WO2013112727A1 - Methods for uv-assisted conformal film deposition - Google Patents

Methods for uv-assisted conformal film deposition Download PDF

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Publication number
WO2013112727A1
WO2013112727A1 PCT/US2013/022977 US2013022977W WO2013112727A1 WO 2013112727 A1 WO2013112727 A1 WO 2013112727A1 US 2013022977 W US2013022977 W US 2013022977W WO 2013112727 A1 WO2013112727 A1 WO 2013112727A1
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reactant
silicon
nitrogen
vapor phase
phase flow
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French (fr)
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Adrien Lavoie
Bhadri Varadarajan
Jon Henri
Dennis Hausmann
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Novellus Systems Inc
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Novellus Systems Inc
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Priority to JP2014554825A priority Critical patent/JP2015510263A/ja
Priority to SG11201404315RA priority patent/SG11201404315RA/en
Priority to CN201380006994.1A priority patent/CN104081505A/zh
Publication of WO2013112727A1 publication Critical patent/WO2013112727A1/en
Anticipated expiration legal-status Critical
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    • 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
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • 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
    • C23C16/455—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]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • 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]
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6338—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition the reactions being activated by other means than plasma or thermal, e.g. photo-CVD
    • H—ELECTRICITY
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    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
    • 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
    • H10P14/6681—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
    • H10P14/6682—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 being a silane, e.g. disilane, methylsilane or chlorosilane
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
    • 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
    • H10P14/6681—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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/6922—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
    • H10P14/6922—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H10P14/6927—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/694—Inorganic materials composed of nitrides
    • H10P14/6943—Inorganic materials composed of nitrides containing silicon
    • H10P14/69433—Inorganic materials composed of nitrides containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz

Definitions

  • the present disclosure relates generally to formation of silicon-containing materials, including SiN, SiCN and SiC materials on substrates. More particularly, the disclosure relates to formation of silicon-containing films on semiconductor substrates.
  • SiN thin films have unique physical, chemical and mechanical properties and thus are used in a variety of applications, particularly semiconductor devices, for example in diffusion barriers, gate insulators, sidewall spacers, encapsulation layers, strained films in transistors, and the like.
  • One issue with SiN films is the relatively high temperatures used to form the films, for example, in Front End of Line (FEOL) applications, SiN films are typically deposited by chemical vapor deposition (CVD) in a reactor at greater than 750°C using dichlorosilane and ammonia.
  • CVD chemical vapor deposition
  • SiN silicon nitride
  • SiCN also referred to as SiNC
  • SiON silicon-containing films
  • the methods involve electromagnetic radiation-assisted activation of one or more reactants.
  • the methods involve ultraviolet (UV) activation of vapor phase amine coreactants.
  • UV ultraviolet
  • the methods can be used to deposit silicon- containing films, including SiN and SiCN films, at temperatures below about 400°C.
  • FIGURES 1 and 2 shows temporal progressions of phases in examples of deposition processes.
  • FIGURES 3 and 4 show example process flows for making a Si-containing film.
  • FIGURE 5 shows an example process flow for making a SiN film.
  • FIGURES 6-13 shows temporal progressions of phases in examples of SiN deposition processes.
  • FIGURE 14 depicts an example of a CFD processing station.
  • FIGURE 15 depicts an example of a schematic view of a multi-station processing tool.
  • the present disclosure relates to formation of silicon-containing films, including SiN, SiCN and SiC films, particularly on semiconductor substrates. Methods described herein include low temperature processes to deposit the films.
  • a "silicon-containing reactant” is a reagent, single or mixture of reagents, used to make a SiN, SiCN, SiC or other Si-containing material, where the reagent contains at least one silicon compound.
  • the silicon compound can be, for example, a silane, a halosilane or an aminosilane.
  • a silane contains hydrogen and/or carbon groups, but does not contain a halogen.
  • silanes examples include silane (SiH 4 ), disilane (Si 2 H 6 ), and organo silanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t- butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t- butyldisilane, and the like.
  • a halosilane contains at least one halogen group and may or may not contain hydrogens and/or carbon groups.
  • halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Although halosilanes, particularly fluorosilanes, may form reactive halide species that can etch silicon materials, in certain embodiments described herein, the silicon-containing reactant is not present when a plasma is struck.
  • chlorosilanes are tetrachlorosilane (S1CI 4 ), trichlorosilane (HS1CI 3 ), dichlorosilane (H 2 S1CI 2 ), monochlorosilane (CIS1H 3 ), chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t- butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, and the like.
  • aminosilane includes at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogens, oxygens, halogens and carbons.
  • aminosilanes are mono-, di-, tri- and tetra-aminosilane (H 3 Si(NI3 ⁇ 4)4, H 2 Si(NH 2 )2, HSi(NH 2 )3 and Si(NH 2 )4, respectively), as well as substituted mono-, di-, tri- and tetra-aminosilanes, for example, t-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tertiarybutylamino)silane (SiH 2 (NHC(CH 3 )3)2 (BTBAS), tert-butyl silylcarbamate, SiH(CH 3 )-(N(CH 3 )2) 2 , SiHCl-(N(CH 3 ) 2 ) 2 , (Si(CH 3 ) 2
  • a further example of an aminosilane is trisilylamine (N(SiH 3 )).
  • a "nitrogen-containing reactant" contains at least one nitrogen, for example, ammonia, hydrazine, amines (amines bearing carbon) such as methylamine, dimethylamine, ethylamine, isopropylamine, t-butylamine, di-t-butylamine, cyclopropylamine, sec- butylamine, cyclobutylamine, isoamylamine, 2-methylbutan-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, di-t-butylhydrazine, as well as aromatic containing amines such as anilines, pyridines, and benzylamines.
  • Amines may be primary, secondary, tertiary or quaternary (for example, tetraalkylammonium compounds).
  • a nitrogen-containing reactant can contain heteroatoms other than nitrogen, for example, hydroxylamine, t- butyloxycarbonyl amine and N-t-butyl hydroxylamine are nitrogen-containing reactants.
  • Plasmas refers to a plasma ignited in a reaction chamber or remotely and brought into the reaction chamber.
  • Plasmas can include the reactants described herein and may include other agents, for example, a carrier gas, or reactive species such as hydrogen gas.
  • the reactants and other agents may be present in a reaction chamber when a plasma is struck, or a remote plasma may be flowed into a chamber where the reactants are present and/or the reactants and/or carrier gas may be ignited into a plasma remotely and brought into the reaction chamber.
  • a "plasma” is meant to include any plasma known to be technologically feasible, including inductively-coupled plasmas and microwave surface wave plasmas.
  • Thermally removable group refers to a moiety, on either or both of the nitrogen- containing reactant and the silicon-containing reactant, that breaks down into volatile components at between about 200°C and about 550°C. Described herein are non- limiting examples such as secondary and tertiary carbon group, which undergo elimination reactions in this temperature range.
  • groups thermally decompose as described by other mechanisms, for example, a t-butyloxycarbonyl (t-BOC or "BOC”) group thermally decomposes via both an elimination mechanism where the t-butyl portion of the group forms isobutylene, but also the decomposition forms carbon dioxide.
  • a thermally removable group is not limited to a particular mechanism or combination of mechanisms. As long as the group breaks down under the specified temperature range to produce at least one volatile component, then it qualifies as a thermally decomposable group. For example, under a given set of conditions, t-butylethylamine will undergo thermal decomposition of the t-butyl group to form isobutylene while the ethyl group remains, and thus isobutylene and ethylamine are the products of the thermal decomposition.
  • the volatility of a component depends, in part, on the reaction conditions under which the component is generated.
  • isobutylene may be volatile and be removed from a reaction chamber under the conditions of heating and low press because it does not react with the adsorbed reactants, while, for example, ammonia, although generally a volatile compound, undergoes reaction with a silicon-containing reactant adsorbed on the surface of a substrate.
  • SiN and other silicon-containing dielectric films including SiCN and SiC films.
  • silicon-containing films are made using UV-activated conformal film deposition (CFD).
  • CFD conformal film deposition
  • S1 3 N 4 and other SiN films can be deposited, including Si-containing films that contain oxygen and/or carbon.
  • CFD the methods described herein are not limited to CFD.
  • Other suitable methods include ALD, PEALD, CVD, PECVD, and plasma enhanced cyclic chemical vapor deposition (PECCVD).
  • Methods for forming films using CFD are described in US Patent application, serial number 13/084,399, filed on April 11, 2011, and which is incorporated by reference herein for all purposes. For context, a short description of CFD is provided.
  • Manufacture of semiconductor devices typically involves depositing one or more thin films on a non-planar substrate in an integrated fabrication process.
  • a silicon nitride film may be deposited on top of an elevated gate stack to act as a spacer layer for protecting lightly-doped source and drain regions from subsequent ion implantation processes.
  • CVD chemical vapor deposition
  • a silicon nitride film on the non-planar substrate, which is then anisotropically etched to form the spacer structure.
  • mass transport limitations of CVD gas phase reactions may cause "bread- loafing" deposition effects. Such effects typically exhibit thicker deposition at top surfaces of gate stacks and thinner deposition at the bottom corners of gate stacks.
  • mass transport effects across the wafer surface may result in within-die and within-wafer film thickness variation. These thickness variations may result in over-etching of some regions and under-etching of other regions. This may degrade device performance and/or die yield.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis.
  • a substrate surface including a population of surface active sites, is exposed to a gas phase distribution of a first reactant (A).
  • A a first reactant
  • Some molecules of reactant A may form a condensed phase atop the substrate surface, including chemisorbed species and physisorbed molecules of reactant A.
  • the reactor is then evacuated to remove gas phase and physisorbed reactant A so that only chemisorbed species remain.
  • a second film reactant (B) is then introduced to the reactor so that some molecules of reactant B adsorb to the substrate surface.
  • Thermal energy provided to the substrate activates surface reactions between adsorbed molecules of reactants A and B, forming a film layer.
  • the reactor is evacuated to remove reaction by-products and unreacted reactant B, ending the ALD cycle. Additional ALD cycles may be included to build film thickness. Plasma, or other energetic means, may be used in conjunction with heating, or as alternatives to heating the substrate in order to drive the reaction between reactant A and B.
  • each ALD cycle may deposit a film layer of, in one example, between one-half and three angstroms thick.
  • ALD processes may be time consuming when depositing films more than a few nanometers thick.
  • some reactants may have long exposure times to deposit a conformal film, which may also reduce wafer throughput time.
  • Conformal films may also be deposited on planar substrates.
  • antireflective layers for lithographic patterning applications may be formed from planar stacks including alternating film types. Such antireflective layers may be approximately 100 to 1000 angstroms thick, making ALD processes less attractive than CVD processes. However, such anti-reflective layers may also have a lower tolerance for within-wafer thickness variation than many CVD processes may provide. For example, a 600-angstrom thick antireflective layer may tolerate a thickness range of less than 3 angstroms.
  • Various embodiments described herein include CFD to deposit SiN, SiCN, SiC, SiO, SiON and SiOCN films and other silicon-containing films.
  • CFD does not rely on complete purges of one or more reactants prior to reaction to form the silicon-containign film.
  • plasma activation of deposition reactions may result in lower deposition temperatures than thermally-activated reactions, potentially reducing the thermal budget of an integrated process.
  • FIGURE 1 shows a temporal progression of exemplary phases in a CFD process, 100, for various process parameters, for example, inert gas flow, reactant A, reactant B and when an energy source is switched on.
  • process parameters for example, inert gas flow, reactant A, reactant B and when an energy source is switched on.
  • two deposition cycles 110A and HOB are shown.
  • Example CFD process parameters include, but are not limited to, flow rates for inert and reactant species, plasma power and frequency, ultraviolet light wavelength, duration and intensity, substrate temperature, and process station pressure.
  • a cycle is the minimum set of operations required to perform a surface deposition reaction one time.
  • the result of one cycle is production of at least a partial film layer on a substrate surface.
  • a CFD cycle will include only those steps necessary to deliver and adsorb each reactant to the substrate surface, and then react those adsorbed reactants to form the partial layer of film.
  • the cycle may include certain ancillary steps such as sweeping one of the reactants or byproducts and/or treating the partial film as deposited.
  • a cycle contains only one instance of a unique sequence of operations.
  • a cycle may include the following operations: (i) delivery/adsorption of reactant A, (ii) delivery/adsorption of reactant B, (iii) sweep B out of the reaction chamber, and (iv) apply activation to drive a surface reaction of A and B to form the partial film layer on the surface.
  • an inert gas is flowed during all phases of process 100.
  • reactant A exposure phase, 120 A reactant A is supplied at a controlled flow rate to a process station to saturate exposed surfaces of a substrate.
  • Reactant A may be any suitable deposition reactant, for example, a nitrogen-containing reactant.
  • reactant A flows continuously throughout deposition cycles 11 OA and HOB.
  • reactants A and B may be allowed to mingle in the gas phase of some embodiments of a CFD process.
  • Continuously supplying reactant A to the process station may reduce or eliminate a reactant A flow rate turn-on and stabilization time compared to an ALD process where reactant A is first turned on, then stabilized and exposed to the substrate, then turned off, and finally removed from a reactor.
  • reactant A exposure phase 120 A may have a duration that exceeds a substrate surface saturation time for reactant A.
  • the embodiment of FIGURE 1 includes a reactant A post-saturation exposure time 130 in reactant A exposure phase 120 A.
  • reactant A exposure phase 120 A may include a controlled flow rate of an inert gas.
  • inert gases include, but are not limited to, nitrogen, argon, and helium.
  • the inert gas may be provided to assist with pressure and/or temperature control of the process station, evaporation of a liquid reactant, more rapid delivery of the reactant and/or as a sweep gas for removing process gases from the process station and/or process station plumbing.
  • reactant B is supplied at a controlled flow rate to the process station to saturate the exposed substrate surface.
  • reactant B can be a silicon-containing reactant, for example.
  • FIGURE 1 depicts reactant B exposure phase 140A as having a constant flow rate, it will be appreciated that any suitable flow of reactant B, including a variable flow, may be employed within the scope of the present disclosure.
  • reactant B exposure phase 140 A may have any suitable duration. In some embodiments, reactant B exposure phase 140 A may have a duration exceeding a substrate surface saturation time for reactant B.
  • FIGURE 1 depicts a reactant B post-saturation exposure time 150 included in reactant B exposure phase 140 A.
  • surface adsorbed B species may exist as discontinuous islands on the substrate surface, making it difficult to achieve surface saturation of reactant B.
  • Various surface conditions may delay nucleation and saturation of reactant B on the substrate surface.
  • ligands released on adsorption of reactants A and/or B may block some surface active sites, preventing further adsorption of reactant B.
  • continuous adlayers of reactant B may be provided by modulating a flow of and/or discretely pulsing reactant B into the process station during reactant B exposure phase 140 A. This may provide extra time for surface adsorption and desorption processes while conserving reactant B compared to a constant flow scenario.
  • one or more sweep phases may be included between consecutive exposures of reactant B.
  • gas phase reactant B may be removed from the process station in sweep phase 160 A in some embodiments. Sweeping the process station may avoid gas phase reactions where reactant B is unstable to plasma activation or where unwanted species might be formed. Further, sweeping the process station may remove surface adsorbed ligands that may otherwise remain and contaminate the film.
  • Example sweep gases may include, but are not limited to, argon, helium, and nitrogen.
  • sweep gas for sweep phase 160A is supplied by the continuous inert gas stream.
  • sweep phase 160A may include one or more evacuation subphases for evacuating the process station. Alternatively, it will be appreciated that sweep phase 160A may be omitted in some embodiments.
  • Sweep phase 160A may have any suitable duration.
  • increasing a flow rate of a one or more sweep gases may decrease the duration of sweep phase 160A.
  • a sweep gas flow rate may be adjusted according to various reactant thermodynamic characteristics and/or geometric characteristics of the process station and/or process station plumbing for modifying the duration of sweep phase 160A.
  • the duration of a sweep phase may be optimized by adjustment of the sweep gas flow rate. This may reduce deposition cycle time, which may improve substrate throughput.
  • energy is provided to activate surface reactions between surface adsorbed reactants A and B.
  • a plasma may directly or indirectly activate gas phase molecules of reactant A to form reactant A radicals. These radicals may then interact with surface adsorbed reactant B, resulting in film-forming surface reactions.
  • ultraviolet (UV) radiation may directly or indirectly activate gas phase molecules of reactant A to form reactant A radicals, which may then interact with surface adsorbed reactant B.
  • activation phase 180A can include one or more of a direct (in situ) plasma, a remote plasma, UV radiation exposure, visible light radiation exposure and microwave radiation exposure.
  • Activation phase 180A concludes deposition cycle 11 OA, which in the embodiment of FIGURE 1 is followed by deposition cycle HOB, commencing with reactant A exposure phase 120B, and continuing with B exposure phase 140B, sweep phase 160B and plasma activation phase 180B.
  • a plasma formed in activation phase 180A may be formed directly above the substrate surface. This may provide a greater plasma density and enhance a surface reaction rate between reactants A and B.
  • plasmas for CFD processes may be generated by applying a radio frequency (RF) field to a low-pressure gas using two capacitively coupled plates. Any suitable gas may be used to form the plasma.
  • the inert gas such as argon or helium can be used along with reactant A, a nitrogen- containing reactant, to form the plasma. Ionization of the gas between the plates by the RF field ignites the plasma, creating free electrons in the plasma discharge region. These electrons are accelerated by the RF field and may collide with gas phase reactant molecules.
  • Electrodes include process gas distribution showerheads and substrate support pedestals. It will be appreciated that plasmas for CFD processes may be formed by one or more suitable methods other than capacitive coupling of an RF field to a gas.
  • a plasma formed in activation phase 180A may be formed by in a remote plasma source.
  • activated species from a remote plasma source can enter the chamber housing the substrate and interact with the reactants.
  • these activated species include ions, electrons, radicals and high energy molecules.
  • the activated species that enter the chamber include radicals with substantially no ions and/or electrons, due to recombination prior to entering the chamber.
  • An ion filter can be used in some embodiments. Examples of gases that may be fed into a remote plasma source, providing the activated species, include argon, helium, ammonia, hydrogen and oxygen.
  • activation phase 180A can involve exposure to radiation from a UV light source.
  • a UV light source can be used including broadband and narrow band UV light sources.
  • radical species that participate in the deposition process may be formed by exposure to the UV radiation.
  • a UV light source may emit light of one or more wavelengths chosen to excite one or more reactants or activate a reaction.
  • UV exposure may occur when a reactant is in the reaction chamber.
  • a UV light source may be mounted within or outside the chamber. UV radiation may pass through a window to reach the reactant(s). In some other embodiments, UV exposure can occur prior to a reactant entering a chamber.
  • a reactant can be exposed to UV radiation prior to be inlet into a chamber, with radicals and/or other activated species entering the chamber.
  • activation phase 180A can be concurrent or overlap with a reactant exposure phase. Examples of such processes are described further below.
  • activation phase 180A can involve exposure to radiation from a visible light source.
  • a visible light source may emit light of one or more wavelengths chosen to excite one or more reactants or activate a reaction.
  • visible light exposure may occur when a reactant is in the reaction chamber.
  • a light source may be mounted within or outside the chamber. Visible light may pass through a window to reach the reactant(s).
  • exposure to visible light that excites a reactant can occur prior to a reactant entering a chamber.
  • a reactant can be exposed to the radiation prior to be inlet into a chamber, with radicals and/or other activated species entering the chamber.
  • activation phase 180A can be concurrent or overlap with a reactant exposure phase. Examples of such processes are described further below.
  • activation phase 180A can involve exposure to microwave radiation.
  • microwave radiation For example, radical species that participate in the deposition process may be formed.
  • a microwave source may emit light at one or more frequencies chosen to excite one or more reactants or activate a reaction.
  • microwave exposure may occur when a reactant is in the reaction chamber.
  • a microwave source may be mounted within or outside the chamber. Microwaves may pass through a window to reach the reactant(s).
  • exposure to microwaves that excite a reactant can occur prior to a reactant entering a chamber.
  • a reactant can be exposed to the radiation prior to be inlet into a chamber, with radicals and/or other activated species entering the chamber.
  • activation phase 180A can be concurrent or overlap with a reactant exposure phase. Examples of such processes are described further below. [0039] In some embodiments, activation phase 180A may involve one or more of the above- described modes of activation. Activation phase 180A may have any suitable duration. In some embodiments, activation phase 180A may have a duration that exceeds a time for activated radicals to interact with all exposed substrate surfaces and adsorbates, forming a continuous film atop the substrate surface. For example, the embodiment shown in FIGURE 1 includes a post-saturation exposure time 190 in activation phase 180A.
  • extending an activation energy exposure time and/or providing a plurality of exposure phases may provide a post-reaction treatment of bulk and/or near-surface portions of the deposited film.
  • decreasing surface contamination may prepare the surface for adsorption of reactant A.
  • a silicon nitride film formed from reaction of a silicon-containing reactant and a nitrogen-containing reactant may have a surface that may resist adsorption of subsequent reactants. Treating the silicon nitride surface with a plasma or other activation energy may create hydrogen bonds for facilitating subsequent adsorption and reaction events.
  • plasma treatments include electromagnetic radiation treatments, thermal treatments (e.g., anneals or high temperature pulses), and the like.
  • any of these treatments may be performed alone or in combination with another treatment, including a plasma treatment.
  • the treatment involves exposing the film to UV radiation.
  • the method involves the application of UV radiation to a film in situ (i.e., during formation of the film) or post deposition of the film. Such treatment serves to reduce or eliminate defect structure and provide improved electrical performance.
  • a UV treatment can be coupled with a plasma treatment. These two operations can be performed concurrently or sequentially. In the sequential option, either operation can take place first. In the concurrent option, the two treatments may be provided from separate sources (e.g., an RF power source for the plasma and a lamp for the UV) or from a single source such as a helium plasma that produces UV radiation as a byproduct.
  • sources e.g., an RF power source for the plasma and a lamp for the UV
  • a single source such as a helium plasma that produces UV radiation as a byproduct.
  • film properties such as film stress, dielectric constant, refractive index, etch rate may be adjusted by varying plasma or other activation energy parameters.
  • a single reactant and an inert gas used to supply plasma energy for a surface reaction can be used.
  • some embodiments may use multiple reactants to deposit a film.
  • a silicon nitride film may be formed by reaction of a silicon-containing reactant and one or more of a nitrogen- containing reactant, or one or more silicon-containing reactants and a single nitrogen- containing reactant, or more than one of both the silicon-containing reactant and the nitrogen- containing reactant.
  • FIGURE 2 shows another example of temporal progression of phases in a process, 200, for various process parameters, for example, inert gas flow, reactant A, reactant B and when an energy source is switched on.
  • process parameters for example, inert gas flow, reactant A, reactant B and when an energy source is switched on.
  • two deposition cycles 21 OA and 210B are shown.
  • Example process parameters include, but are not limited to, flow rates for inert and reactant species, plasma power and frequency, UV radiation wavelength, intensity duration, substrate temperature, process station pressure.
  • reactant A exposure phase 220A reactant A is supplied at a controlled flow rate to a process station to saturate exposed surfaces of a substrate.
  • Reactant A may be any suitable deposition reactant, for example, a silicon- containing reactant. While the embodiment shown in FIGURE 2 depicts reactant A exposure phase 220A as having a constant flow rate, it will be appreciated that any suitable flow of reactant A, including a variable flow, may be employed within the scope of the present disclosure. In some embodiments, reactant A exposure phase 220A may have a duration that exceeds a substrate surface saturation time for reactant A.
  • reactant A exposure phase 220A may include a controlled flow rate of an inert gas.
  • inert gases include, but are not limited to, nitrogen, argon, and helium.
  • the inert gas may be provided to assist with pressure and/or temperature control of the process station, evaporation of a liquid reactant, more rapid delivery of the reactant and/or as a sweep gas for removing process gases from the process station and/or process station plumbing.
  • Gas phase reactant A may be removed from the process station in sweep phase 260A in some embodiments, prior to B exposure phase 240A. Sweeping the process station may purge any reactant A that is not adsorbed on the substrate surface.
  • Example sweep gases may include, but are not limited to, argon, helium, and nitrogen. In the embodiment shown in
  • sweep gas for sweep phase 260A is supplied by the continuous inert gas stream.
  • sweep gas may be supplied only during a sweep phase.
  • sweep phase 260A may include one or more evacuation subphases for evacuating the process station. Alternatively, it will be appreciated that sweep phase 260A may be omitted in some embodiments.
  • reactant B is supplied at a controlled flow rate to the process station to saturate the exposed substrate surface.
  • reactant B can be a nitrogen-containing reactant, for example.
  • reactant B exposure phase 240A may have any suitable duration.
  • reactant B exposure phase 240A may have a duration exceeding a substrate surface saturation time for reactant B.
  • the embodiment shown in FIGURE 2 depicts a reactant B post-saturation exposure time 250 included in reactant B exposure phase 240A.
  • activation phase 280A of the embodiment shown in FIGURE 2 energy is provided to activate surface reactions between surface adsorbed reactants A and B.
  • a plasma may directly or indirectly activate gas phase molecules of reactant B to form reactant B radicals. These radicals may then interact with surface adsorbed reactant A, resulting in film-forming surface reactions.
  • ultraviolet (UV) radiation may directly or indirectly activate gas phase molecules of reactant B to form reactant B radicals, which may then interact with surface adsorbed reactant A.
  • B exposure phase 240A is shown in FIGURE 2 as ending prior to activation phase 280A, in some embodiments, the two phases can overlap.
  • activation phase 280A can include one or more of a direct (in situ) plasma, a remote plasma, UV radiation exposure, visible light radiation exposure and microwave radiation exposure, as described above.
  • Activation phase 280A may have any suitable duration.
  • activation phase 280A may have a duration that exceeds a time for activated radicals to interact with all exposed substrate surfaces and adsorbates, forming a continuous film atop the substrate surface.
  • the embodiment shown in FIGURE 2 includes a post- saturation exposure time 290 in activation phase 280A.
  • FIGURE 2 shows a sweep phase 270A performed after activation 280A.
  • Gas phase reactant B may be removed from the process station in sweep phase 260A in some embodiments. Sweeping the process station may purge any gas phase reactant B as well as unwanted by products and/or contaminants.
  • Example sweep gases may include, but are not limited to, argon, helium, and nitrogen.
  • sweep gas for sweep phase 270A is supplied by the continuous inert gas stream, though it may otherwise be supplied.
  • sweep phase 270A may include one or more evacuation subphases for evacuating the process station. Alternatively, it will be appreciated that sweep phase 270 A may be omitted in some embodiments.
  • Sweep phase 270A concludes deposition cycle 21 OA, which in the embodiment of FIGURE 2 is followed by deposition cycle 210B, commencing with reactant A exposure phase 220B, and continuing with sweep phase 260B, B exposure phase 240B, plasma activation phase 280B, and sweep phase 270B.
  • FIGURE 3 depicts a process flow 300, outlining aspects of an embodiment of a method.
  • a substrate is provided to a reaction chamber, see 305.
  • An optional thermal soak can be performed, see 310, to heat the substrate to a desired temperature.
  • the substrate is heated to between about 50°C and about 550°C, or more particularly from about 300°C to about 450°C, for example about 350°C or 400°C.
  • One or more Si-containing precursors are then delivered to the chamber, see 315.
  • operation 415 can include delivering a coreactant in addition to the silicon-containing reactant, such as oxidant (e.g., for deposition of silicon oxides or silicon oxynitrides) and/or a nitrogen-containing precursor (e.g., for deposition of silicon nitrides or silicon oxynitrides).
  • oxidant e.g., for deposition of silicon oxides or silicon oxynitrides
  • nitrogen-containing precursor e.g., for deposition of silicon nitrides or silicon oxynitrides.
  • the one or more Si-containing precursors can be adsorbed, e.g., chemi- or physi-sorbed, on the substrate surface.
  • An optional purge operation can then be performed, see 320, to leave adsorbed material on the substrate surface.
  • the surface-bound molecules can be activated with UV energy, see 325.
  • the UV energy can interact with one or more of a surface bound silicon-containing reactant and a surface bound coreactant.
  • a UV wavelength or range of UV wavelengths may be chosen to interact with one or more ligands on the reactant(s).
  • a reaction forming a desired silicon-containing film such as SiN, SiC, Si0 2 , SiCN, SiON or SiONC, is activated.
  • a carbon-containing Si-precursor and a nitrogen-containing co-reactant can be used to form SiCN.
  • An oxygen- and carbon-containing Si-precursor and a nitrogen-containing coreactant can be used to form SiONC.
  • a co-reactant can be an oxidizer that can be used to deposit SiO.
  • an oxygen- and carbon-containing Si- precursor and an oxidizer can be used to form silicon oxides.
  • the process 300 can then continue with an optional purge, see 330, to leave only a layer of the SiN, Si0 2 , SiCN, SiON, SiONC or other film on the substrate. Operations 315-330 can be repeated to form a film of the desired thickness.
  • FIGURE 4 depicts a process flow 400, outlining aspects of an embodiment of a method.
  • a substrate is provided to the chamber, see 405.
  • An optional thermal soak is performed as described above, see 410.
  • One or more Si-containing precursors are then delivered to the chamber, see 415.
  • the one or more precursors can be adsorbed, e.g., chemi- or physi-sorbed, on the substrate surface.
  • the process 400 can then continue with an optional purge, see 420, to leave a layer of adsorbed material on the substrate.
  • the layer can include a surface bound Si-containing reactant.
  • a co-reactant precursor or precursor stream can be activated with UV-wavelength energy, see 425.
  • a nitrogen-containing reactant and/or an oxidant can be activated in the vapor phase in or upstream of the reaction chamber.
  • both surface-adsorbed silicon containing reactants and vapor phase coreactants reactants can be activated.
  • a reaction forming a desired silicon-containing film such as SiN, SiCN, SiC, SiO, SiON or SiONC, is activated.
  • the process 400 can then continue with an optional purge, see 430, to leave only a layer of the SiN, SiCN, SiC, SiO, SiON or SiONC or other silicon-containing film on the substrate. Operations 415-430 can be repeated to form a film of the desired thickness.
  • FIGURE 5 depicts an example of a process flow according to certain embodiments for forming a silicon-containing film. It will be appreciated that the processes as illustrated in FIGURE 5 may be used to form SiCN, SiONC and SiON films depending on the particular Si-containing and N-containing reactants used. Forming SiONC and SiON films may include using an oxygen-containing co-reactant in addition to the nitrogen-containing reactant in block 515. Further, the process as illustrated in Figure 5 can be used to form SiO, for example, by using an oxygen-containing reactant instead of the nitrogen-containing reactant in block 515. Examples of oxygen-containing co-reactants include 0 2 . [0055] The process 500 begins with a substrate being provided to a chamber, see 505.
  • the substrate can be any appropriate substrate on which the silicon-containing film is desired.
  • the substrate can be a partially fabricated integrated circuit, flash memory or phase-change memory substrate.
  • the substrate can be provided as a bare substrate, e.g., a bare silicon substrate, or with one or more layers deposited thereon.
  • the surface on which the SiN or other silicon-containing film is to be deposited can be or include, for example, silicon, polysilicon, copper, tituanium, tungsten, silicon dioxide, or a germanium-antimony- tellurium (GST) alloy.
  • the surface includes one or more raised or recessed features.
  • the one or more raised features can have aspect ratios of 2: 1 - 10: 1, for example.
  • the substrate is exposed to a silicon-containing reactant, see 510.
  • operation 510 is a non-plasma operation.
  • the reactor can be pressurized, in some embodiments, to a first pressure between about 5 and 50 Torr, for example. In a particular embodiment, pressure is about 20 Torr during operation 510. Pressures outside this range may be used according to the desired embodiment.
  • the silicon-containing reactant is adsorbed on the substrate surface. After the desired amount of the silicon-containing reactant is adsorbed on the surface, the flow of silicon-containing reactant can be stopped (not shown).
  • the substrate is exposed to one or more nitrogen-containing reactants, see 515.
  • Activation energy is provided while the nitrogen-containing reactant is present in the vapor phase, see 520, thus forming a SiN or other Si- and N-containing film on the substrate.
  • the nitrogen-containing reactant may be flowed continuously through-out the process (e.g., as reactant A is in FIGURE 1) or flow intermittently (e.g., as reactant B is in FIGURE 2).
  • operation 520 may be performed intermittently, while in some embodiments of the latter case, the energy source may be left on even when nitrogen-containing reactants are not present.
  • operation 520 can include one or more of a direct (in situ) plasma, a remote plasma, UV radiation exposure, visible light radiation exposure and microwave radiation exposure.
  • operation 520 can include a direct plasma formed directly above the substrate surface. This may provide a greater plasma density and enhance a surface reaction rate between reactants.
  • plasmas may be generated by applying a radio frequency (RF) field to a low-pressure gas using two capacitively coupled plates. Any suitable gas may be used to form the plasma. Ionization of the gas between the plates by the RF field ignites the plasma, creating free electrons in the plasma discharge region. These electrons are accelerated by the RF field and may collide with gas phase reactant molecules.
  • RF radio frequency
  • RF field may be coupled via any suitable electrodes.
  • electrodes include process gas distribution showerheads and substrate support pedestals.
  • plasmas may be formed by one or more suitable methods other than capacitive coupling of an RF field to a gas.
  • remotely generated or downstream plasma may provide all or part of the activation energy in 520.
  • activated species from a remote plasma source can enter the chamber housing the substrate and interact with the reactants.
  • these activated species include ions, electrons, radicals and high energy molecules.
  • the activated species that enter the chamber include radicals with substantially no ions and/or electrons, due to recombination prior to entering the chamber.
  • block 520 can occur prior to block 515 by providing the nitrogen-containing reactant or other co-reactant to the remote plasma generator; for example, an ammonia co-reactant can be fed to a remote plasma source in the formation of SiN, SiCN, SiOCN, and SiON films.
  • oxygen can be fed to a remote plasma source in the formation of SiO films, SiOCN and SiON films.
  • operation 520 can involve exposure to radiation from a UV light source.
  • a UV light source can be used including broadband and narrow band UV light sources.
  • radical species that participate in the deposition process may be formed by exposure to the UV radiation.
  • a UV light source may emit light of one or more wavelengths chosen to excite one or more reactants or activate a reaction.
  • UV exposure may occur when the nitrogen-containing reactant is in the reaction chamber.
  • a UV light source may be mounted within or outside the chamber. UV radiation may pass through a window to reach the reactant(s).
  • UV exposure can occur prior to the nitrogen-containing reactant entering a chamber.
  • the reactant can be exposed to UV radiation prior to be inlet into the chamber, with radicals and/or other activated species entering the chamber.
  • the UV radiation can be broadband or a narrow band selected to activate a co-reactant or other species.
  • wavelengths that can be used to activate ammonia, and primary, secondary and tertiary amines are less than about 240 nm.
  • wavelengths that can be used to activate oxygen are less than about 300 nm.
  • Example intensities can be about 0.5 W/cm 2 over the entire UV range for a broadband source or about 10 mW/cm 2 for a single wavelength excimer.
  • operation 520 can involve exposure to radiation from a visible light source.
  • a visible light source may emit light of one or more wavelengths chosen to excite one or more reactants or activate a reaction.
  • visible light exposure may occur when the nitrogen-containing reactant is in the reaction chamber.
  • a light source may be mounted within or outside the chamber. Visible light may pass through a window to reach the reactant(s).
  • exposure to visible light that excites the nitrogen-containing reactant can occur prior to the reactant entering a chamber.
  • the reactant can be exposed to the radiation prior to be inlet into a chamber, with radicals and/or other activated species entering the chamber.
  • operation 520 can involve exposure to microwave radiation.
  • microwave radiation For example, radical species that participate in the deposition process may be formed.
  • a microwave source may emit light at one or more frequencies chosen to excite one or more reactants or activate a reaction.
  • microwave exposure may occur when the nitrogen-containing reactant is in the reaction chamber.
  • a microwave source may be mounted within or outside the chamber. Microwaves may pass through a window to reach the reactant(s).
  • exposure to microwaves that excite the nitrogen-containing reactant can occur prior to the reactant entering the chamber.
  • the reactant can be exposed to the radiation prior to be inlet into a chamber, with radicals and/or other activated species entering the chamber.
  • the pressure in the reactor is cycled such that it is lower during operations 515 and/or 520 than operation 510.
  • the pressure during these operations can be between about 1 and 5 Torr, for example 2 Torr.
  • the flow of the nitrogen- containing reactant(s) can be stopped (not shown) after 520 in some embodiments.
  • the silicon-containing reactant and/or nitrogen-containing reactant can be purged.
  • One or more iterations of 510-520 can be performed to build up a SiN or other Si- containing layer. In one embodiment, these operations are repeated to form a conformal layer on the substrate between about 1 nm and about 100 nm thick. In another embodiment, between about 5 nm and about 50 nm thick. In another embodiment, between about 5 nm and about 30 nm thick.
  • the substrate is heated to between about 50°C and about 550°C, or more particularly from about 300°C to about 450°C, for example about 350°C or 400°C. In one embodiment, the substrate is heated throughout the deposition, in other embodiments the substrate is heated periodically during the deposition or after the deposition steps as an anneal.
  • FIGURES 6-13 provide examples of temporal progressions of one or two SiN deposition cycles for various process parameters, for example, a silicon-containing precursor flow, a nitrogen-containing reactant, and UV light source intensity. Other parameters, such as inert gas flow, that may be present are not shown for ease of illustration.
  • FIGURES 6-13 chiefly refer to SiN films, it will be appreciated that other reactants may be used in addition to or instead of the nitrogen-containing reactants to form, for example, Si02, SiCN or SiONC. Similarly, it will be appreciated that the processes as illustrated in FIGURES 6-13 may be used to form SiCN, SiOCN and SiON films depending on the particular Si-containing and N-containing reactants used. Similarly, while FIGURES 6-13 refer to UV energy, it will be appreciated that one or more other energy sources as discussed above may be used in addition to or instead of UV energy.
  • the silicon-containing reactant may be UV transparent, while the nitrogen-containing reactant can be UV-activated.
  • the silicon-containing reactant can include a ligand that can be UV-activated.
  • NH 3 can be activated by UV radiation having a wavelength of less than about 240 nm.
  • 0 2 - containing ligands can be activated by UV radiation of less than about 240 nm.
  • SiH 4 and most of its derivatives can be activated by UV radiation have a wavelength less than about 200 nm.
  • FIGURE 6 shows two cycles 61 OA and 610B, each of which results in deposition on of a layer of SiN.
  • Deposition cycle 61 OA begins with a Si-containing reactant flow in a phase 620A. While the embodiment shown in FIGURE 6 depicts phase 620A as having a constant flow rate of the Si-containing reactant, it will be appreciated that any suitable flow of any reactant shown in the figures, including a variable flow, may be employed.
  • An optional purge phase 20A follows phase 620A. A nitrogen-containing reactant is flowed into the chamber in phase 63 OA. Also during this phase, UV light is switched on such that the vapor phase molecules and/or surface-bound molecules in the chamber are exposed to, and may be activated by, UV radiation.
  • vapor phase nitrogen-containing reactant can be activated by the UV radiation.
  • the embodiment shown in FIGURE 6 depicts the UV intensity as constant, it will be appreciated that it can be variable or pulsed. Moreover, in some embodiments, the UV radiation may overlap temporally with the nitrogen-containing flow but start or stop before or after it.
  • Cycle 61 OA concludes with an optional purge 3 OA.
  • a second cycle 610B is depicted including phases 620B and 630B and optional purge phases 20B and 30B.
  • FIGURE 7 shows two cycles 71 OA and 71 OB, with cycle 71 OA including phase 720 A followed by phase 73 OA and cycle 71 OB including phase 720B followed by phase 730B.
  • Phases 720A and 720B include flows of both a Si-containing reactant and a nitrogen- containing reactant, with no UV. Although not depicted, these phases can be followed by optional purge phases in some embodiments.
  • the nitrogen-containing reactant continues to flow in phases 730A and 730B, with the UV light also turned on in these phases.
  • FIGURE 8 depicts two cycles 81 OA and 810B of an embodiment in which UV light is on while a silicon-containing reactant if flowed in a chamber in phases 820A and 820B of the cycles 81 OA and 810B respectively.
  • the UV light may activate surface bound Si- containing molecules.
  • Optional purge operations 20 A and 20B may follow phases 820 A and 820B, respectively, before a nitrogen-containing reactant is flowed into the chamber in phases 830A and 830B. Each cycle may end with an optional purge operation 30A or 30B.
  • FIGURE 9 shows two cycles 91 OA and 910B of an example embodiment in which UV light is on for the duration of each cycle.
  • Each cycle includes a flow of silicon- containing reactant (phase 920A in cycle 91 OA and phase 920B in cycle 910B), followed by an optional purge phase (phase 20 A in cycle 91 OA and phase 20B in cycle 910B) and a flow of nitrogen-containing reactant (phase 93 OA in cycle 91 OA and phase 930B in cycle 910B) followed by an optional purge phase (phase 30A in cycle 91 OA and phase 30B in cycle 910B).
  • the UV light may be switched off during portions of cycles 91 OA and 910B, for example during the optional purge phases, if performed.
  • FIGURE 10 shows two cycles 1010A and 1010B of an example embodiment in which the nitrogen-containing reactant enters the reaction chamber after having been activated by UV radiation.
  • Deposition cycle 1010A includes a flow of a Si-containing reactant (phase 1020A) followed by an optional purge phase 20A.
  • the UV-activated nitrogen-containing reactant is then flowed into the chamber (phase 103 OA) where it can react with surface-bound Si-containing reactant forming a layer of SiN.
  • An optional purge phase 3 OA can then be performed to end the cycle 1010A.
  • Deposition cycle 1010B includes phases 1020B and 1030B and optional purge phases 20B and 30B.
  • FIGURES 11 and 12 show examples three-stage cycles of deposition processes in which the Si-containing reactant flow, the nitrogen-containing reactant flow and the UV exposure are sequential.
  • FIGURE 11 depicts a deposition cycle 1110A that begins with flowing the Si-containing reactant in a phase 1120 A. This is followed by an optional purge 20A.
  • the UV light source is switched on to expose at least surface-bound Si-containing reactant to UV radiation in a phase 1140 A.
  • Phase 1140 A can also be followed by an optional purge phase 40A.
  • the nitrogen-containing reactant is flowed into the reactor to react with activated surface-bound Si-containing reactant in a phase 1130A.
  • SiN is formed.
  • the cycle can end after this phase, or after an optional purge phase 3 OA. Additional cycles can be performed to deposit a SiN film of the desired thickness.
  • FIGURE 12 shows a deposition cycle 121 OA that begins with flowing the Si- containing reactant in a phase 1220A followed by an optional purge 20A. Next, the nitrogen- containing reactant is flowed into the reactor in a phase 123 OA, followed by an optional purge 3 OA. The reactants are exposed to UV radiation in a phase 1240 A, activating a reaction to form SiN. One or both of the surface-bound silicon-containing reactant and nitrogen-containing reactant can be activated. In some embodiments, optional purge 30A is not performed, such that vapor phase nitrogen-containing reactant may be present during phase 1240A.
  • a UV exposure phase may also occur after phase 1220A and prior to phase 1230A (e.g., as in FIGURE 11) in addition to occurring after phase 123 OA.
  • FIGURE 13 depicts a temporal progression of an example of an embodiment in which the Si-containing reactant and nitrogen-containing reactant are flowed together in the presence of UV radiation in phase 1320A.
  • the Si-containing reactant can be UV transparent, while the nitrogen-containing reactant is activated. This can then generates radicals on the silicon-containing reactant which then gets deposited.
  • An optional purge phase 20A may follow phase 1320A to complete cycle 1310A. One or more additional cycles may be performed.
  • examples of silicon-containing reactants can include a silane, a halosilane or an aminosilane.
  • a silane contains hydrogen and/or carbon groups, but does not contain a halogen.
  • examples of silanes are silane (S1H 4 ), disilane (Si 2 H 6 ), and organo silanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t- butyldisilane, and the like.
  • halosilane contains at least one halogen group and may or may not contain hydrogens and/or carbon groups.
  • halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes.
  • halosilanes, particularly fluorosilanes may form reactive halide species that can etch silicon materials, in certain embodiments described herein, the silicon-containing reactant is not present when a plasma is struck.
  • chlorosilanes are tetrachlorosilane (S1CI 4 ), trichlorosilane (HS1CI 3 ), dichlorosilane (H 2 SiCl 2 ), monochlorosilane (CIS1H 3 ), chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t- butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, and the like.
  • aminosilane includes at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogens, oxygens, halogens and carbons.
  • Examples of aminosilanes are mono-, di-, tri- and tetra-aminosilane (H 3 Si(NH 2 )4, H 2 Si(NH 2 ) 2 , HSi(NH 2 )3 and Si(NH 2 )4, respectively), as well as substituted mono-, di-, tri- and tetra-aminosilanes, for example, t-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tertiarybutylamino)silane (SiH 2 (NHC(CH 3 )3)2 (BTBAS), bis(dimethylamino)dimethyl silane and other similar compounds where carbon substitutes on both silicon and the amino group, tert-butyl silylcarbamate, SiH(CH 3 )-(N(
  • an aminosilane is trisilylamine (N(SiH 3 )).
  • the silicon-containing reactant may or may not be UV-transparent. If a UV-transparent silicon-containing reactant is used, UV exposure will generally be timed when a nitrogen coreactant is present to be activated by the UV radiation, such as described above with respect to FIGURES 5, 6-7 and 9-13, for example.
  • any suitable nitrogen-containing reactant can be used.
  • the nitrogen-containing reactant is selected from the group consisting of ammonia, a hydrazine, an amine and mixtures thereof.
  • the nitrogen-containing reactant can be activated by UV in the vapor phase. Examples include NH 3 , NR 3 , NR 2 H and NRH 2 , N 2 and forming gas (N 2 /H 2 ).
  • the nitrogen-containing reactant includes a C 1-10 alkyl amine or a mixture of C 1-10 alkyl amines.
  • the C 1-10 alkyl amine is a primary alkyl amine or a secondary alkyl amine.
  • the C 1-10 alkyl amine is a primary alkyl amine.
  • the C 1-10 alkyl amine is according to formula I:
  • each of R 1 , R 2 and R 3 is, independent of the others, H or Ci_ 3 alkyl; or two of R 1 , R 2 and R 3 , together with the carbon atom to which they are attached form a C 3 _ 7 cycloalkyl and the other of R 1 , R 2 and R 3 is H or Ci_ 3 alkyl.
  • the Ci_io alkyl amine has a secondary or tertiary carbon attached directly to the nitrogen.
  • the Ci_io alkyl amine is selected from the group consisting of isopropylamine, cyclopropylamine, sec- butylamine, tert-butyl amine, cyclobutylamine, isoamylamine, 2-methylbutan-2-amine and thexylamine (2,3-dimethylbutan-2-amine).
  • each of R 1 , R 2 and R 3 is Ci_ 3 alkyl.
  • the Ci_io alkyl amine is tert-butyl amine (TBA). TBA can be used.
  • the SiN film produced has an undesirable carbon content.
  • This in-film carbon may result in electrical leakage and may render the film unusable for some dielectric barrier applications.
  • Carbon content can vary, but in some embodiments approximately 10% carbon (by weight) can be considered too high.
  • Methods described herein address unwanted carbon in SiN films. Methods described herein produce SiN films with less than 2% carbon, in one embodiment less than 1% carbon, in yet another embodiment less than 0.5% carbon.
  • the reduction in carbon residue is readily observable in FTIR spectra, although other analytical methods are known to one of ordinary skill in the art that can measure carbon content in these ranges.
  • the nitrogen-containing reactant can contain a thermally removable group.
  • a thermally removable group is a group that breaks down into volatile components at between about 200°C and about 550°C.
  • secondary and particularly tertiary carbon groups can undergo elimination reactions in this temperature range.
  • t-butyl groups break down to form isobutylene in this temperature range.
  • t-butylamine when heated, undergoes an elimination reaction to form isobutylene and ammonia.
  • t-butoxycarbonyl groups also thermally decompose, for example at about 150°C, to form isobutylene, carbon dioxide and theradical to which the t-BOC group was attached.
  • t- butylcarbamate thermally decomposes to give isobutylene ammonia and carbon dioxide.
  • the substrate can be heated to between about 200°C and about 550°C so that such groups decompose and release their carbon content and thus reduce the carbon content of the SiN film.
  • the reactants are adsorbed onto the substrate, a plasma is used to convert the reactants to a SiN material. Remaining carbon groups can be removed by heating the substrate.
  • the heating can be performed during the entire deposition or periodically to decompose the thermally removable groups.
  • the substrate is heated to between about 200°C and about 550°C, in another embodiment between about 350°C and about 550°C, in another embodiment between about 450°C and about 550°C, and in another embodiment, between about 450°C and about 500°C.
  • the SiN film can be heated to between about 450°C and about 500°C, for between about 1 second and about 30 seconds, or between about 1 second and about 20 seconds, or between about 1 second and about 10 seconds.
  • a higher temperature may be used to increase the rate of decomposition and/or as an anneal to improve the properties of the SiN film.
  • the thermally removable group may include a secondary or tertiary carbon functionality.
  • Either or both of the silicon-containing reactant and the nitrogen-containing reactant can include one or more of the same or different thermally removable groups.
  • the thermally removable group is according to Formula II:
  • each of R 1 , R 2 and R 3 is, independent of the others, H or Ci_ 3 alkyl; or two of R 1 , R 2 and R 3 , together with the carbon atom to which they are attached form a C 3 _ 7 cycloalkyl and the other of R 1 , R 2 and R 3 is H or Ci_ 3 alkyl; and where each of said thermally removable group, when part of the nitrogen-containing reactant, is attached to a nitrogen or an oxygen of the nitrogen-containing reactant, and, when part of the silicon-containing reactant, is attached to a silicon or a nitrogen or an oxygen of the silicon-containing reactant.
  • each of R 1 , R 2 and R 3 is, independent of the others, Ci_ 3 alkyl.
  • the thermally removable group is a t-butyl group. Apparatus
  • a suitable apparatus includes hardware for accomplishing the process operations and a system controller having instructions for controlling process operations in accordance with the present invention.
  • FIGURE 14 schematically shows a CFD process station 2300.
  • CFD process station 2300 is depicted as a standalone process station having a process chamber body 2302 for maintaining a low- pressure environment.
  • a plurality of CFD process stations 2300 may be included in a common low-pressure process tool environment.
  • FIGURE 14 shows one process station, it will be appreciated that, in some embodiments, a plurality of process stations may be included in a processing tool.
  • FIGURE 15 depicts an embodiment of a multi-station processing tool 2400.
  • one or more hardware parameters of CFD process station 2300 may be adjusted programmatically by one or more computer controllers.
  • a CFD process station 2300 fluidly communicates with reactant delivery system 2301 for delivering process gases to a distribution showerhead 2306.
  • Reactant delivery system 2301 includes a mixing vessel 2304 for blending and/or conditioning process gases for delivery to showerhead 2306.
  • One or more mixing vessel inlet valves 2320 may control introduction of process gases to mixing vessel 2304.
  • the apparatus of FIGURE 14 includes a vaporization point 2303 for vaporizing liquid reactant to be supplied to mixing vessel 2304.
  • vaporization point 2303 may be a heated vaporizer.
  • the saturated reactant vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc.
  • sweeping the delivery piping may increase process station cycle time, degrading process station throughput.
  • delivery piping downstream of vaporization point 2303 is heat traced.
  • mixing vessel 2304 is also heat traced.
  • piping downstream of vaporization point 2303 has an increasing temperature profile extending from approximately 100°C to approximately 150°C at mixing vessel 2304.
  • reactant liquid is vaporized at a liquid injector.
  • a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel.
  • a liquid injector vaporizes reactant by flashing the liquid from a higher pressure to a lower pressure.
  • a liquid injector atomizes the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. It will be appreciated that smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length of piping downstream from vaporization point 2303.
  • a liquid injector is mounted directly to mixing vessel 2304. In another embodiment, a liquid injector is mounted directly to showerhead 2306. [0087]
  • a liquid flow controller upstream of vaporization point 2303 is provided for controlling a mass flow of liquid for vaporization and delivery to process station 1300.
  • the liquid flow controller includes a thermal mass flow meter (MFM) located downstream of the LFC.
  • a plunger valve of the LFC is adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.
  • PID proportional-integral-derivative
  • the LFC is dynamically switched between a feedback control mode and a direct control mode.
  • the LFC is dynamically switched from a feedback control mode to a direct control mode by disabling a sense tube of the LFC and the PID controller.
  • showerhead 2306 distributes process gases toward substrate 2312.
  • substrate 2312 is located beneath showerhead 2306, and is shown resting on a pedestal 1308. It will be appreciated that showerhead 2306 may have any suitable shape, and may have any suitable number and arrangement of ports for distributing processes gases to substrate 2312.
  • a microvolume 2307 is located beneath showerhead 2306. Performing a CFD process in a microvolume rather than in the entire volume of a process station may reduce reactant exposure and sweep times, may reduce times for altering CFD process conditions (e.g., pressure, temperature, etc.), may limit an exposure of process station robotics to process gases, etc.
  • Example microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters.
  • pedestal 2308 may be raised or lowered to expose substrate 2312 to microvolume 2307 and/or to vary a volume of microvolume 2307. For example, in a substrate transfer phase, pedestal 2308 is lowered to allow substrate 2312 to be loaded onto pedestal 2308.
  • microvolume 2307 completely encloses substrate 2312 as well as a portion of pedestal 2308 to create a region of high flow impedance during a CFD process.
  • pedestal 2308 may be lowered and/or raised during portions the CFD process to modulate process pressure, reactant concentration, etc., within microvolume 2307.
  • process chamber body 2302 remains at a base pressure during the CFD process
  • lowering pedestal 2308 allows microvolume 2307 to be evacuated.
  • Example ratios of microvolume to process chamber volume include, but are not limited to, volume ratios between 1 :500 and 1 : 10. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller.
  • adjusting a height of pedestal 2308 allows a plasma density to be varied during plasma activation and/or treatment cycles included in the CFD process.
  • pedestal 2308 is lowered during another substrate transfer phase to allow removal of substrate 2312 from pedestal 2308.
  • a position of showerhead 2306 may be adjusted relative to pedestal 2308 to vary a volume of microvolume 2307.
  • a vertical position of pedestal 2308 and/or showerhead 2306 may be varied by any suitable mechanism.
  • One of ordinary skill in the art would appreciate that such mechanism would include, for example, hydraulics, pneumatics, spring mechanisms, solenoids and the like.
  • pedestal 2308 may include a rotational mechanism, for example along an axis perpendicular to the surface of the substrate, for rotating an orientation of substrate 2312. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers.
  • showerhead 2306 and pedestal 1308 electrically communicate with RF power supply 2314 and matching network 2316 for powering a plasma.
  • the plasma energy is controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing.
  • RF power supply 2314 and matching network 2316 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers include, but are not limited to, powers between 100W and 5000 W.
  • RF power supply 2314 may provide RF power of any suitable frequency.
  • RF power supply 2314 may be configured to control high- and low-frequency RF power sources independently of one another.
  • Example low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 500 kHz.
  • Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.
  • the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface relative to continuously powered plasmas. [0095] In some embodiments, the plasma is monitored in-situ by one or more plasma monitors.
  • plasma power is monitored by one or more voltage, current sensors (e.g., VI probes).
  • plasma density and/or process gas concentration is measured by one or more optical emission spectroscopy sensors (OES).
  • OES optical emission spectroscopy sensors
  • one or more plasma parameters are programmatically adjusted based on measurements from such in-situ plasma monitors.
  • an OES sensor may be used in a feedback loop for providing programmatic control of plasma power.
  • other monitors may be used to monitor the plasma and other process characteristics. Such monitors include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.
  • the plasma is controlled via input/output control (IOC) sequencing instructions.
  • IOC input/output control
  • the instructions for setting plasma conditions for a plasma process phase may be included in a corresponding plasma activation recipe phase of a CFD process recipe.
  • process recipe phases may be sequentially arranged, so that all instructions for a CFD process phase are executed concurrently with that process phase.
  • time delays may be predictable. Such time delays may include a time to strike the plasma and a time to stabilize the plasma at the indicted power setting.
  • pedestal 2308 may be temperature controlled via heater 2310.
  • pressure control for CFD process station 2300 may be provided by butterfly valve 2318. As shown in FIGURE 14, butterfly valve 2318 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 2300 may also be adjusted by varying a flow rate of one or more gases introduced to CFD process station 2300.
  • FIGURE 15 shows a schematic view of a multi-station processing tool, 2400, with an inbound load lock 2402 and an outbound load lock 2404, either or both of which may comprise a remote plasma source.
  • a robot 2406 at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 2408 into inbound load lock 2402 via an atmospheric port 2410.
  • a wafer is placed by the robot 2406 on a pedestal 2412 in the inbound load lock 2402, the atmospheric port 2410 is closed, and the load lock is pumped down.
  • the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 2414. Further, the wafer also may be heated in the inbound load lock 2402 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 2416 to processing chamber 2414 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in FIGURE 15 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided.
  • the depicted processing chamber 2414 comprises four process stations, numbered from 1 to 4 in the embodiment shown in FIGURE 15. Each station has a heated pedestal (shown at 2418 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. For example, in some embodiments, a process station may be switchable between a CFD and PECVD process mode. Additionally or alternatively, in some embodiments, processing chamber 2414 may include one or more matched pairs of CFD and PECVD process stations. Still further, in some embodiments, processing chamber 2414 maty include one or more UV cure stations or remote plasma treatment stations.
  • processing chamber 2414 comprises four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations.
  • FIGURE 15 also depicts a wafer handling system 2490 for transferring wafers within processing chamber 2414.
  • wafer handling system 2490 may transfer wafers between various process stations and/or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots.
  • FIGURE 15 also depicts a system controller 2450 employed to control process conditions and hardware states of process tool 2400.
  • System controller 2450 may include one or more memory devices 2456, one or more mass storage devices 2454, and one or more processors 2452.
  • Processor 2452 may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc.
  • system controller 2450 controls all of the activities of process tool 2400.
  • System controller 2450 executes system control software 2458 stored in mass storage device 2454, loaded into memory device 2456, and executed on processor 2452.
  • System control software 2458 may include instructions for controlling the timing, mixture of gases, chamber and/or station pressure, chamber and/or station temperature, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck and/or susceptor position, and other parameters of a particular process performed by process tool 2400.
  • System control software 2458 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes.
  • System control software 2458 may be coded in any suitable computer readable programming language.
  • system control software 2458 may include input/output control (IOC) sequencing instructions for controlling the various parameters described above.
  • IOC input/output control
  • each phase of a CFD process may include one or more instructions for execution by system controller 2450.
  • the instructions for setting process conditions for a CFD process phase may be included in a corresponding CFD recipe phase.
  • the CFD recipe phases may be sequentially arranged, so that all instructions for a CFD process phase are executed concurrently with that process phase.
  • Other computer software and/or programs stored on mass storage device 2454 and/or memory device 2456 associated with system controller 2450 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.
  • a substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 2418 and to control the spacing between the substrate and other parts of process tool 2400.
  • a process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station.
  • a pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc.
  • a heater control program may include code for controlling the current to a heating unit that is used to heat the substrate.
  • the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate.
  • a plasma control program may include code for setting RF power levels applied to the process electrodes in one or more process stations.
  • the user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.
  • parameters adjusted by system controller 2450 may relate to process conditions.
  • Non- limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), pressure, temperature, etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.
  • Signals for monitoring the process may be provided by analog and/or digital input connections of system controller 2450 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 2400.
  • Non- limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.
  • System controller 2450 may provide program instructions for implementing the above-described deposition processes.
  • the program instructions may control a variety of process parameters, such as DC power level, RF bias power level, pressure, temperature, etc.
  • the instructions may control the parameters to operate in-situ deposition of film stacks according to various embodiments described herein.
  • the system controller will typically include one or more memory devices and one or more processors configured to execute the instructions so that the apparatus will perform a method in accordance with the present invention.
  • Machine-readable media containing instructions for controlling process operations in accordance with the present invention may be coupled to the system controller.
  • UV ALD Bis(dimethylamono)dimethyl silane exposure on Stations 1 & 3 (UV lamps OFF), UV with NH3 exposure on Stations 2 & 4.
  • Sequence Bis(dimethylamono)dimethyl silane exposure -7 purge - purge -7 index to next station -7 UV in NH3 -7 purge -7 index to next station.
  • Typical bis(dimethylamono)dimethyl exposure time was 20s, with 2mL/min of flow with 1 slm carrier (Ar) on Stations 1 & 3. The wafer was allowed to soak for 60 s in Stations 1 & 3.
  • the film contained SiN with C likely to be present based on width of the SiNC peak. Significant amounts of both N-H and Si-H were present.
  • Remote plasma ALD Bis(dimethylamono)dimethyl silane exposure on Stations 3 & 4, remote plasma with NH3 (+Ar) exposure on Stations 1 & 2. UV lamps off on all stations. 1 slm NH 3 / 5 slm Ar used to generate NH X radicals remotely using an Astron (20s exposure). Sequence: Bis(dimethylamono)dimethyl silane exposure exposure -> Purge -> index 2 stations -7 remote plasm NH 3 - Purge - index 2 stations. The wafer was allowed to soak in stations 3 & 4 for 60 s. The film was primarily a SiN film, with the possible carbon content. No Si-H bonds were present. Reducing RP time to 5 s (from 20s) had no impact on film thickness or film quality.
  • the apparatus/process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility.
  • Lithographic patterning of a film typically comprises some or all of the following steps, each step enabled with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma- assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.
  • a SiN film is formed using a method as described herein. The SiN film is used, for example, for one of the purposes described herein. Further, the method includes one or more steps (l)-(6) described above.

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US20130196516A1 (en) 2013-08-01
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JP2015510263A (ja) 2015-04-02
US20140051262A9 (en) 2014-02-20
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