US20140065844A1 - Amino Vinylsilane Precursors for Stressed SiN Films - Google Patents

Amino Vinylsilane Precursors for Stressed SiN Films Download PDF

Info

Publication number
US20140065844A1
US20140065844A1 US14/070,957 US201314070957A US2014065844A1 US 20140065844 A1 US20140065844 A1 US 20140065844A1 US 201314070957 A US201314070957 A US 201314070957A US 2014065844 A1 US2014065844 A1 US 2014065844A1
Authority
US
United States
Prior art keywords
bis
vinylsilane
dimethylamino
film
vinylmethylsilane
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
US14/070,957
Inventor
Vasil Vorsa
Andrew David Johnson
Manchao Xiao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Versum Materials US LLC
Original Assignee
Air Products And Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Products And Chemicals, Inc. filed Critical Air Products And Chemicals, Inc.
Priority to US14/070,957 priority Critical patent/US20140065844A1/en
Publication of US20140065844A1 publication Critical patent/US20140065844A1/en
Assigned to AIR PRODUCTS AND CHEMICALS, INC. reassignment AIR PRODUCTS AND CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JOHNSON, ANDREW DAVID, VORSA, VASIL, XIAO, MANCHAO
Assigned to VERSUM MATERIALS US, LLC reassignment VERSUM MATERIALS US, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AIR PRODUCTS AND CHEMICALS, INC.
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]

Definitions

  • Compressive stress enhances “P” type field effect transistors (pFET) devices through increases of hole mobility, while tensile stress is beneficial for “N” type field effect transistors (nFET) devices through enhancing electron mobility. Stress is generated from differences in the thermal expansion between two materials in contact. Plasma enhanced chemical vapor deposition (PECVD) silicon nitride films generally generate compressive stress.
  • PECVD Plasma enhanced chemical vapor deposition
  • compressively stressed films are deposited using silane and ammonia with reported compressive stresses up to ⁇ 3.5 giga pascales (GPa). Increasing compressive stress further is becoming particularly challenging. The industry is currently aiming for compressively stressed films of ⁇ 4 GPa or higher.
  • Patents related to this technology include: US 2006/0045986; EP 1 630 249; US 2006/0258173; EP 1 724 373; U.S. Pat. No. 7,288,145; U.S. Pat. No. 7,122,222; US20060269692; WO2006/127462; and US2008/0146007, as well as the literature reference; “Methods of producing plasma enhanced chemical vapor deposition silicon nitride thin films with high compressive and tensile stress.”; M. Belyansky et al. J. Vac. Sci. Technol. A 26(3),517 (2008).
  • the present invention is a method to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) silicon nitride (SiN) and silicon carbonitride (SiCN) thin films, comprising depositing the film from an amino vinylsilane-based precursor.
  • PECVD plasma enhanced chemical vapor deposition
  • SiN silicon nitride
  • SiCN silicon carbonitride
  • the present invention uses the amino vinylsilane-based precursor selected from the formula: [RR 1 N] x SiR 3 y (R 2 ) z
  • R, R 1 and R 3 can be hydrogen, C 1 to C 10 alkane, alkene, or C 4 to C 12 aromatic; each R 2 is a vinyl, allyl or vinyl-containing functional group.
  • FIGS. 1 A and B are depictions of structural formulae of species of chemical precursors for the present invention.
  • FIG. 2 is a graph of stress values for films formed by PECVD depositions of BIPAVMS and ammonia under various process conditions.
  • FIG. 3 is a FTIR spectra of silicon nitride films deposited with PECVD using BIPAVMS and ammonia.
  • FIG. 4 is a graph plotting the ratio of nitrogen bonded hydrogen (NH x ) to silicon bonded hydrogen (SiH) content versus film stress.
  • FIG. 5 is a graph plotting NH x and SiH content versus film stress.
  • the present invention provides amino vinylsilane-based precursors as a way to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) silicon nitride (SiN) and silicon carbonitride (SiCN) thin films.
  • PECVD plasma enhanced chemical vapor deposition
  • SiN silicon nitride
  • SiCN silicon carbonitride
  • the main feature of these amino vinylsilane precursors is one or two vinyl functional groups bonded to the central silicon atom.
  • the precursors have the general formula:
  • R, R 1 and R 3 can be hydrogen, C 1 to C 10 alkane, alkene, or C 4 to C 12 aromatic; each R 2 is a vinyl, allyl or other vinyl-containing functional group. The addition of a vinyl group to the aminosilane is found to increase the intrinsic compressive stress of SiN and SiCN films deposited using these precursors.
  • the amino vinylsilane precursors include, but not limited to, Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)diallylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylaminoamino)divinylsilane, Bis(t-butylaminoamino)vinylsilane, Bis(t-butylaminoamino)allylmethylsilane, Bis(t-butylaminoamino)diallylsilane, Bis(t-butylaminoamino)allylsilane, Bis(diethylamino
  • BIPAVMS Bis(iso-propylamino)vinylmethylsilane
  • BIPADVS Bis(iso-propylamino)divinylsilane
  • PECVD silicon nitride films Stress engineering of PECVD silicon nitride films is currently being used to enhance the performance of cutting edge MOSFET technology. Device speed has been significantly increased through the application of highly stressed SiN films deposited on top of MOSFET gate structures. Compressive stress enhances pFET devices through increases of hole mobility, while tensile stress is beneficial for nFET devices through enhancing electron mobility. Stress is generated from differences in the thermal expansion between two materials in contact. PECVD silicon nitride films generally generate compressive stress. Presently, compressively stressed films are deposited using silane and ammonia with reported compressive stresses up to ⁇ 3.5 GPa. Increasing compressive stress further is becoming particularly challenging. The industry is currently aiming for compressively stressed films of ⁇ 4 GPa or higher.
  • ⁇ 4 GPa compressively stressed films may be realized through the use of the above described amino vinylsilane precursors.
  • compressive stress of ⁇ 0.7 to ⁇ 4.5 GPa ⁇ 700 to ⁇ 4500 MPa
  • This invention is the first to specifically use a unique type of silicon-containing precursor to increase film stress.
  • Standard deposition methods have a limit to the amount of stress they can generate.
  • Current targets for stress are 1.5 GPa for tensile stress and ⁇ 4 GPa for compressive stress.
  • aminosilanes containing vinyl functional groups such as BIPADVS and BIPAVMS
  • BIPADVS and BIPAVMS have been found to increase compressive stress further.
  • Vinyl groups play important roles in creating film stress.
  • carbon-carbon double bonds may form cross-linking points, which increase the density of film by holding atoms closer.
  • Si—H bonds of the precursor react with carbon-carbon double bonds with hydrosilylation reaction, forming ethylene bridges between silicon atoms. Ethylene bridges hold the silicon atoms close, and are consequently replaced by ammonia, and that process helps the formation of Si—N—Si structure.
  • the present invention is directed to overcome limits of intrinsic stress generation through the use of this special class of aminosilane precursors, namely amino vinylsilanes, to deposit highly stressed silicon nitride (SiN) films or silicon carbonitride (SiCN) films using PEVCD.
  • aminosilane precursors namely amino vinylsilanes
  • SiN silicon nitride
  • SiCN silicon carbonitride
  • the addition of a vinyl group to the aminosilane is found to increase the intrinsic compressive stress of SiN and SiCN films deposited using these precursors.
  • the amino vinylsilane is reacted with a nitrogen-containing gas in a PECVD chamber at wafer temperatures of 500° C. or less.
  • the nitrogen containing gas can be ammonia, nitrogen, or a combination thereof.
  • a diluent gas such as, but not limited to, He, Ar, Ne, Xe, or hydrogen can be introduced to modify the film properties.
  • BIPAVMS Bis(iso-propylamino)vinylmethylsilane
  • BIPADVS Bis(iso-propylamino)divinylsilane
  • a suitable BIPAVMS flow rate may range from 50 to about 1000 mg/min.
  • a suitable ammonia and/or nitrogen flow rate may range from 500 to 10,000 sccm, and the diluent gases can range from 50 to 50,000 sccm.
  • Depositions conditions for Runs A-F and the corresponding film stress obtained in Table 1, below, are as follows.
  • Deposition temperature was 400 C.
  • properties were obtained from sample films that were deposited onto medium resistivity (8-12 ⁇ cm) single crystal silicon wafer substrates. All depositions were performed on an Applied Materials Precision 5000 system in a 200 mm DXZ chamber fitted with an Advanced Energy 2000 RF generator. The plasma is single frequency of 13.56 MHz.
  • FTIR Fourier Infrared Spectroscopy
  • Thermo Nicolet 750 system in a nitrogen purged cell. Background spectra were collected on similar medium resistivity wafers to eliminate CO 2 and water from the spectra. Data was obtained in the range of from 4000 to 400 cm ⁇ 1 by collecting 32 scans with a resolution of 4 cm ⁇ 1 .
  • the OMNIC software package was used to process the data. Film stress measurements were made using a laser beam scattering tool (Toho Technology Corp., Model: FLX2320S).
  • FIG. 2 Film stress data of silicon nitride films deposited at 400° C. using Bis(iso-propylamino)vinylmethylsilane and ammonia is shown in FIG. 2 .
  • the films were deposited under various process conditions, such as precursor and gas flow rate, pressure, and RF power.
  • the films were single layer, with thicknesses ranging from 100 to 350 nm.
  • the plasma was generated using a single frequency of 13.56 MHz.
  • the compressive stress of these films ranged from ⁇ 700 to ⁇ 2400 mega pascales (MPa). These films produced ⁇ 1.5 to 1.8 ⁇ higher compressive stress, than BTBAS under comparable process conditions.
  • FIG. 3 shows the FTIR spectra of films from FIG. 2 with the lowest (Film C) and highest (Film E) compressive stress. Both films exhibit NH x stretching and bending modes of similar intensity. However, there is a distinct difference in the SiH peak at ⁇ 2190 cm ⁇ 1 , thus suggesting the main difference is in whether hydrogen is bonded to nitrogen or silicon.
  • FIG. 4 depicts the correlation between the ratio of NH x to SiH with stress. As can be seen from this figure, stress increases with higher NH x to SiH ratio.
  • the deposited thin film has a N—H to Si—H ratio of 25 to 85, most preferably 70.
  • FIG. 5 depicts the correlation of nitrogen bonded hydrogen (NH x ) to stress and silicon bonded hydrogen to stress. This data indicates that reduction of SiH groups in addition to high levels of NH x moiety is important in generating high levels of compressive stress. Hydrogen contents derived from NH x moieties increase compressive stress in the range of 2.9 to 3.5 H content/cm 3 ⁇ 10 22 , preferably 3.3 to 3.6 H content/cm 3 ⁇ 10 22

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Abstract

The present invention is a method to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) silicon nitride (SiN) and silicon carbonitride (SiCN) thin films, comprising depositing the film from an amino vinylsilane-based precursor. More specifically the present invention uses the amino vinylsilane-based precursor selected from the formula: [RR1N]xSiR3 y(R2)z, where x+y+z=4, x=1-3, y=0-2, and z=1-3; R, R1 and R3 can be hydrogen, C1 to C10 alkane, alkene, or C4 to C12 aromatic; each R2 is a vinyl, allyl or vinyl-containing functional group.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • The Present application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/113,624 filed Nov. 12, 2008.
    • BACKGROUND OF THE INVENTION
  • The Present Invention is in the field of integrated circuit fabrication and particularly materials of construction in the films that are adjacent to or are a part of electronic devices in the integrated circuit, such as transistors, capacitors, vias, electrically conductive lines and buss bars. As the dimensions of such electronic devices continue to shrink and the density of such devices in a given area increases, the films adjacent to or a part of such electronic devices must exhibit higher electrical properties. Designing stress into such films can alter their electrical properties. Stress engineering of PECVD silicon nitride films is currently being used to enhance the performance of cutting edge metal oxide semiconductor field effect transistor (MOSFET) technology. Device speed has been significantly increased through the application of highly stressed SiN films deposited on top of MOSFET gate structures. Compressive stress enhances “P” type field effect transistors (pFET) devices through increases of hole mobility, while tensile stress is beneficial for “N” type field effect transistors (nFET) devices through enhancing electron mobility. Stress is generated from differences in the thermal expansion between two materials in contact. Plasma enhanced chemical vapor deposition (PECVD) silicon nitride films generally generate compressive stress.
  • Presently, compressively stressed films are deposited using silane and ammonia with reported compressive stresses up to ˜−3.5 giga pascales (GPa). Increasing compressive stress further is becoming particularly challenging. The industry is currently aiming for compressively stressed films of −4 GPa or higher.
  • Patents related to this technology include: US 2006/0045986; EP 1 630 249; US 2006/0258173; EP 1 724 373; U.S. Pat. No. 7,288,145; U.S. Pat. No. 7,122,222; US20060269692; WO2006/127462; and US2008/0146007, as well as the literature reference; “Methods of producing plasma enhanced chemical vapor deposition silicon nitride thin films with high compressive and tensile stress.”; M. Belyansky et al. J. Vac. Sci. Technol. A 26(3),517 (2008).
    • BRIEF SUMMARY OF THE INVENTION
  • The present invention is a method to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) silicon nitride (SiN) and silicon carbonitride (SiCN) thin films, comprising depositing the film from an amino vinylsilane-based precursor.
  • More specifically the present invention uses the amino vinylsilane-based precursor selected from the formula: [RR1N]xSiR3 y(R2)z
  • where x+y+z=4, x=1-3, y=0-2, and z=1-3; R, R1 and R3 can be hydrogen, C1 to C10 alkane, alkene, or C4 to C12 aromatic; each R2 is a vinyl, allyl or vinyl-containing functional group.
    • BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
  • FIGS. 1 A and B are depictions of structural formulae of species of chemical precursors for the present invention.
  • FIG. 2 is a graph of stress values for films formed by PECVD depositions of BIPAVMS and ammonia under various process conditions.
  • FIG. 3 is a FTIR spectra of silicon nitride films deposited with PECVD using BIPAVMS and ammonia.
  • FIG. 4 is a graph plotting the ratio of nitrogen bonded hydrogen (NHx) to silicon bonded hydrogen (SiH) content versus film stress.
  • FIG. 5 is a graph plotting NHx and SiH content versus film stress.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • The present invention provides amino vinylsilane-based precursors as a way to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) silicon nitride (SiN) and silicon carbonitride (SiCN) thin films. The main feature of these amino vinylsilane precursors is one or two vinyl functional groups bonded to the central silicon atom. The precursors have the general formula:

  • [RR1N]xSiR3 y(R2)z
  • where x+y+z=4, x=1-3, y=0-2, and z=1-3. R, R1 and R3 can be hydrogen, C1 to C10 alkane, alkene, or C4 to C12 aromatic; each R2 is a vinyl, allyl or other vinyl-containing functional group. The addition of a vinyl group to the aminosilane is found to increase the intrinsic compressive stress of SiN and SiCN films deposited using these precursors.
  • The amino vinylsilane precursors include, but not limited to, Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)diallylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylaminoamino)divinylsilane, Bis(t-butylaminoamino)vinylsilane, Bis(t-butylaminoamino)allylmethylsilane, Bis(t-butylaminoamino)diallylsilane, Bis(t-butylaminoamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)diallylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)divinylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)diallylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinodivinylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinodivinylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, Dipyrrolidinoallylsilane.
  • The particular precursor used in tests is Bis(iso-propylamino)vinylmethylsilane (BIPAVMS). Another similar precursor is Bis(iso-propylamino)divinylsilane (BIPADVS).
  • Stress engineering of PECVD silicon nitride films is currently being used to enhance the performance of cutting edge MOSFET technology. Device speed has been significantly increased through the application of highly stressed SiN films deposited on top of MOSFET gate structures. Compressive stress enhances pFET devices through increases of hole mobility, while tensile stress is beneficial for nFET devices through enhancing electron mobility. Stress is generated from differences in the thermal expansion between two materials in contact. PECVD silicon nitride films generally generate compressive stress. Presently, compressively stressed films are deposited using silane and ammonia with reported compressive stresses up to ˜−3.5 GPa. Increasing compressive stress further is becoming particularly challenging. The industry is currently aiming for compressively stressed films of −4 GPa or higher.
  • The goal of −4 GPa compressively stressed films may be realized through the use of the above described amino vinylsilane precursors. In the present invention, compressive stress of −0.7 to −4.5 GPa (−700 to −4500 MPa) can be obtained. Up to now, most of the increases in stress generation have been through processing techniques, such as plasma surface treatment, multilayer deposition, dual frequency plasma and other similar methods. This invention is the first to specifically use a unique type of silicon-containing precursor to increase film stress.
  • Standard deposition methods have a limit to the amount of stress they can generate. Current targets for stress are 1.5 GPa for tensile stress and −4 GPa for compressive stress.
  • It has been observed that higher hydrogen incorporation into SiN films leads to higher compressive stress. We propose that PECVD SiN films deposited using amino vinylsilanes such as BIPADVS and BIPAVMS can generate highly compressive stress due to overall hydrogen incorporation and, moreover, through the type of hydrogen incorporation, i.e. nitrogen bonded hydrogen vs silicon bonded hydrogen. We have shown for both bis(tertiary-butylamino)silane (BTBAS) and BIPAVMS a strong correlation between N—H to Si—H ratio and compressive stress, with high N—H to Si—H ratio leading to higher compressive stress. Films deposited using a mixture of an aminosilane and ammonia naturally lead to films containing high N—H to Si—H content through transamination reactions
  • Furthermore, aminosilanes containing vinyl functional groups, such as BIPADVS and BIPAVMS, have been found to increase compressive stress further. Vinyl groups play important roles in creating film stress. Under plasma conditions, carbon-carbon double bonds may form cross-linking points, which increase the density of film by holding atoms closer. Si—H bonds of the precursor react with carbon-carbon double bonds with hydrosilylation reaction, forming ethylene bridges between silicon atoms. Ethylene bridges hold the silicon atoms close, and are consequently replaced by ammonia, and that process helps the formation of Si—N—Si structure.
  • Figure US20140065844A1-20140306-C00001
  • The present invention is directed to overcome limits of intrinsic stress generation through the use of this special class of aminosilane precursors, namely amino vinylsilanes, to deposit highly stressed silicon nitride (SiN) films or silicon carbonitride (SiCN) films using PEVCD. The addition of a vinyl group to the aminosilane is found to increase the intrinsic compressive stress of SiN and SiCN films deposited using these precursors.
  • To deposit compressively stressed silicon nitride or silicon carbonitride films, the amino vinylsilane is reacted with a nitrogen-containing gas in a PECVD chamber at wafer temperatures of 500° C. or less. The nitrogen containing gas can be ammonia, nitrogen, or a combination thereof. Additionally, a diluent gas such as, but not limited to, He, Ar, Ne, Xe, or hydrogen can be introduced to modify the film properties. For example, Bis(iso-propylamino)vinylmethylsilane (BIPAVMS) (FIG. 1 A) or Bis(iso-propylamino)divinylsilane (BIPADVS) (FIG. 1 B) and ammonia are introduced into a PECVD chamber and allowed to react, resulting in the deposition of a compressively stressed SiN thin film. A suitable BIPAVMS flow rate may range from 50 to about 1000 mg/min. A suitable ammonia and/or nitrogen flow rate may range from 500 to 10,000 sccm, and the diluent gases can range from 50 to 50,000 sccm.
    • Example
  • Depositions conditions for Runs A-F and the corresponding film stress obtained in Table 1, below, are as follows. Deposition temperature was 400 C. In these examples, properties were obtained from sample films that were deposited onto medium resistivity (8-12 Ωcm) single crystal silicon wafer substrates. All depositions were performed on an Applied Materials Precision 5000 system in a 200 mm DXZ chamber fitted with an Advanced Energy 2000 RF generator. The plasma is single frequency of 13.56 MHz.
  • In the Table 1 examples, thickness and optical properties, such as refractive index of the dielectric films, were measured on an SCI Filmtek Reflectometer. The refractive index is measured using 632 nm wavelength light. Fourier Infrared Spectroscopy (FTIR) data was collected on the wafers using a Thermo Nicolet 750 system in a nitrogen purged cell. Background spectra were collected on similar medium resistivity wafers to eliminate CO2 and water from the spectra. Data was obtained in the range of from 4000 to 400 cm−1 by collecting 32 scans with a resolution of 4 cm−1. The OMNIC software package was used to process the data. Film stress measurements were made using a laser beam scattering tool (Toho Technology Corp., Model: FLX2320S).
  • TABLE 1
    BIPAVMS flow NH3 P Power Stress
    Film (mg/min) (sccm) (Torr) (W) (MPa)
    A 250 2500 2.5 400 −1849
    B 250 1250 2.5 400 −934
    C 250 2500 4 400 −757
    D 250 2500 2.5 600 −2249
    E 125 2500 2.5 400 −2357
    F 125 2500 2.5 600 −2260
  • Film stress data of silicon nitride films deposited at 400° C. using Bis(iso-propylamino)vinylmethylsilane and ammonia is shown in FIG. 2. The films were deposited under various process conditions, such as precursor and gas flow rate, pressure, and RF power. The films were single layer, with thicknesses ranging from 100 to 350 nm. The plasma was generated using a single frequency of 13.56 MHz. The compressive stress of these films ranged from −700 to −2400 mega pascales (MPa). These films produced ˜1.5 to 1.8× higher compressive stress, than BTBAS under comparable process conditions.
  • FIG. 3 shows the FTIR spectra of films from FIG. 2 with the lowest (Film C) and highest (Film E) compressive stress. Both films exhibit NHx stretching and bending modes of similar intensity. However, there is a distinct difference in the SiH peak at ˜2190 cm−1, thus suggesting the main difference is in whether hydrogen is bonded to nitrogen or silicon.
  • FIG. 4 depicts the correlation between the ratio of NHx to SiH with stress. As can be seen from this figure, stress increases with higher NHx to SiH ratio. Preferably, the deposited thin film has a N—H to Si—H ratio of 25 to 85, most preferably 70.
  • FIG. 5 depicts the correlation of nitrogen bonded hydrogen (NHx) to stress and silicon bonded hydrogen to stress. This data indicates that reduction of SiH groups in addition to high levels of NHx moiety is important in generating high levels of compressive stress. Hydrogen contents derived from NHx moieties increase compressive stress in the range of 2.9 to 3.5 H content/cm3×1022, preferably 3.3 to 3.6 H content/cm3×1022
  • Experimental data indicate that films possessing higher stress values were found not to contain carbon. It is inferred that the carbon is etched away by the ammonia, which is in high excess compared to the precursor. In higher stress SiN films, more Si—H bonds are removed by the hydrosilylation of vinyl group, and replaced with N—H by the removal of ethylene bridge by ammonia.
    • Example 2
  • Under process condition A listed in Table 1, the stress of films using non-vinyl precursor (such as BTBAS) is lower than that for (BIPAVMS)
  • TABLE 2
    Thickness Dep. Rate Stress
    Precursor (nm) (nm/min) RI (MPa)
    BIPAVMS 208 13.9 1.97 −1849
    BTBAS 136 13.6 1.97 −1034
    • Example 3
  • Under process condition A listed in Table 1, but an alternative tool and showerhead configuration, the stress of films deposited increases as the number of vinyl groups increases in precursor.
  • TABLE 3
    Precursor Vinyl groups Stress (MPa)
    BIPAVMS 1 −1200
    BIPADVS 2 −1705

Claims (22)

1. A method to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) of silicon nitride (SiN) and silicon carbonitride (SiCN) thin films, comprising depositing the film from an amino vinylsilane-based precursor.
2. The method of claim 1 wherein the amino vinylsilane-based precursor is selected from the formula: [RR1N]xSiR3 y(R2)z
where x+y+z=4, x=1-3, y=0-2, and z=1-3; R, R1 and R3 can be hydrogen, C1 to C10 alkane, alkene, or C4 to C12 aromatic; each R2 is a vinyl, allyl or vinyl-containing functional group.
3. The method of claim 2 wherein the amino vinylsilane based precursor is selected from the group consisting of Bis(iso-propylamino)vinylmethylsilane (BIPAVMS), Bis(iso-propylamino)divinylsilane (BIPADVS) and mixtures thereof.
4. The method of claim 1 wherein the compressively stressed films have a compressive stress of −4 GPa or higher.
5. The method of claim 1 wherein a nitrogen containing reactant is reacted with the amino vinylsilane-based precursor.
6. The method of claim 5 wherein the nitrogen containing reactant is selected from the group consisting of ammonia, nitrogen and mixtures thereof.
7. The method of claim 1 wherein the deposition is conducted at an elevated temperature at or below 500° C.
8. The method of claim 1 wherein the deposition is conducted in the presence of a diluent gas selected from the group consisting of helium, argon, neon, xenon and mixtures thereof.
9. The method of claim 1 wherein the flow rate of the amino vinylsilane-based precursor is 50 to 1000 mg/min.
10. The method of claim 5 wherein the flow rate of the nitrogen containing reactant is 500 to 10,000 mg/min.
11. The method of claim 8 wherein the flow rate of the diluents gas is 50 to 50,000 mg/min.
12. The method of claim 1 wherein the deposited thin film has a compressive stress of −700 to −2400 MPa.
13. The method of claim 1 wherein the deposited thin film has a N—H to Si—H ratio of 25 to 85.
14. The method of claim 1 wherein the deposited thin film has a N—H derived H content/cm3×1022 in the range of 3.3 to 3.6.
15. The method of claim 1 wherein the deposited thin film has a compressive stress of −700 to −4500 MPa.
16-18. (canceled)
19. A method for depositing a film selected from a silicon nitride film or a silicon carbonitride film comprising:
reacting a nitrogen-containing gas with a precursor having the general formula:

[RR1N]xSiR3 y(R2)z
where x+y+z=4, x=1-3, y=0-2, and z=1-3 and wherein R, R1 and R3 are individually selected from the group consisting of hydrogen, C1 to C10 alkane, O2 to C10 alkene, or C4 to C12 aromatic; R2 is selected from the group consisting of a vinyl, allyl or other vinyl-containing functional group and wherein when R2 is vinyl, x=2, y=0, and z=2, R and R1 cannot both be methyl to provide the film.
20. The precursor of claim 19 selected from the group consisting of Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)diallylsilane, Bis(t-butylamino)divinylsilane, Bis(t-butylamino)diallylsilane, Bis(diethylamino)diallylsilane, Bis(methyethylamino)diallylsilane, and Bis(methyethylamino)divinylsilane
21. A composition for depositing a film selected from a silicon nitride and a silicon carbonitride film comprising:
an aminosilane precursor which is at least one selected from the group consisting of Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylamino)vinylsilane, Bis(t-butylamino)allylmethylsilane, Bis(t-butylamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, and Dipyrrolidinoallylsilane.
22. The composition of claim 21 further comprising a nitrogen-containing gas.
23. The composition of claim 21 further comprising an inert gas.
24. A method for depositing a film selected from a silicon nitride film or a silicon carbonitride film comprising:
reacting a nitrogen-containing gas with an aminosilane precursor to provide the film wherein the amino silane precursor is at least one selected from the group consisting of Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylamino)vinylsilane, Bis(t-butylamino)allylmethylsilane, Bis(t-butylamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, and Dipyrrolidinoallylsilane.
US14/070,957 2008-11-12 2013-11-04 Amino Vinylsilane Precursors for Stressed SiN Films Abandoned US20140065844A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/070,957 US20140065844A1 (en) 2008-11-12 2013-11-04 Amino Vinylsilane Precursors for Stressed SiN Films

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11362408P 2008-11-12 2008-11-12
US12/609,542 US8580993B2 (en) 2008-11-12 2009-10-30 Amino vinylsilane precursors for stressed SiN films
US14/070,957 US20140065844A1 (en) 2008-11-12 2013-11-04 Amino Vinylsilane Precursors for Stressed SiN Films

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US12/609,542 Division US8580993B2 (en) 2008-11-12 2009-10-30 Amino vinylsilane precursors for stressed SiN films

Publications (1)

Publication Number Publication Date
US20140065844A1 true US20140065844A1 (en) 2014-03-06

Family

ID=41509788

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/609,542 Expired - Fee Related US8580993B2 (en) 2008-11-12 2009-10-30 Amino vinylsilane precursors for stressed SiN films
US14/070,957 Abandoned US20140065844A1 (en) 2008-11-12 2013-11-04 Amino Vinylsilane Precursors for Stressed SiN Films

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US12/609,542 Expired - Fee Related US8580993B2 (en) 2008-11-12 2009-10-30 Amino vinylsilane precursors for stressed SiN films

Country Status (6)

Country Link
US (2) US8580993B2 (en)
EP (2) EP2465861A1 (en)
JP (2) JP5175261B2 (en)
KR (2) KR101396139B1 (en)
CN (2) CN102491990B (en)
TW (2) TWI412622B (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8580993B2 (en) 2008-11-12 2013-11-12 Air Products And Chemicals, Inc. Amino vinylsilane precursors for stressed SiN films
US8889235B2 (en) * 2009-05-13 2014-11-18 Air Products And Chemicals, Inc. Dielectric barrier deposition using nitrogen containing precursor
US9997357B2 (en) 2010-04-15 2018-06-12 Lam Research Corporation Capped ALD films for doping fin-shaped channel regions of 3-D IC transistors
US8637411B2 (en) 2010-04-15 2014-01-28 Novellus Systems, Inc. Plasma activated conformal dielectric film deposition
US9257274B2 (en) 2010-04-15 2016-02-09 Lam Research Corporation Gapfill of variable aspect ratio features with a composite PEALD and PECVD method
US9892917B2 (en) 2010-04-15 2018-02-13 Lam Research Corporation Plasma assisted atomic layer deposition of multi-layer films for patterning applications
US9373500B2 (en) 2014-02-21 2016-06-21 Lam Research Corporation Plasma assisted atomic layer deposition titanium oxide for conformal encapsulation and gapfill applications
US8460753B2 (en) 2010-12-09 2013-06-11 Air Products And Chemicals, Inc. Methods for depositing silicon dioxide or silicon oxide films using aminovinylsilanes
US8647993B2 (en) * 2011-04-11 2014-02-11 Novellus Systems, Inc. Methods for UV-assisted conformal film deposition
US9447287B2 (en) * 2011-06-03 2016-09-20 Air Products And Chemicals, Inc. Compositions and processes for depositing carbon-doped silicon-containing films
JP6538300B2 (en) 2012-11-08 2019-07-03 ノベラス・システムズ・インコーポレーテッドＮｏｖｅｌｌｕｓ Ｓｙｓｔｅｍｓ Ｉｎｃｏｒｐｏｒａｔｅｄ Method for depositing a film on a sensitive substrate
US9564312B2 (en) 2014-11-24 2017-02-07 Lam Research Corporation Selective inhibition in atomic layer deposition of silicon-containing films
US10566187B2 (en) 2015-03-20 2020-02-18 Lam Research Corporation Ultrathin atomic layer deposition film accuracy thickness control
KR20170019668A (en) * 2015-08-12 2017-02-22 (주)디엔에프 The manufacturing method of the silicon nitride film by using plasma enhanced atomic layer deposition
US9773643B1 (en) 2016-06-30 2017-09-26 Lam Research Corporation Apparatus and method for deposition and etch in gap fill
US10062563B2 (en) 2016-07-01 2018-08-28 Lam Research Corporation Selective atomic layer deposition with post-dose treatment
WO2018016871A1 (en) * 2016-07-22 2018-01-25 (주)디엔에프 Method for manufacturing silicon nitride thin film using plasma atomic layer deposition
US10037884B2 (en) 2016-08-31 2018-07-31 Lam Research Corporation Selective atomic layer deposition for gapfill using sacrificial underlayer
US10269559B2 (en) 2017-09-13 2019-04-23 Lam Research Corporation Dielectric gapfill of high aspect ratio features utilizing a sacrificial etch cap layer
KR20210118284A (en) * 2020-03-19 2021-09-30 삼성디스플레이 주식회사 Display device
CN114447435A (en) * 2022-01-21 2022-05-06 恒实科技发展(南京)有限公司 Non-aqueous electrolyte for lithium secondary battery and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8580993B2 (en) * 2008-11-12 2013-11-12 Air Products And Chemicals, Inc. Amino vinylsilane precursors for stressed SiN films

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2854787B2 (en) * 1993-08-31 1999-02-03 信越化学工業株式会社 Method for producing silicone rubber composition
JP3430097B2 (en) 1999-12-22 2003-07-28 日本電気株式会社 Method of manufacturing thin film transistor array substrate
JP2002246381A (en) * 2001-02-15 2002-08-30 Anelva Corp Cvd method
JP2004223769A (en) * 2003-01-20 2004-08-12 Dainippon Printing Co Ltd Transparent laminated film, antireflection film, polarizing plate using the same and liquid crystal display device
US7122222B2 (en) 2003-01-23 2006-10-17 Air Products And Chemicals, Inc. Precursors for depositing silicon containing films and processes thereof
US7579496B2 (en) * 2003-10-10 2009-08-25 Advanced Technology Materials, Inc. Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same
JP2005310861A (en) 2004-04-19 2005-11-04 Mitsui Chemicals Inc Sintered silicon nitride film forming method
US7129187B2 (en) * 2004-07-14 2006-10-31 Tokyo Electron Limited Low-temperature plasma-enhanced chemical vapor deposition of silicon-nitrogen-containing films
US20060045986A1 (en) 2004-08-30 2006-03-02 Hochberg Arthur K Silicon nitride from aminosilane using PECVD
JP2006120992A (en) 2004-10-25 2006-05-11 C Bui Res:Kk Method for manufacturing silicon nitride film, and its manufacturing apparatus
US20060182885A1 (en) * 2005-02-14 2006-08-17 Xinjian Lei Preparation of metal silicon nitride films via cyclic deposition
JP2006294485A (en) 2005-04-13 2006-10-26 Konica Minolta Holdings Inc Organic electroluminescent element, its manufacturing method and display device
US7875556B2 (en) 2005-05-16 2011-01-25 Air Products And Chemicals, Inc. Precursors for CVD silicon carbo-nitride and silicon nitride films
US7732342B2 (en) * 2005-05-26 2010-06-08 Applied Materials, Inc. Method to increase the compressive stress of PECVD silicon nitride films
WO2006129773A1 (en) * 2005-05-31 2006-12-07 Toho Catalyst Co., Ltd. Aminosilane compounds, catalyst components and catalysts for olefin polymerization, and process for production of olefin polymers with the same
JP2007092166A (en) * 2005-09-02 2007-04-12 Japan Advanced Institute Of Science & Technology Hokuriku Apparatus and method for thin film deposition, and compound thin film
US20080142046A1 (en) * 2006-12-13 2008-06-19 Andrew David Johnson Thermal F2 etch process for cleaning CVD chambers
US7790635B2 (en) * 2006-12-14 2010-09-07 Applied Materials, Inc. Method to increase the compressive stress of PECVD dielectric films
JPWO2008096616A1 (en) 2007-02-05 2010-05-20 コニカミノルタホールディングス株式会社 Transparent gas barrier film and method for producing the same
JP5391557B2 (en) * 2007-02-28 2014-01-15 住友化学株式会社 Conjugated diene polymer, process for producing conjugated diene polymer, and conjugated diene polymer composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8580993B2 (en) * 2008-11-12 2013-11-12 Air Products And Chemicals, Inc. Amino vinylsilane precursors for stressed SiN films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Aoki et al. Journal of polymer science: Part A: Polymer Chemistry, 1997, 35, 2827-2833 *

Also Published As

Publication number Publication date
TW201211303A (en) 2012-03-16
JP5508496B2 (en) 2014-05-28
KR101553863B1 (en) 2015-09-17
CN102491990B (en) 2015-12-09
JP2010118664A (en) 2010-05-27
EP2465861A1 (en) 2012-06-20
JP2013016859A (en) 2013-01-24
KR20130016171A (en) 2013-02-14
US8580993B2 (en) 2013-11-12
JP5175261B2 (en) 2013-04-03
US20100120262A1 (en) 2010-05-13
CN101899651A (en) 2010-12-01
TWI412622B (en) 2013-10-21
EP2192207B1 (en) 2012-06-20
EP2192207A1 (en) 2010-06-02
KR20100053471A (en) 2010-05-20
KR101396139B1 (en) 2014-05-19
CN101899651B (en) 2012-12-26
CN102491990A (en) 2012-06-13
TW201018741A (en) 2010-05-16
TWI437117B (en) 2014-05-11

Similar Documents

Publication Publication Date Title
US8580993B2 (en) Amino vinylsilane precursors for stressed SiN films
KR101640153B1 (en) Non-oxygen containing silicon-based films and methods of forming the same
US6572923B2 (en) Asymmetric organocyclosiloxanes and their use for making organosilicon polymer low-k dielectric film
TWI660961B (en) Precursors and flowable cvd methods for making low-k films to fill surface features
US6303047B1 (en) Low dielectric constant multiple carbon-containing silicon oxide dielectric material for use in integrated circuit structures, and method of making same
CN100437933C (en) Method of improving interlayer adhesion
US8802882B2 (en) Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films
US20030194496A1 (en) Methods for depositing dielectric material
KR101144535B1 (en) Dielectric barrier deposition using nitrogen containing precursor
CN102460679A (en) Boron film interface engineering
US7326444B1 (en) Methods for improving integration performance of low stress CDO films
US20180371612A1 (en) Low Temperature Process for Forming Silicon-Containing Thin Layer
EP2302667A1 (en) Insulating film for semiconductor device, process and apparatus for producing insulating film for semiconductor device, semiconductor device, and process for producing the semiconductor device
JP5731841B2 (en) Method for forming silicon nitride film
US20220388033A1 (en) Precursors for depositing films with high elastic modulus
US20230386825A1 (en) Alkoxydisiloxanes and dense organosilica films made therefrom
Cho et al. A Study Of The Characteristics Of Organic–Inorganic Hybrid Plasma-Polymer Thin Films By Co-Deposition Of Toluene And Teos

Legal Events

Date Code Title Description
AS Assignment

Owner name: AIR PRODUCTS AND CHEMICALS, INC., PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VORSA, VASIL;JOHNSON, ANDREW DAVID;XIAO, MANCHAO;SIGNING DATES FROM 20140616 TO 20140806;REEL/FRAME:033507/0259

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: VERSUM MATERIALS US, LLC, ARIZONA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AIR PRODUCTS AND CHEMICALS, INC.;REEL/FRAME:041772/0733

Effective date: 20170214