WO2010047869A1 - Cvd precursors - Google Patents

Cvd precursors Download PDF

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Publication number
WO2010047869A1
WO2010047869A1 PCT/US2009/053364 US2009053364W WO2010047869A1 WO 2010047869 A1 WO2010047869 A1 WO 2010047869A1 US 2009053364 W US2009053364 W US 2009053364W WO 2010047869 A1 WO2010047869 A1 WO 2010047869A1
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WIPO (PCT)
Prior art keywords
bisaminosilacyclobutane
providing gas
gas
film
nitrogen
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Ceased
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PCT/US2009/053364
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French (fr)
Inventor
Xiaobing Zhou
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.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
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Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Priority to EP20090822363 priority Critical patent/EP2373830B1/en
Priority to JP2011532103A priority patent/JP5491512B2/en
Priority to KR1020167005023A priority patent/KR101639432B1/en
Priority to US13/122,745 priority patent/US8772524B2/en
Priority to CN200980141783.2A priority patent/CN102187011B/en
Publication of WO2010047869A1 publication Critical patent/WO2010047869A1/en
Anticipated expiration legal-status Critical
Priority to US14/280,770 priority patent/US9117664B2/en
Ceased legal-status Critical Current

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    • 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
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
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    • 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
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    • 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
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • 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
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    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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    • 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
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    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
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    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/6903—Inorganic materials containing silicon
    • H10P14/6905—Inorganic materials containing silicon being a silicon carbide or silicon carbonitride and not containing oxygen, e.g. SiC or SiC:H
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    • H10P14/6336—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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    • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
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    • H10P14/6687—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
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Definitions

  • PECVD Plasma Enhanced Chemical Vapor Deposition
  • thermal silicon nitrides or silicon carbonitrides have been used as dielectrics, passivation coating, barrier coating, spacers, liners or stressors in semiconductor devices. Limited by tight thermal budget and heat sensitive components in devices, the semiconductor fabrication industry are looking for new precursors allowing deposition of these films at decreasing temperatures. It is projected that the film deposition temperature could be as low as 400 to 450 0 C at 22 nm tech node when the mass production starts. To allow the films to be deposited at such a low temperature, the precursors need to decompose at nearly 200 0 C and, meanwhile, still meet the requirement for shelf stability.
  • hydrazinosilanes developed by Air Products. It has been disclosed that bis( 1,1 -dimethylhydrazino)ethylsilane, HEtSi(NH-NMe 2 ) 2 , gives 15 A/min film growth rate at 370 0 C in ammonia.
  • the 1,1-dimethylhydrazino ligand containing a weak N-N bond is known to decompose below 200 0 C on a silicon surface.
  • the silicon carbonitride films deposited from hydrazinosilanes had the problem of low density.
  • Bisaminosilacyclobutanes are proposed as a new family of precursors for low temperature deposition of silicon containing films. These molecules have a strained four- membered silacyclobutane ring which may decompose at a low temperature. However because bisaminosilacyclobutanes decompose through different mechanisms than hydrazinosilanes, bisaminosilacyclobutanes are expected to give superior thin film properties. Bisaminosilacyclobutanes have been prepared in 99+% purity, and found to decompose at 200 to 250 0 C.
  • the invention pertains to a method of producing silicon containing thin films by the thermal polymerization of a reactive gas mixture comprising bisaminosilacyclobutane and source gas selected from a nitrogen providing gas, an oxygen providing gas and mixtures thereof.
  • the films deposited may be silicon nitride, silicon carbonitride, silicon dioxide or carbon doped silicon dioxide. These films are useful as dielectrics, passivation coatings, barrier coatings, spacers, liners and/or stressors in semiconductor devices.
  • FIG 1 shows the process for the deposition of silicon carbonitride film in a Low Pressure CVD reactor using bis(t-butylamino)silacyclobutane (BTBSCB).
  • BTBSCB bis(t-butylamino)silacyclobutane
  • This invention pertains to a method for producing silicon containing films on a substrate wherein the film may be silicon nitride, silicon carbonitride, silicon dioxide or carbon doped silicon dioxide.
  • Typical substrates include but are not limited to, semiconductor substrates, liquid crystal devices, a light emitting diode display device, and an organic light emitting display device.
  • semiconductor substrate it is meant to include, but not be limited to, silicon based devices and gallium arsenide based devices intended for use in the manufacture of a semiconductor components including focal plane arrays, opto-electronic devices, photovoltaic cells, optical devices, transistor-like devices, 3-D devices, silicon-on- insulator devices, super lattice devices and the like.
  • the semiconductor substrates may contain one or more layers of wiring. The semiconductor substrate may also be those substrates prior to the formation of any wiring layers.
  • each R , R , R R , R and R is independently selected from hydrogen or monovalent hydrocarbon (linear, branched or cyclic; saturated or unsaturated) groups having 1 to 6 carbons and m, n have a value of 0 to 10.
  • Each R , R , R R , R and R may be exemplified by, but not limited to methyl, ethyl, propyl, iso-propyl, n-butyl, sec -butyl, t-butyl, cyclohexyl, cyclopropyl, phenyl, vinyl, hexenyl and others.
  • Bisaminosilacyclobutanes useful herein may be exemplified by compounds having the formulas
  • the reactive gas mixture used to produce the films may also comprise a controlled amount of a source gas selected from a nitrogen providing gas, an oxygen providing gas or mixtures thereof.
  • the amount of source gas may be controlled by the type of gas used, or by the film deposition process conditions.
  • Nitrogen providing gases include, but are not limited to nitrogen N 2 , ammonia NH3, hydrazine N 2 H4, hydrazoic acid HN3, and mixtures thereof.
  • the nitrogen providing gas is ammonia, although hydrazine and hydrazoic acid may be used for low temperature deposition.
  • the amount of nitrogen providing gas is typically 0.1 to 50 volume parts nitrogen providing gas per volume part of bisaminosilacyclobutane, alternatively from 0.2 to 7 volume parts of nitrogen providing gas per volume part of bisaminosilacyclobutane.
  • One skilled in the art will be able to readily determine the amount of nitrogen providing gas based on the type of nitrogen providing gas and the deposition conditions.
  • Oxygen providing gases include but not limited to oxygen, air, nitrous oxide, nitric oxide, carbon monoxide, peroxides, sulfur dioxide and mixtures thereof.
  • the amount of nitrogen providing gas is typically 0.1 to 50 volume parts oxygen providing gas per volume part of bisaminosilacyclobutane, alternatively from 0.2 to 7 volume parts of oxygen providing gas per volume part of bisaminosilacyclobutane.
  • One skilled in the art will be able to readily determine the amount of oxygen providing gas based on the type of oxygen providing gas and the deposition conditions.
  • the reactive gas mixture is introduced into a deposition chamber containing a substrate, preferably a semiconductor substrate, wherein the polymerization of the bisaminosilacyclobutane is induced resulting in the deposition of a film on the substrate.
  • Thermal chemical vapor deposition such as Low Pressure Chemical Vapor Deposition (LPCVD) or Atomic Layer Deposition (ALD) is preferred due to the low temperatures that can be used and wide use in the industry.
  • Plasma-assisted CVD may also be used to deposit silicon dioxide or carbon doped silicon oxide films from bisaminosilacyclobutanes with or without an oxygen providing gas, or silicon nitride or carbonitride films from bisaminosilacyclobutane with or without a nitrogen providing gas.
  • PECVD the gas mixture is reacted by passing it through a plasma field.
  • the plasmas used in such processes comprise energy derived from a variety of sources such as electric discharges, electromagnetic fields in the radio frequency or microwave range, lasers or particle beams.
  • radio frequency 10 kHz to 10 ⁇ MHz
  • microwave (1.0 to 10 GHz) energy at moderate power densities (0.1 to 5 watts/cm ⁇ ).
  • the specific frequency, power and pressure are generally tailored to the equipment.
  • the films are deposited using PECVD at a power of 20 to 1000 W; a pressure of 0.13 to 1333 Pa; and a temperature of 25 to 500 0 C.
  • Confined, low pressure (0.13-0.65 Pa) microwave frequency plasmas often referred to as high density plasmas, can be combined with a RF frequency excitation in a process which helps planarize a varying surface topography during CVD growth.
  • One type of film that may be deposited herein is a silicon carbonitride film. These films typically have the formula Si w C ⁇ H y N z wherein the ratio of C:Si can be in the range of about 0: 1 to about 10:1 and the ratio of N:Si can be in the range of about 0: 1 to about 1.5:1 with the balance being hydrogen.
  • the co-reactant is a nitrogen providing gas. It is theorized that when the film is deposited from bisaminosilacyclobutane and nitrogen providing gas, the amino groups are replaced with nitrogen source gas through transamination, and the silacyclobutane groups decompose to release gaseous organic species.
  • the amount of bisaminosilacyclobutane to nitrogen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 parts of nitrogen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of nitrogen providing gas.
  • Another type of film that may be deposited herein is a silicon nitride film. These films typically have the formula SibH c N d wherein the ratio of H:Si can be in the range of about 0: 1 to about 5:1 and the ratio of N:Si can be in the range of about 0: 1 to about 1.5: 1.
  • These films are typically deposited using a nitrogen providing gas as the co-reactant.
  • the amount of bisaminosilacyclobutane to nitrogen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 parts of nitrogen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of nitrogen providing gas.
  • Another type of film that may be deposited herein is a silicon oxide film. These films typically have the formula SiO x where x is from 0 to 3. These films are typically deposited using an oxygen providing gas as the co-reactant.
  • the amount of bisaminosilacyclobutane to oxygen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 part of oxygen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of oxygen providing gas.
  • a fourth type of film that may be deposited herein is a carbon doped silicon dioxide film.
  • These films are typically deposited using an oxygen providing gas as the co-reactant.
  • the amount of bisaminosilacyclobutane to oxygen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 parts of oxygen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of oxygen providing gas.
  • the films deposited herein may be of varying thicknesses. Films having thicknesses of 0.01 to 10 ⁇ m may be deposited by the method of this invention. Alternatively, the films have a thickness of 0.5 to 3.0 ⁇ m. [0021] The films deposited herein, are particularly suited as dielectrics or barrier metal coatings in semiconductor integrated circuit manufacturing including, but not limited to, gate dielectrics, premetal and intermetal dielectrics and passivation coatings. [0022] Figure 1 shows the typical process for the deposition of a silicon nitride or carbonitride thin film from bisaminosilacyclobutanes.
  • wafer substrates are loaded into a Low Pressure CVD (LPCVD) reactor and the LPCVD reactor is heated to a target temperature, and evacuated below 10 "4 torr.
  • Ammonia gas is mixed with diluting nitrogen gas, and the mixed NH3-N2 gas is then metered into the LPCVD reactor.
  • Nitrogen carrier gas is flowed through the sample cylinder containing liquid BTBSCB. The vapor of BTBSCB carried in nitrogen is metered into the LPCVD reactor.
  • the LPCVD reactor is cooled down and backfilled with nitrogen up to atmospheric pressure. Finally the coated wafer is removed from the LPCVD reactor.
  • the bisaminosilacyclobutanes produced in Examples 1-3 were analyzed with Differential Scanning Calorimetry (DSC). Thermal decomposition of the molecules starts at the temperature where the exotherm curves start to ramp on the DSC spectra.
  • the thermal decomposition temperatures were determined to be 200 0 C, 200 0 C and 250 0 C for bis(t- butylamino)silacyclobutane (BTBSCB), bis(ethylamino)silacyclobutane and bis(pyrrolidino)silacyclobutane respectively.
  • BBSCB bis(t- butylamino)silacyclobutane
  • the DSC samples that had gone through the thermal treatment were analyzed with GC-MS to confirm the decomposition of these materials.
  • the decomposition of BTBSCB was further verified with headspace GC run at 200 0 C and 295°C.

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Abstract

A method of producing silicon containing thin films by the thermal polymerization of a reactive gas mixture bisaminosilacyclobutane and source gas selected from a nitrogen providing gas, an oxygen providing gas and mixtures thereof. The films deposited may be silicon nitride, silicon carbonitride, silicon dioxide or carbon doped silicon dioxide. These films are useful as dielectrics, passivation coatings, barrier coatings, spacers, liners and/or stressors in semiconductor devices.

Description

CVD PRECURSORS
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] None
BACKGROUND OF THE INVENTION
[0002] Thin films of silicon dioxide and carbon doped silicon oxide are common dielectrics used in fabrication of semiconductor devices. Deposition of the thin films of these materials at low temperatures is typically achieved with Plasma Enhanced Chemical Vapor Deposition (PECVD) process. However, due to concern over potential plasma damage to transistors, a low temperature process is preferred in some circumstances.
[0003] Thermal silicon nitrides or silicon carbonitrides have been used as dielectrics, passivation coating, barrier coating, spacers, liners or stressors in semiconductor devices. Limited by tight thermal budget and heat sensitive components in devices, the semiconductor fabrication industry are looking for new precursors allowing deposition of these films at decreasing temperatures. It is projected that the film deposition temperature could be as low as 400 to 4500C at 22 nm tech node when the mass production starts. To allow the films to be deposited at such a low temperature, the precursors need to decompose at nearly 200 0C and, meanwhile, still meet the requirement for shelf stability. Perhaps the only silane precursors that have been demonstrated thus far to have such a low thermal decomposition temperature and a good shelf life are the hydrazinosilanes developed by Air Products. It has been disclosed that bis( 1,1 -dimethylhydrazino)ethylsilane, HEtSi(NH-NMe2)2, gives 15 A/min film growth rate at 370 0C in ammonia. The 1,1-dimethylhydrazino ligand containing a weak N-N bond is known to decompose below 2000C on a silicon surface. However, the silicon carbonitride films deposited from hydrazinosilanes had the problem of low density. [0004] Bisaminosilacyclobutanes are proposed as a new family of precursors for low temperature deposition of silicon containing films. These molecules have a strained four- membered silacyclobutane ring which may decompose at a low temperature. However because bisaminosilacyclobutanes decompose through different mechanisms than hydrazinosilanes, bisaminosilacyclobutanes are expected to give superior thin film properties. Bisaminosilacyclobutanes have been prepared in 99+% purity, and found to decompose at 200 to 2500C.
BRIEF SUMMARY OF THE INVENTION [0005] The invention pertains to a method of producing silicon containing thin films by the thermal polymerization of a reactive gas mixture comprising bisaminosilacyclobutane and source gas selected from a nitrogen providing gas, an oxygen providing gas and mixtures thereof. The films deposited may be silicon nitride, silicon carbonitride, silicon dioxide or carbon doped silicon dioxide. These films are useful as dielectrics, passivation coatings, barrier coatings, spacers, liners and/or stressors in semiconductor devices.
BRIEF DESCRIPRTION OF THE DRAWINGS
[0006] FIG 1 shows the process for the deposition of silicon carbonitride film in a Low Pressure CVD reactor using bis(t-butylamino)silacyclobutane (BTBSCB).
DETAILED DESCRPTION OF THE INVENTION
[0007] This invention pertains to a method for producing silicon containing films on a substrate wherein the film may be silicon nitride, silicon carbonitride, silicon dioxide or carbon doped silicon dioxide. Typical substrates include but are not limited to, semiconductor substrates, liquid crystal devices, a light emitting diode display device, and an organic light emitting display device. By "semiconductor substrate" it is meant to include, but not be limited to, silicon based devices and gallium arsenide based devices intended for use in the manufacture of a semiconductor components including focal plane arrays, opto-electronic devices, photovoltaic cells, optical devices, transistor-like devices, 3-D devices, silicon-on- insulator devices, super lattice devices and the like. The semiconductor substrates may contain one or more layers of wiring. The semiconductor substrate may also be those substrates prior to the formation of any wiring layers.
[0008] Bisaminosilacyclobutanes useful herein are selected from compounds having the formulas and mixtures thereof (CH9)n
R1R2
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000004_0003
R1R2 —(CH9)n- - R3R4
Figure imgf000004_0005
Figure imgf000004_0004
Figure imgf000004_0006
RiR2 N- NR3R4
Figure imgf000005_0001
Figure imgf000005_0002
where each R , R , R R , R and R is independently selected from hydrogen or monovalent hydrocarbon (linear, branched or cyclic; saturated or unsaturated) groups having 1 to 6 carbons and m, n have a value of 0 to 10. Each R , R , R R , R and R may be exemplified by, but not limited to methyl, ethyl, propyl, iso-propyl, n-butyl, sec -butyl, t-butyl, cyclohexyl, cyclopropyl, phenyl, vinyl, hexenyl and others. [0009] Bisaminosilacyclobutanes useful herein may be exemplified by compounds having the formulas
Figure imgf000005_0003
i-PrHN
Figure imgf000005_0004
HPr-i
Figure imgf000006_0001
[0010] The reactive gas mixture used to produce the films may also comprise a controlled amount of a source gas selected from a nitrogen providing gas, an oxygen providing gas or mixtures thereof. The amount of source gas may be controlled by the type of gas used, or by the film deposition process conditions.
[0011] Nitrogen providing gases include, but are not limited to nitrogen N2, ammonia NH3, hydrazine N2H4, hydrazoic acid HN3, and mixtures thereof. Typically the nitrogen providing gas is ammonia, although hydrazine and hydrazoic acid may be used for low temperature deposition. The amount of nitrogen providing gas is typically 0.1 to 50 volume parts nitrogen providing gas per volume part of bisaminosilacyclobutane, alternatively from 0.2 to 7 volume parts of nitrogen providing gas per volume part of bisaminosilacyclobutane. One skilled in the art will be able to readily determine the amount of nitrogen providing gas based on the type of nitrogen providing gas and the deposition conditions.
[0012] Oxygen providing gases include but not limited to oxygen, air, nitrous oxide, nitric oxide, carbon monoxide, peroxides, sulfur dioxide and mixtures thereof. The amount of nitrogen providing gas is typically 0.1 to 50 volume parts oxygen providing gas per volume part of bisaminosilacyclobutane, alternatively from 0.2 to 7 volume parts of oxygen providing gas per volume part of bisaminosilacyclobutane. One skilled in the art will be able to readily determine the amount of oxygen providing gas based on the type of oxygen providing gas and the deposition conditions.
[0013] Other materials may be present in the reactive gas mixture. For example, carrier gases such as helium, nitrogen, or argon, dopants such as phosphine or diborane, halogens such as fluorine, halogen-containing gases such as S1F4, CF4, C3F6 and C4F8, or any other material that provides additional desirable properties to the film may be present. [0014] The reactive gas mixture is introduced into a deposition chamber containing a substrate, preferably a semiconductor substrate, wherein the polymerization of the bisaminosilacyclobutane is induced resulting in the deposition of a film on the substrate. Thermal chemical vapor deposition such as Low Pressure Chemical Vapor Deposition (LPCVD) or Atomic Layer Deposition (ALD) is preferred due to the low temperatures that can be used and wide use in the industry. Plasma-assisted CVD may also be used to deposit silicon dioxide or carbon doped silicon oxide films from bisaminosilacyclobutanes with or without an oxygen providing gas, or silicon nitride or carbonitride films from bisaminosilacyclobutane with or without a nitrogen providing gas. [0015] In PECVD the gas mixture is reacted by passing it through a plasma field. The plasmas used in such processes comprise energy derived from a variety of sources such as electric discharges, electromagnetic fields in the radio frequency or microwave range, lasers or particle beams. Generally preferred in the plasma deposition processes is the use of radio frequency (10 kHz to 10^MHz) or microwave (1.0 to 10 GHz) energy at moderate power densities (0.1 to 5 watts/cm^). The specific frequency, power and pressure, however are generally tailored to the equipment. Preferably the films are deposited using PECVD at a power of 20 to 1000 W; a pressure of 0.13 to 1333 Pa; and a temperature of 25 to 5000C. Confined, low pressure (0.13-0.65 Pa) microwave frequency plasmas, often referred to as high density plasmas, can be combined with a RF frequency excitation in a process which helps planarize a varying surface topography during CVD growth. [0016] One type of film that may be deposited herein is a silicon carbonitride film. These films typically have the formula SiwCχHyNz wherein the ratio of C:Si can be in the range of about 0: 1 to about 10:1 and the ratio of N:Si can be in the range of about 0: 1 to about 1.5:1 with the balance being hydrogen. To deposit a silicon carbonitride film, the co-reactant is a nitrogen providing gas. It is theorized that when the film is deposited from bisaminosilacyclobutane and nitrogen providing gas, the amino groups are replaced with nitrogen source gas through transamination, and the silacyclobutane groups decompose to release gaseous organic species. It is therefore expected that the C:Si ratio in the film would be very different from the C: Si ratio in the precursor. The amount of bisaminosilacyclobutane to nitrogen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 parts of nitrogen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of nitrogen providing gas. [0017] Another type of film that may be deposited herein is a silicon nitride film. These films typically have the formula SibHcNd wherein the ratio of H:Si can be in the range of about 0: 1 to about 5:1 and the ratio of N:Si can be in the range of about 0: 1 to about 1.5: 1. These films are typically deposited using a nitrogen providing gas as the co-reactant. The amount of bisaminosilacyclobutane to nitrogen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 parts of nitrogen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of nitrogen providing gas. [0018] Another type of film that may be deposited herein is a silicon oxide film. These films typically have the formula SiOx where x is from 0 to 3. These films are typically deposited using an oxygen providing gas as the co-reactant. The amount of bisaminosilacyclobutane to oxygen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 part of oxygen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of oxygen providing gas.
[0019] A fourth type of film that may be deposited herein is a carbon doped silicon dioxide film. The films deposited typically have the composition of SIeCfOgHj1 where e has a value of 10 to 33, alternatively 18 to 20 atomic %, f has a value of 1 to 66, alternatively 18 to 21 atomic %, g has a value of 1 to 66, alternatively 31 to 38 atomic % and h has a value of 0.1 to 60, alternatively 25 to 32 atomic %; and e + f + g + h = 100 atomic %. These films are typically deposited using an oxygen providing gas as the co-reactant. The amount of bisaminosilacyclobutane to oxygen providing gas is in the range of 1 part of bisaminosilacyclobutane to 100 parts of oxygen providing gas, alternatively 1 part of bisaminosilacyclobutane to 10 parts of oxygen providing gas.
[0020] The films deposited herein may be of varying thicknesses. Films having thicknesses of 0.01 to 10 μm may be deposited by the method of this invention. Alternatively, the films have a thickness of 0.5 to 3.0 μm. [0021] The films deposited herein, are particularly suited as dielectrics or barrier metal coatings in semiconductor integrated circuit manufacturing including, but not limited to, gate dielectrics, premetal and intermetal dielectrics and passivation coatings. [0022] Figure 1 shows the typical process for the deposition of a silicon nitride or carbonitride thin film from bisaminosilacyclobutanes. In this process, wafer substrates are loaded into a Low Pressure CVD (LPCVD) reactor and the LPCVD reactor is heated to a target temperature, and evacuated below 10"4 torr. Ammonia gas is mixed with diluting nitrogen gas, and the mixed NH3-N2 gas is then metered into the LPCVD reactor. Nitrogen carrier gas is flowed through the sample cylinder containing liquid BTBSCB. The vapor of BTBSCB carried in nitrogen is metered into the LPCVD reactor. After films are deposited, the LPCVD reactor is cooled down and backfilled with nitrogen up to atmospheric pressure. Finally the coated wafer is removed from the LPCVD reactor.
EXAMPLES
[0023] The following examples are included to demonstrate embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention. However, those skilled in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. All percentages are in wt. %.
EXAMPLE 1 [0024] Bis(t-butylamino)silacyclobutane (BTBSCB) was synthesized by reacting 1,1- dichlorosilacyclobutane with an excess amount of t-butylamine (Equation 1). To do so, 19.7 ml (0.166 mol) lj-dichlorosilacyclobutane was added to 105 ml (0.999 mol) t-butylamine in 1 L hexanes at 0 0C. After bodying for three days at the room temperature, the reaction slurry was filtered to remove t-butylamine hydrochloride salt. The filtrant was vacuum dried to give a crude liquid product which was then vacuum distilled. 16 g Product was isolated at 99.2 % purity in 45 % yield at 71 0C under 50 torr pressure. The structure of the product analyzed with 1H, 13C and 29Si NMR, FT-IR and GC-MS was in consistence with bis(t- butylamino)silacyclobutane.
+ 4 X t-BuNH 2 X t-BuNH2.HCl
Figure imgf000010_0001
Figure imgf000010_0002
(Equation 1)
EXAMPLE 2
[0025] Bis(ethylamino)silacyclobutane was synthesized by reacting 1,1- dichlorosilacyclobutane with an excess amount of ethylamine (Equation 2). To do so, 20.0 ml (0.169 mol) 1,1 -dichlorosilacyclobutane was added to 66.2 ml (1.01 mol) ethylamine in 1 L pentane at -10 0C. After bodying for one day at the room temperature, the reaction slurry was filtered to remove ethylamine hydrochloride salt. The filtrant was vacuum dried to give a crude liquid product which was then vacuum distilled. 9.8 g Product was isolated at a purity of at least 99 % in 36 % yield at 42 0C under 30 torr pressure. The structure of the product analyzed with 1H, 13C and 29Si NMR, FT-IR and GC-MS was in consistence with bis(ethylamino)silacyclobutane.
Figure imgf000010_0003
(Equation 2)
EXAMPLE 3
[0026] Bis(pyrrolidino)silacyclobutane was synthesized by reacting 1,1- dichlorosilacyclobutane with an excess amount of pyrrolidine (Equation 3). To do so, 23.7 ml (0.200 mol) 1,1 -dichlorosilacyclobutane was added to 100.0 ml (1.20 mol) pyrrolidine in 1 L hexanes at -10 0C. After bodying for two day at the room temperature, the reaction slurry was filtered to remove pyrrolidine hydrochloride salt. The filtrant was vacuum dried to give a liquid crude product which was then vacuum distilled. 15.4 g Product was isolated at 99.7 % purity in 34 % yield at 51 0C under 1 torr pressure. The structure of the product analyzed with 1H, 13C and 29Si NMR, FT-IR and GC-MS was in consistence with bis(pyrrolidino)silacyclobutane.
+ 2 X (CH2)4NH.HC1
Figure imgf000011_0001
(Equation 3)
EXAMPLE 4: Determination of Thermal Decomposition Temperatures of Bisaminosilacyclobutanes.
[0027] The bisaminosilacyclobutanes produced in Examples 1-3 were analyzed with Differential Scanning Calorimetry (DSC). Thermal decomposition of the molecules starts at the temperature where the exotherm curves start to ramp on the DSC spectra. The thermal decomposition temperatures were determined to be 2000C, 2000C and 2500C for bis(t- butylamino)silacyclobutane (BTBSCB), bis(ethylamino)silacyclobutane and bis(pyrrolidino)silacyclobutane respectively. The DSC samples that had gone through the thermal treatment were analyzed with GC-MS to confirm the decomposition of these materials. The decomposition of BTBSCB was further verified with headspace GC run at 2000C and 295°C.

Claims

Claims:
1. A method for producing silicon containing films on a substrate wherein the method comprises the thermal polymerization of a reactive gas mixture comprising bisaminosilacyclobutane and source gas selected from a nitrogen providing gas, an oxygen providing gas and mixtures thereof.
2. The method as claimed in claim 1 wherein the bisaminosilacyclobutane is selected from
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000013_0001
RiR2 N- R3R4
Figure imgf000013_0002
Figure imgf000013_0003
where each R , R , R R , R and R is independently selected from hydrogen or monovalent hydrocarbon group having 1 to 6 carbons and m, n have a value of 0 to 10.
3. The method as claimed in claim 2 wherein the bisaminosilacyclobutane is Bis(t- butylamino)silacyclobutane.
4. The method as claimed in claim 2 wherein the bisaminosilacyclobutane is Bis(ethylamino)silacyclobutane.
5. The method as claimed in claim 2 wherein the bisaminosilacyclobutane is
Bis(pyrrolidino)silacyclobutane.
6. The method as claimed in claim 1 wherein the source gas is a nitrogen providing gas.
7. The method as claimed in claim 6 wherein the source gas is selected from nitrogen N2, ammonia NH3, hydrazine N2H4, hydrazoic acid HN3, and mixtures thereof.
8. The method as claimed in claim 6 wherein there is 0.1 to 50 volume parts of nitrogen providing gas per volume part of bisaminosilacyclobutane.
9. The method as claimed in claim 8 wherein there is 0.2 to 7 volume parts of nitrogen providing gas per volume part bisaminosilacyclobutane.
10. The method as claimed in claim 7 wherein the source gas is ammonia.
11. The method as claimed in claim 1 wherein the source gas is an oxygen providing gas.
12. The method as claimed in claim 11 wherein the source gas is selected from oxygen, air, nitrous oxide, nitric oxide, carbon monoxide, peroxides, sulfur dioxide and mixtures thereof.
13. The method as claimed in claim 11 wherein there is 0.1 to 50 volume parts of oxygen providing gas per volume part of bisaminosilacyclobutane.
14. The method as claimed in claim 11 wherein there is 0.2 to 7 volume parts of oxygen providing gas per volume part bisaminosilacyclobutane.
15. The method as claimed in claim 1 wherein there is also present a material selected from carrier gases, dopants, halogens and halogen-containing gases.
16. The method as claimed in claim 1 wherein the substrate is a semiconductor substrate.
17. The method as claimed in claim 1 wherein the thermal polymerization is carried out by low pressure chemical vapor deposition.
18. The method as claimed in claim 1 wherein the thermal polymerization is carried out by atomic layer deposition.
19. The method as claimed in claim 1 wherein the film deposited is a silicon carbonitride film.
20. The method as claimed in claim 1 wherein the film deposited is a silicon nitride film.
21. The method as claimed in claim 1 wherein the film deposited is a silicon oxide film.
22. The method as claimed in claim 1 wherein the film deposited is a carbon doped silicon dioxide film.
23. The method as claimed in claim 1 wherein the film deposited has a thickness of 0.01 to 10 μm.
24. A composition comprising Bis(ethylamino)silacyclobutane.
25. A composition comprising Bis(pyrrolidino)silacyclobutane.
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US8772524B2 (en) 2014-07-08
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US9117664B2 (en) 2015-08-25
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