanospheres and their use as a low dielectric constant material for semiconductor devices

Cited By (91)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040013858A1 (en) * 2000-06-23 2004-01-22 Hacker Nigel P. Method to restore hydrophobicity in dielectric films and materials
US20070190735A1 (en) * 2000-06-23 2007-08-16 Hacker Nigel P Method to restore hydrophobicity in dielectric films and materials
US8440388B2 (en) 2000-06-23 2013-05-14 Honeywell International Inc. Method to restore hydrophobicity in dielectric films and materials
US7029826B2 (en) 2000-06-23 2006-04-18 Honeywell International Inc. Method to restore hydrophobicity in dielectric films and materials
US7858294B2 (en) 2000-06-23 2010-12-28 Honeywell International Inc. Method to restore hydrophobicity in dielectric films and materials
US20060078827A1 (en) * 2000-06-23 2006-04-13 Hacker Nigel P Method to restore hydrophobicity in dielectric films and materials
US6531344B1 (en) * 2000-07-06 2003-03-11 Motorola, Inc. High frequency gallium arsenide MMIC die coating method
US6943431B2 (en) * 2002-08-02 2005-09-13 Fujitsu Limited Semiconductor device using low-k material as interlayer insulating film and including a surface modifying layer
US20050250309A1 (en) * 2002-08-02 2005-11-10 Fujitsu Limited Semiconductor device using low-K material as interlayer insulating film and its manufacture method
US20040021224A1 (en) * 2002-08-02 2004-02-05 Fujitsu Limited Semiconductor device using low-k material as interlayer insulating film and its manufacture method
US7256118B2 (en) 2002-08-02 2007-08-14 Fujitsu Limited Semiconductor device using low-K material as interlayer insulating film and its manufacture method
US20060141641A1 (en) * 2003-01-25 2006-06-29 Wenya Fan Repair and restoration of damaged dielectric materials and films
US20050095840A1 (en) * 2003-01-25 2005-05-05 Bhanap Anil S. Repairing damage to low-k dielectric materials using silylating agents
WO2004068555A3 (en) * 2003-01-25 2005-02-03 Honeywell Int Inc Repair and restoration of damaged dielectric materials and films
US7709371B2 (en) 2003-01-25 2010-05-04 Honeywell International Inc. Repairing damage to low-k dielectric materials using silylating agents
US7915181B2 (en) * 2003-01-25 2011-03-29 Honeywell International Inc. Repair and restoration of damaged dielectric materials and films
US7241704B1 (en) 2003-03-31 2007-07-10 Novellus Systems, Inc. Methods for producing low stress porous low-k dielectric materials using precursors with organic functional groups
US7176144B1 (en) 2003-03-31 2007-02-13 Novellus Systems, Inc. Plasma detemplating and silanol capping of porous dielectric films
US20090239390A1 (en) * 2003-03-31 2009-09-24 Novellus Systems, Inc. Methods for producing low stress porous and cdo low-k dielectric materials using precursors with organic functional groups
US7208389B1 (en) 2003-03-31 2007-04-24 Novellus Systems, Inc. Method of porogen removal from porous low-k films using UV radiation
US7923385B2 (en) 2003-03-31 2011-04-12 Novellus Systems, Inc. Methods for producing low stress porous and CDO low-K dielectric materials using precursors with organic functional groups
US7473653B1 (en) 2003-03-31 2009-01-06 Novellus Systems, Inc. Methods for producing low stress porous low-k dielectric materials using precursors with organic functional groups
US7799705B1 (en) 2003-03-31 2010-09-21 Novellus Systems, Inc. Methods for producing low stress porous low-k dielectric materials using precursors with organic functional groups
US7265061B1 (en) 2003-05-09 2007-09-04 Novellus Systems, Inc. Method and apparatus for UV exposure of low dielectric constant materials for porogen removal and improved mechanical properties
US20060156934A1 (en) * 2003-09-19 2006-07-20 Gallus Druckmaschinen Ag Rotary printing press
US7390537B1 (en) 2003-11-20 2008-06-24 Novellus Systems, Inc. Methods for producing low-k CDO films with low residual stress
US7737525B1 (en) 2004-03-11 2010-06-15 Novellus Systems, Inc. Method for producing low-K CDO films
US20100330284A1 (en) * 2004-03-11 2010-12-30 The Regents Of The University Of California Procedure for preparing redox-active polymers on surfaces
US7452572B1 (en) 2004-03-11 2008-11-18 The North Carolina State University Procedure for preparing redox-active polymers on surfaces
US8231941B2 (en) 2004-03-11 2012-07-31 The Regents Of The University Of California Procedure for preparing redox-active polymers on surfaces
US7381662B1 (en) 2004-03-11 2008-06-03 Novellus Systems, Inc. Methods for improving the cracking resistance of low-k dielectric materials
US7094713B1 (en) 2004-03-11 2006-08-22 Novellus Systems, Inc. Methods for improving the cracking resistance of low-k dielectric materials
US20080280047A1 (en) * 2004-03-11 2008-11-13 The Regents Of The University Of California Procedure for preparing redox-active polymers on surfaces
US7341761B1 (en) 2004-03-11 2008-03-11 Novellus Systems, Inc. Methods for producing low-k CDO films
US7781351B1 (en) 2004-04-07 2010-08-24 Novellus Systems, Inc. Methods for producing low-k carbon doped oxide films with low residual stress
US8715788B1 (en) 2004-04-16 2014-05-06 Novellus Systems, Inc. Method to improve mechanical strength of low-K dielectric film using modulated UV exposure
US7611757B1 (en) 2004-04-16 2009-11-03 Novellus Systems, Inc. Method to improve mechanical strength of low-K dielectric film using modulated UV exposure
US8043667B1 (en) 2004-04-16 2011-10-25 Novellus Systems, Inc. Method to improve mechanical strength of low-K dielectric film using modulated UV exposure
US7253125B1 (en) 2004-04-16 2007-08-07 Novellus Systems, Inc. Method to improve mechanical strength of low-k dielectric film using modulated UV exposure
US7622400B1 (en) 2004-05-18 2009-11-24 Novellus Systems, Inc. Method for improving mechanical properties of low dielectric constant materials
US7326444B1 (en) 2004-09-14 2008-02-05 Novellus Systems, Inc. Methods for improving integration performance of low stress CDO films
US8475666B2 (en) 2004-09-15 2013-07-02 Honeywell International Inc. Method for making toughening agent materials
US20060057837A1 (en) * 2004-09-15 2006-03-16 Bhanap Anil S Treating agent materials
US20060057855A1 (en) * 2004-09-15 2006-03-16 Ramos Teresa A Method for making toughening agent materials
US7915159B2 (en) 2004-09-15 2011-03-29 Honeywell International Inc. Treating agent materials
US9659769B1 (en) 2004-10-22 2017-05-23 Novellus Systems, Inc. Tensile dielectric films using UV curing
US7790633B1 (en) 2004-10-26 2010-09-07 Novellus Systems, Inc. Sequential deposition/anneal film densification method
US7695765B1 (en) 2004-11-12 2010-04-13 Novellus Systems, Inc. Methods for producing low-stress carbon-doped oxide films with improved integration properties
US8062983B1 (en) 2005-01-31 2011-11-22 Novellus Systems, Inc. Creation of porosity in low-k films by photo-disassociation of imbedded nanoparticles
US7629224B1 (en) 2005-01-31 2009-12-08 Novellus Systems, Inc. VLSI fabrication processes for introducing pores into dielectric materials
US7972976B1 (en) 2005-01-31 2011-07-05 Novellus Systems, Inc. VLSI fabrication processes for introducing pores into dielectric materials
US7510982B1 (en) 2005-01-31 2009-03-31 Novellus Systems, Inc. Creation of porosity in low-k films by photo-disassociation of imbedded nanoparticles
US7166531B1 (en) 2005-01-31 2007-01-23 Novellus Systems, Inc. VLSI fabrication processes for introducing pores into dielectric materials
US7678712B2 (en) 2005-03-22 2010-03-16 Honeywell International, Inc. Vapor phase treatment of dielectric materials
US20060216952A1 (en) * 2005-03-22 2006-09-28 Bhanap Anil S Vapor phase treatment of dielectric materials
US8734663B2 (en) 2005-04-26 2014-05-27 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US8889233B1 (en) 2005-04-26 2014-11-18 Novellus Systems, Inc. Method for reducing stress in porous dielectric films
US8980769B1 (en) 2005-04-26 2015-03-17 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US10121682B2 (en) 2005-04-26 2018-11-06 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US8629068B1 (en) 2005-04-26 2014-01-14 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US8518210B2 (en) 2005-04-26 2013-08-27 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US9384959B2 (en) 2005-04-26 2016-07-05 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US8282768B1 (en) 2005-04-26 2012-10-09 Novellus Systems, Inc. Purging of porogen from UV cure chamber
US9873946B2 (en) 2005-04-26 2018-01-23 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US8454750B1 (en) 2005-04-26 2013-06-04 Novellus Systems, Inc. Multi-station sequential curing of dielectric films
US8137465B1 (en) 2005-04-26 2012-03-20 Novellus Systems, Inc. Single-chamber sequential curing of semiconductor wafers
US20060281010A1 (en) * 2005-06-14 2006-12-14 Seok-Soo Lee Organic electrolytic solution and lithium battery employing the same
US7781105B2 (en) * 2005-06-14 2010-08-24 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium battery employing the same
US8062756B2 (en) 2005-08-26 2011-11-22 The Regents oft the University of California Stepwise growth of oligomeric redox-active molecules on a surface without the use of protecting groups
US20070123618A1 (en) * 2005-08-26 2007-05-31 The Regents Of The University Of California Stepwise growth of oligomeric redox-active molecules on a surface without the use of protecting groups
WO2007025114A3 (en) * 2005-08-26 2007-07-05 Univ California Stepwise growth of oligomeric redox-active molecules on a surface without the use of protecting groups
WO2007025114A2 (en) * 2005-08-26 2007-03-01 The Regents Of The University Of California Stepwise growth of oligomeric redox-active molecules on a surface without the use of protecting groups
US7892985B1 (en) 2005-11-15 2011-02-22 Novellus Systems, Inc. Method for porogen removal and mechanical strength enhancement of low-k carbon doped silicon oxide using low thermal budget microwave curing
US7381644B1 (en) 2005-12-23 2008-06-03 Novellus Systems, Inc. Pulsed PECVD method for modulating hydrogen content in hard mask
US8110493B1 (en) 2005-12-23 2012-02-07 Novellus Systems, Inc. Pulsed PECVD method for modulating hydrogen content in hard mask
US7923376B1 (en) 2006-03-30 2011-04-12 Novellus Systems, Inc. Method of reducing defects in PECVD TEOS films
US20110045610A1 (en) * 2006-10-30 2011-02-24 Van Schravendijk Bart Uv treatment for carbon-containing low-k dielectric repair in semiconductor processing
US7851232B2 (en) 2006-10-30 2010-12-14 Novellus Systems, Inc. UV treatment for carbon-containing low-k dielectric repair in semiconductor processing
US20110117678A1 (en) * 2006-10-30 2011-05-19 Varadarajan Bhadri N Carbon containing low-k dielectric constant recovery using uv treatment
US8465991B2 (en) 2006-10-30 2013-06-18 Novellus Systems, Inc. Carbon containing low-k dielectric constant recovery using UV treatment
US7906174B1 (en) 2006-12-07 2011-03-15 Novellus Systems, Inc. PECVD methods for producing ultra low-k dielectric films using UV treatment
US7500397B2 (en) 2007-02-15 2009-03-10 Air Products And Chemicals, Inc. Activated chemical process for enhancing material properties of dielectric films
US20080199977A1 (en) * 2007-02-15 2008-08-21 Air Products And Chemicals, Inc. Activated Chemical Process for Enhancing Material Properties of Dielectric Films
US8242028B1 (en) 2007-04-03 2012-08-14 Novellus Systems, Inc. UV treatment of etch stop and hard mask films for selectivity and hermeticity enhancement
US7622162B1 (en) 2007-06-07 2009-11-24 Novellus Systems, Inc. UV treatment of STI films for increasing tensile stress
US20090026924A1 (en) * 2007-07-23 2009-01-29 Leung Roger Y Methods of making low-refractive index and/or low-k organosilicate coatings
US8211510B1 (en) 2007-08-31 2012-07-03 Novellus Systems, Inc. Cascaded cure approach to fabricate highly tensile silicon nitride films
US8512818B1 (en) 2007-08-31 2013-08-20 Novellus Systems, Inc. Cascaded cure approach to fabricate highly tensile silicon nitride films
US9050623B1 (en) 2008-09-12 2015-06-09 Novellus Systems, Inc. Progressive UV cure
US10037905B2 (en) 2009-11-12 2018-07-31 Novellus Systems, Inc. UV and reducing treatment for K recovery and surface clean in semiconductor processing
US9847221B1 (en) 2016-09-29 2017-12-19 Lam Research Corporation Low temperature formation of high quality silicon oxide films in semiconductor device manufacturing

Also Published As

Publication number Publication date Type
CN1345464A (en) 2002-04-17 application
KR100716022B1 (en) 2007-05-08 grant
US6799303B2 (en) 2004-09-28 grant
US6770572B1 (en) 2004-08-03 grant
US20030038735A1 (en) 2003-02-27 application
JP4947836B2 (en) 2012-06-06 grant
WO2000044036A1 (en) 2000-07-27 application
CN1236480C (en) 2006-01-11 grant
JP2004513503A (en) 2004-04-30 application
EP1153426A1 (en) 2001-11-14 application

Similar Documents

Publication Publication Date Title
US6022812A (en) Vapor deposition routes to nanoporous silica
US6037275A (en) Nanoporous silica via combined stream deposition
US6313045B1 (en) Nanoporous silicone resins having low dielectric constants and method for preparation
US5527872A (en) Electronic device with a spin-on glass dielectric layer
US6372666B1 (en) Process for producing dielectric thin films
US20050260420A1 (en) Low dielectric materials and methods for making same
US6143855A (en) Organohydridosiloxane resins with high organic content
US7186613B2 (en) Low dielectric materials and methods for making same
US6329062B1 (en) Dielectric layer including silicalite crystals and binder and method for producing same for microelectronic circuits
US6232424B1 (en) Soluble silicone resin compositions having good solution stability
US6541107B1 (en) Nanoporous silicone resins having low dielectric constants
US5807607A (en) Polyol-based method for forming thin film aerogels on semiconductor substrates
US5955140A (en) Low volatility solvent-based method for forming thin film nanoporous aerogels on semiconductor substrates
US5853808A (en) Method of using siloxane polymers
US6399210B1 (en) Alkoxyhydridosiloxane resins
US20040048960A1 (en) Compositions for preparing low dielectric materials
US7404990B2 (en) Non-thermal process for forming porous low dielectric constant films
US20050113472A1 (en) Porous materials
US6048804A (en) Process for producing nanoporous silica thin films
US6380105B1 (en) Low volatility solvent-based method for forming thin film nanoporous aerogels on semiconductor substrates
US20050196974A1 (en) Compositions for preparing low dielectric materials containing solvents
US5043789A (en) Planarizing silsesquioxane copolymer coating
US6204202B1 (en) Low dielectric constant porous films
US6015457A (en) Stable inorganic polymers
US7029826B2 (en) Method to restore hydrophobicity in dielectric films and materials