WO2014152826A1 - Dépôt de films à l'aide de précurseurs de disiloxane - Google Patents

Dépôt de films à l'aide de précurseurs de disiloxane Download PDF

Info

Publication number
WO2014152826A1
WO2014152826A1 PCT/US2014/027899 US2014027899W WO2014152826A1 WO 2014152826 A1 WO2014152826 A1 WO 2014152826A1 US 2014027899 W US2014027899 W US 2014027899W WO 2014152826 A1 WO2014152826 A1 WO 2014152826A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
disiloxane
substrate
precursor
deposition
Prior art date
Application number
PCT/US2014/027899
Other languages
English (en)
Inventor
David Thompson
Mark Saly
Original Assignee
Applied Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Applied Materials, Inc. filed Critical Applied Materials, Inc.
Publication of WO2014152826A1 publication Critical patent/WO2014152826A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • 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
    • 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
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]

Definitions

  • the present invention relates generally to methods of depositing thin films.
  • the invention relates to atomic layer deposition processes for the deposition of Si- containing films.
  • CVD chemical vapor deposition
  • One aspect of the invention pertains to a method of depositing a film.
  • the method comprises exposing a substrate surface to a first precursor and a co-reactant, the first precursor comprising disiloxane to provide a film comprising Si x O y .
  • the co-reactant comprises an oxygen source, and the deposited film comprises Si x O y .
  • x has a value of 1 to 2 and y has a value of 1 to 2.
  • the substrate surface is exposed to the first precursor and the co- reactant simultaneously.
  • the co-reactant comprises a plasma.
  • the co-reactant comprises SiX m H 4 _ m , wherein X is a halogen selected from CI, Br and I, and m has a value between 2 and 4, and the deposited film comprises Si x O y .
  • the co-reactant comprises X z H3_ z Si-SiX z H3_ z , wherein X is a halogen selected from CI, Br and I, and z has a value between 1 and 3, and the deposited film comprises Si x O y .
  • the co-reactant comprises a metal precursor, and the deposited film comprises a metal oxide.
  • the metal comprises a transition metal and the metal precursor comprises a metal halide.
  • Another aspect of the invention pertains to a method of depositing a film comprising SiOC, the method comprising exposing a substrate surface to a first precursor and a co-reactant, the first precursor comprising a compound having a structure represented by:
  • each R is independently hydrogen, CnH2n+2 or OR', wherein R' is CnH2n+2 and n has a value of 1 to 5, to provide a film comprising SiOC.
  • each R group is hydrogen.
  • the co-reactant comprises carbon.
  • the co-reactant comprises acetylene, ethylene or a carbosilane.
  • the co-reactant comprises SiX m H 4 _ m , wherein X is a halogen selected from CI, Br and I, and m has a value between 2 and 4.
  • the co-reactant comprises X z H3_ z Si-SiX z H3_ z , wherein X is a halogen selected from CI, Br and I, and z has a value between 1 and 3.
  • the co-reactant comprises an organic hydroxide containing at least two hydroxide groups.
  • at least one of the R groups is not hydrogen, and the co-reactant is selected from the group consisting of H 2 0, H 2 0 2 , 0 2 , or 0 3 .
  • Another aspect of the invention pertains to a method of depositing a film comprising silicon and oxygen.
  • the method comprises exposing a substrate surface to a first precursor comprising a compound having a structure represented by formula (I): Si SI
  • R R R R wherein each R is independently hydrogen, C1-C6 alkyl, or OR', wherein R' is C1-C6 alkyl or (CH 2 ) P NH 2 , wherein p has a value ranging from 1 to 6, with the proviso that at least one R group is 0(CH 2 ) p NH 2 , to provide a film comprising silicon and oxygen.
  • Si0 2 is deposited.
  • the method further comprises contacting the substrate surface with a co-reagent comprising one or more of H 2 0, H 2 0 2 , 0 2 , and 0 3 .
  • FIGURE 1 is a proposed chemical schematic of a process in accordance with one or more embodiments of the invention.
  • FIGURE 2 is a graph of the growth per cycle and refractive indices as a function of temperature of films according to one or more embodiments of the invention.
  • FIGURE 3 is a graph of the growth per cycle and refractive indices as a function of temperature of films according to one or more embodiments of the invention.
  • Disiloxane (H 3 Si-0-SiH 3 ) may be an effective compound during various deposition processes. Specifically, disiloxane may be useful as a precursor for the deposition of silicon oxides (Si x O y ) or silicon oxycarbides (SiOC), and as a co-reagent for the deposition of metal oxides.
  • one aspect of the invention pertains to method of depositing a film comprising silicon oxide. The method comprises exposing a substrate surface to a first precursor and a co-reactant, the first precursor comprising disiloxane to provide a film comprising Si x O y .
  • Si x O y comprises Si0 2 .
  • the deposited silicon oxide film may be represented as having an empirical formula Si x O y . In some embodiments, x ranges from 1 to 2 and y ranges from 1 to 2.
  • the deposited film comprises Si0 2 .
  • the resulting silicon oxide film is silicon-rich.
  • "silicon-rich" means that the ratio of silicon to oxygen is about 2 to about 1 (i.e., Si 2 O - While not wishing to be bound to any particular theory, Si0 2 is generally considered to be thermally stable, and would therefore be the predicted ratio of silicon and oxygen in a deposited film.
  • one or more embodiments of the invention provides films which can maintain the ratio of silicon to carbon of the precursors in the deposited film.
  • a "substrate” as used throughout this specification refers to any substrate or material surface formed on a substrate upon which film processing is performed during a fabrication process.
  • a substrate surface on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon doped silicon oxides, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application.
  • Substrates include, without limitation, semiconductor wafers.
  • Substrates may be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal and/or bake the substrate surface.
  • any of the film processing steps disclosed may also be performed on an underlayer formed on the substrate as disclosed in more detail below, and the term "substrate surface" is intended to include such underlayer as the context indicates.
  • a substrate can be any type of substrate described above.
  • An optional process step involves preparation of a substrate by treating the substrate with a plasma or other suitable surface treatment to provide active sites on the surface of the substrate. Examples of suitable active sites include, but are not limited to O-H, N-H, or S-H terminated surfaces.
  • the disiloxane may be used with an oxygenating plasma to achieve films comprising Si x O y .
  • Si x O y comprises Si0 2 .
  • the co-reactant comprises an oxygen source (i.e., is an oxygen precursor).
  • the oxygen source comprises H 2 0, H 2 0 2 , 0 2 , (3 ⁇ 4, or an oxygen plasma.
  • the substrate surface may be exposed to the disiloxane and plasma sequentially or substantially sequentially.
  • substantially sequentially means that the majority of the duration of the disiloxane exposure does not overlap with the exposure of the co-reagent, although there may be some overlap.
  • the substrate surface may be exposed to the disiloxane and plasma simultaneously or substantially simultaneously.
  • substantially simultaneously means that the majority of the duration of the disiloxane exposure overlaps with the exposure of the co- reagent, although they may not be co-extensive.
  • FIGURE shows a possible chemical schematic for an exemplary process.
  • a substrate surface containing -OH surface functionality is exposed to disiloxane.
  • the disiloxane reacts with the surface, and a SiH 3 group becomes bonded to the surface.
  • Silanol is released as a byproduct.
  • the substrate surface may then be exposed to ozone, an 0 2 plasma or water to provide more -OH groups for the next reaction.
  • a layer of is deposited, and the film comprises silicon and oxygen.
  • one or more of the reactants may be purged.
  • the method further comprises purging the first precursor after the substrate is exposed to the first precursor, and purging the co-reactant after the substrate surface is exposed to the co-reactant.
  • Carbon doping also be incorporated into the films in one or more embodiments.
  • One way of achieving this is through reaction with a disiloxane derivative, wherein one or more of the hydrogen atoms is replaced with a carbon containing group.
  • a disiloxane derivative wherein one or more of the hydrogen atoms is replaced with a carbon containing group.
  • Such examples include C1-C6 alkyl, and in further embodiments, ethyl or methyl.
  • Another way of achieving carbon doping is to further use a carbon precursor.
  • Such precursors include, but are not limited to compounds having the formulae (X m H 3 _ m Si )z CH 4 _ z , or (X m H _ m Si)(CH 2 ) n (SiX m H _ m ), wherein X is a halogen, m has a value of between 1 and 3, and z has a value of between 1 and 3, and n has a value between 2 and 5.
  • Another aspect of the invention pertains to method of depositing a film comprising Si x O y , the method comprising exposing a substrate surface to a first precursor and a co-reactant, the first precursor comprising disiloxane to provide a film comprising Si x O y , wherein the co-reactant comprises an oxygen-containing compound.
  • the co-reactant comprises H 2 0, H 2 0 2 , 0 2 or 0 3 .
  • the film contains substantially no nitrogen.
  • Si x O y comprises Si0 2 .
  • the deposition may take place at a substrate temperature in the range of about
  • the temperature ranges from about 65 to about 250 °C.
  • the substrate temperature may be from about 50, 60, 70, 80, 90, or 100 to about 200, 225, 250, 275, 300, 325, 350, 375 or 400 °C.
  • Another aspect of the invention is a method of depositing a film comprising silicon and oxygen.
  • the method comprises exposing a substrate surface to a first precursor comprising a compound having a structure represented by formula (I):
  • R R R R wherein each R is independently hydrogen, C1-C6 alkyl, or OR', wherein R' is C1-C6 alkyl or (CH 2 ) P NH 2 , wherein p has a value ranging from 1 to 6, with the proviso that at least one R group is 0(CH 2 ) p NH 2 , to provide a film comprising silicon and oxygen.
  • the -NH 2 group may act as a catalyst during deposition. Accordingly, the compound is able to self-catalyze reaction. In some embodiments, it may be used with a co-reagent.
  • the method further comprises contacting the substrate surface with a co-reagent comprising one or more of H 2 0, H 2 0 2 , 0 2 , and 0 3 .
  • the co-reagent comprises H 2 0, and/or 0 2 , and particularly 0 2 .
  • the deposited film comprises Si0 2 . [0025] The deposition may take place at a substrate temperature in the range of about
  • the temperature ranges from about 65 to about 250 °C.
  • the substrate temperature may be from about 50, 60, 70, 80, 90, or 100 to about 200, 225, 250, 275, 300, 325, 350, 375 or 400 °C.
  • the temperature ranges from about 120 to about 200 °C.
  • Carbon doping also be incorporated into the films in one or more embodiments.
  • One way of achieving this is through reaction with a disiloxane derivative, wherein one or more of the hydrogen atoms is replaced with a carbon containing group.
  • a disiloxane derivative wherein one or more of the hydrogen atoms is replaced with a carbon containing group.
  • Such examples include C1-C6 alkyl, and in further embodiments, ethyl or methyl.
  • Another way of achieving carbon doping is to further use a carbon precursor.
  • Such precursors include, but are not limited to compounds having the formulae (X m H3_ m Si )z CH 4 _ z , or (X m H 3 _ m Si)(CH 2 ) n (SiX m H 3 _ m ), wherein X is a halogen, m has a value of between 1 and 3, and z has a value of between 1 and 3, and n has a value between 2 and 5.
  • An exemplary embodiment of the invention pertains to method of depositing a film comprising Si x O y , the method comprising exposing a substrate surface to a first precursor and a co-reactant, the first precursor comprising disiloxane to provide a film comprising Si x O y , wherein the co-reactant contains a silicon-halide bond.
  • Si x O y comprises Si0 2 .
  • the co-reactant comprises SiX m H4_ m , wherein X is a halogen, and m has a value between 2 and 4.
  • X is selected from CI, Br and I.
  • X is CI.
  • suitable co-reactants include, but are not limited to, dichlorosilane, tetrachlorosilane, and diiodosilane. While not wishing to be bound by any particular theory, it is thought that at least two halides are required for continued film deposition. That is, upon reaction of the co-reactant with the film surface, one halide will be reacted.
  • the co-reactant comprises X z H3_ z Si-SiX z H3_ z , wherein X is a halogen, and z has a value between 1 and 3.
  • X is selected from CI, Br and I.
  • X is CI.
  • suitable co-reactants include, but are not limited to, hexachlorodisilane.
  • Additional compounds which can be used as a carbon source include those with formula (X m H 3 _ m Si )z CH 4 _ z , or (X m H 3 _ m Si)(CH 2 ) n (SiX m H 3 _ m ), wherein X is a halogen, m has a value of between 1 and 3, and z has a value of between 1 and 3, and n has a value between 2 and 5.
  • a film comprising SiOC is provided.
  • the first precursor has a formula (X y H 3 _ y Si) z CH 4 _ z .
  • each X is independently selected from CI, Br and I.
  • embodiments at least one of the X groups is CI.
  • all X groups are CI.
  • Such a compound is known as bis(trichlorosilyl)methane, hexachlorodisilylmethylene, 1,1' -methylenebis( 1 ,1,1 -trichlorosilane), or methylenebis(trichlorosilane), and has a structure represented by:
  • Suitable precursors include, but are not limited to those having a structure represented by:
  • the compound has a formula (X y H _ y Si)(CH 2 ) n (SiX y H _ y ).
  • n has a value of 2 or 3, or in even further embodiments, 2. Compounds of this formula may be used to further increase the carbon content, as the starting C:Si ratio will be higher.
  • each X is independently selected from CI, Br and I.
  • embodiments at least one of the X groups is CI.
  • all X groups are CI.
  • a catalyst may be utilized to facilitate the deposition process.
  • the catalyst comprises a neutral two electron donor base.
  • the catalyst comprises an amine.
  • the catalyst comprises a tertiary amine.
  • the catalyst comprises pyridine.
  • the catalyst comprises N3 ⁇ 4.
  • a tertiary amine with a vapor pressure lower than pyridine (which is less than about 20 torr at 20 °C) can be used.
  • the deposition may take place at a substrate temperature in the range of about
  • the temperature ranges from about 65 to about 250 °C.
  • the substrate temperature may be from about 50, 60, 70, 80, 90, or 100 to about 200, 225, 250, 275, 300, 325, 350, 375 or 400 °C.
  • Yet another aspect of the invention pertains to a method of depositing a film comprising SiOC, the method comprising exposing a substrate surface to a first precursor and a co-reactant, the first precursor comprising a compound having a structure represented by formula (I):
  • each R is independently hydrogen, C n H 2n+ 2 or OR', wherein R' is C n H 2n+2 and n has a value of 1 to 5, to provide a film comprising SiOC.
  • OR' is an alkoxy group, which in some embodiments can comprise methoxy or ethoxy. In such examples, the precursor may contribute more oxygen into the film.
  • the co-reactant is a carbon source, so that the resulting film may comprise SiOC.
  • the carbon precursor is any precursor known in the art to contribute carbon. Examples of suitable co-reactants comprising carbon include, but are not limited to ethylene, acetylene, carbosilanes, etc.
  • the carbon precursor may be plasma or non-plasma.
  • the co-reagent comprises a compound containing carbon and at least two hydroxyl groups. Such co-reactants can act as a source of carbon and oxygen. In further embodiments, the co-reagent comprises a diol.
  • diols may be used which contain carbon.
  • carbon incorporated into the film may come from both the first and co-reagents.
  • Suitable co-reagents include, but are not limited to, ethylene glycol, propylene glycol and butane- 1,4-diol.
  • the diol comprises ethylene glycol. While not wishing to be bound to any particular theory, it is thought that at least two hydroxyl groups are necessary in order to allow for subsequent deposition cycles. That is, one OH group is used to deposit the co-reagent, and then the second may be used for the next cycle to react with the Si-Cl in the first precursor.
  • the compound of formula (I) contains carbon (i.e., at least one of the R groups contains a carbon atom), it can act as both a carbon source and a silicon source.
  • the R group is C1-C6 alkyl.
  • the R group is methyl.
  • the co-reagent may be an oxygen source.
  • the co-reagent may comprise water. In embodiments where the co-reagent comprises water, the resulting film will still contain carbon from the first precursor.
  • the co-reagent may comprise a compound containing carbon and at least two hydroxyl groups.
  • the co-reagent comprises a diol.
  • diols may be used which contain carbon.
  • carbon incorporated into the film may come from both the first and co-reagents.
  • Suitable co-reagents include, but are not limited to, ethylene glycol, propylene glycol and butane- 1,4-diol.
  • the diol comprises ethylene glycol.
  • the co- reactant comprises a triol. While not wishing to be bound to any particular theory, it is thought that at least two hydroxyl groups are necessary in order to allow for subsequent deposition cycles. That is, one OH group is used to deposit the co-reagent, and then the second may be used for the next cycle to react with the Si-Cl in the first precursor.
  • the co-reagent may not comprise carbon. That is, in some embodiments, at least one of the R groups is not hydrogen, and the co-reagent comprising one or more of H 2 0, H 2 0 2 , 0 2 , and 0 3 . In further embodiments, the co-reagent comprises H 2 0, and/or 0 2 , and particularly 0 2 .
  • Various disiloxane/disiloxane derivatives and co-reagents can be selected to tune the amount of carbon in the deposited film. The higher the carbon: silicon ratio of the precursors, the higher the ratio will be in the resulting SiOC film. Thus, for example, longer carbon chains may be selected where a higher amount of carbon is desired.
  • the deposition may take place at a substrate temperature in the range of about
  • the temperature ranges from about 65 to about 250 °C.
  • the substrate temperature may be from about 50, 60, 70, 80, 90, or 100 to about 200, 225, 250, 275, 300, 325, 350, 375 or 400 °C.
  • One or more embodiments of the invention may have a nucleation delay. Accordingly, one aspect of the invention pertains to activation of the substrate surface to a plasma. That is, in some embodiments, the methods described further comprise exposing the substrate surface to a plasma. It is also thought that this activation procedure will help to increase growth rate at higher temperatures. While not wishing to be bound to any particular theories, it is thought that at higher temperatures, the disiloxane or disiloxane-based molecules will not adhere to the substrate surface as easily. As such, the plasma is thought to help the compound adhere to the surface. In one or more embodiments, the plasma comprises an oxygen plasma. In some embodiments, the substrate has a temperature of above 200, 250 or 300 °C while being exposed to the plasma.
  • metal oxides may be deposited using water as a co-reactant. Problems can occur using water, as water has a high "sticking coefficient," due to its hydrogen bonding, sticking to the chamber lines, wall, etc. Thus, as water is flowed through a chamber, it can It is thought that disiloxane will have a much lower sticking coefficient, as it is a linear molecule with no hydrogen bonding.
  • another aspect of the invention pertains to a method of depositing a film comprising a metal oxide.
  • the method comprises exposing a substrate surface to a metal precursor and disiloxane to provide a film comprising a metal oxide. It is thought that the disiloxane will react with metal halides as water does. The byproduct produced from such a reaction would be could be a mono halo silane precursor. Such a byproduct is expected to be volatile, allowing for easy removal.
  • the metal comprises a transition metal.
  • the metal precursor comprises a metal halide. Any currently used transition metal halides that are used with water are suitable for use with disiloxane. Examples include, but are not limited to halides of W, Zr, Hf and Ti.
  • the film comprises tungsten oxide.
  • a suitable metal precursor for this film comprises WC1 5.
  • the film comprises zirconium oxide.
  • a suitable metal precursor for this film comprises ZrCl 5 .
  • the film comprises hafnium oxide.
  • a suitable metal precursor for this film comprises HfCl 2 .
  • the film comprises titanium oxide.
  • a suitable metal precursor for this film comprises T1CI 4 .
  • the deposition may take place at a substrate temperature in the range of about 50 to about 600 °C. In further embodiments, the temperature ranges from about 65 to about 250 °C. In some embodiments the substrate temperature may be from about 50, 60, 70, 80, 90, or 100 to about 200, 225, 250, 275, 300, 325, 350, 375 or 400 °C.
  • the reaction conditions for the ALD reaction will be selected based on the properties of the film precursors and substrate surface.
  • the deposition may be carried out at atmospheric pressure, but may also be carried out at reduced pressure.
  • the vapor pressure of the reagents should be low enough to be practical in such applications.
  • the substrate temperature should be low enough to keep the bonds of the substrate surface intact and to prevent thermal decomposition of gaseous reactants. However, the substrate temperature should also be high enough to keep the film precursors in the gaseous phase and to provide sufficient energy for surface reactions.
  • the specific temperature depends on the specific substrate, film precursors, and pressure. The properties of the specific substrate, film precursors, etc.
  • the deposition is carried out at a temperature less than about 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 125, or 100 °C, and greater than 23 °C, 50 or 75 °C.
  • the films are deposited using an ALD or CVD process.
  • the substrate may be exposed to more than one precursor continuously simultaneously, or substantially simultaneously, as appropriate.
  • substantially simultaneously means that a majority of the flow of one component overlaps with the flow of another, although there may be some time where they are not co-flowed.
  • films are deposited using an atomic layer deposition (ALD) process. Therefore, in one embodiment, contacting the substrate surface with two or more precursors occurs sequentially or substantially sequentially.
  • ALD atomic layer deposition
  • one or more layers may be formed during a plasma enhanced atomic layer deposition (PEALD) process.
  • PEALD plasma enhanced atomic layer deposition
  • the use of plasma provides sufficient energy to promote a species into the excited state where surface reactions become favorable and likely.
  • Introducing the plasma into the process can be continuous or pulsed.
  • sequential pulses of precursors (or reactive gases) and plasma are used to process a layer.
  • the reagents may be ionized either locally (i.e., within the processing area) or remotely (i.e., outside the processing area). In some embodiments, remote ionization can occur upstream of the deposition chamber such that ions or other energetic or light emitting species are not in direct contact with the depositing film.
  • the plasma is generated external from the processing chamber, such as by a remote plasma generator system.
  • the plasma may be generated via any suitable plasma generation process or technique known to those skilled in the art.
  • plasma may be generated by one or more of a microwave (MW) frequency generator or a radio frequency (RF) generator.
  • MW microwave
  • RF radio frequency
  • the frequency of the plasma may be tuned depending on the specific reactive species being used. Suitable frequencies include, but are not limited to, 2 MHz, 13.56 MHz, 40 MHz, 60 MHz and 100 MHz.
  • plasmas may be used during the deposition processes disclosed herein, it should be noted that plasmas are not necessarily required.
  • the substrate is subjected to processing prior to and/or after forming the layer.
  • This processing can be performed in the same chamber or in one or more separate processing chambers.
  • the substrate is moved from the first chamber to a separate, second chamber for further processing.
  • the substrate can be moved directly from the first chamber to the separate processing chamber, or it can be moved from the first chamber to one or more transfer chambers, and then moved to the desired separate processing chamber.
  • the processing apparatus may comprise multiple chambers in communication with a transfer station. An apparatus of this sort may be referred to as a "cluster tool" or "clustered system", and the like.
  • a cluster tool is a modular system comprising multiple chambers which perform various functions including substrate center-finding and orientation, degassing, annealing, deposition and/or etching.
  • a cluster tool includes at least a first chamber and a central transfer chamber.
  • the central transfer chamber may house a robot that can shuttle substrates between and among processing chambers and load lock chambers.
  • the transfer chamber is typically maintained at a vacuum condition and provides an intermediate stage for shuttling substrates from one chamber to another and/or to a load lock chamber positioned at a front end of the cluster tool.
  • processing chambers which may be used include, but are not limited to, cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, chemical clean, thermal treatment such as RTP, plasma nitridation, degas, orientation, hydroxylation and other substrate processes.
  • CLD cyclical layer deposition
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • etch pre-clean
  • thermal treatment such as RTP, plasma nitridation, degas, orientation, hydroxylation and other substrate processes.
  • the substrate is continuously under vacuum or "load lock” conditions, and is not exposed to ambient air when being moved from one chamber to the next.
  • the transfer chambers are thus under vacuum and are "pumped down” under vacuum pressure.
  • Inert gases may be present in the processing chambers or the transfer chambers.
  • an inert gas is used as a purge gas to remove some or all of the reactants after forming the layer on the surface of the substrate.
  • a purge gas is injected at the exit of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and/or additional processing chamber. Thus, the flow of inert gas forms a curtain at the exit of the chamber.
  • the substrate can be processed in single substrate deposition chambers, where a single substrate is loaded, processed and unloaded before another substrate is processed.
  • the substrate can also be processed in a continuous manner, like a conveyer system, in which multiple substrate are individually loaded into a first part of the chamber, move through the chamber and are unloaded from a second part of the chamber.
  • the shape of the chamber and associated conveyer system can form a straight path or curved path.
  • the processing chamber may be a carousel in which multiple substrates are moved about a central axis and are exposed to deposition, etch, annealing, cleaning, etc. processes throughout the carousel path.
  • the substrate can be heated or cooled. Such heating or cooling can be accomplished by any suitable means including, but not limited to, changing the temperature of the substrate support and flowing heated or cooled gases to the substrate surface.
  • the substrate support includes a heater/cooler which can be controlled to change the substrate temperature conductively.
  • the gases (either reactive gases or inert gases) being employed are heated or cooled to locally change the substrate temperature.
  • a heater/cooler is positioned within the chamber adjacent the substrate surface to convectively change the substrate temperature.
  • the substrate can also be stationary or rotated during processing. A rotating substrate can be rotated continuously or in discreet steps.
  • a substrate may be rotated throughout the entire process, or the substrate can be rotated by a small amount between exposures to different reactive or purge gases. Rotating the substrate during processing (either continuously or in steps) may help produce a more uniform deposition or etch by minimizing the effect of, for example, local variability in gas flow geometries.
  • the substrate can be exposed to the first and co-reagents either spatially or temporally separated processes.
  • Temporal ALD is a traditional process in which the first precursor flows into the chamber to react with the surface. The first precursor is purged from the chamber before flowing the co-reagent.
  • spatial ALD both the first and co-reagents are simultaneously flowed to the chamber but are separated spatially so that there is a region between the flows that prevents mixing of the precursors.
  • the substrate In spatial ALD, the substrate must be moved relative to the gas distribution plate, or vice- versa.
  • the substrate and chamber may be exposed to a purge step after stopping the flow of the disiloxane, precursor, co-reagent, etc.
  • a purge gas may be flowed after any of the precursors is flowed/exposed to a substrate surface.
  • a purge gas may be administered into the processing chamber with a flow rate within a range from about 10 seem to about 2,000 seem, for example, from about 50 seem to about 1,000 seem, and in a specific example, from about 100 seem to about 500 seem, for example, about 200 seem.
  • the purge step removes any excess precursor, byproducts and other contaminants within the processing chamber.
  • the purge step may be conducted for a time period within a range from about 0.1 seconds to about 8 seconds, for example, from about 1 second to about 5 seconds, and in a specific example, from about 4 seconds.
  • the carrier gas, the purge gas, the deposition gas, or other process gas may contain nitrogen, hydrogen, argon, neon, helium, or combinations thereof.
  • the carrier gas comprises nitrogen.
  • Example 1 Silicon Oxide Deposition Using Disiloxane and Oxygen Plasma
  • a substrate surface comprising -OH functional groups is provided in a deposition chamber.
  • Disiloxane is then flowed into the chamber, and the substrate surface is exposed to the disiloxane.
  • the disiloxane reacts with the -OH functionality so that SiH 3 is deposited onto the surface, with silanol as a byproduct.
  • the substrate is then exposed to an 0 2 plasma, thereby providing a layer of Si-O, as well as -OH functionality at the substrate surface again.
  • Example 3 Si0 2 Deposition Using Disiloxane and Oxygen Gas
  • Thin films of Si0 2 were deposited by ALD using disiloxane and oxygen gas at substrate temperatures of 100, 150, and 200 °C.
  • the parameters for deposition were as follows in Table 2:
  • the growth rates and refractive indices were determined using ellipsometry. In order of increasing deposition temperature (100, 150, 200 °C), the growth rates observed on Si(100)-native and Si0 2 IK were 1.09, 0.95, and 0.72 A/cycle and 0.81, 0.73, and 0.42
  • Si0 2 films were deposited using disiloxane and 0 2 .
  • the pulse length of disiloxane was 0.3 seconds, and it was flowed at a rate of 200 seem. This was followed by a purge of N 2 for 4.0 seconds at 200 seem. Next, 0 2 was flowed for 0.5 seconds at a rate of 200 seem.
  • the chamber was again purged with N 2 for 4.0 seconds at 200 seem. The chamber had a pressure of 1.5 Torr.
  • the film was deposited on Si0 2 IK at temperatures ranging from about 75 to 130 °C, and on Si(native) at temperatures ranging from about 75 to 100 °C.
  • FIGURE 2 A graph of the growth per cycle (GPC) and refractive indices (RI) versus temperature is shown in FIGURE 2.
  • the plot was generated with sub-saturative conditions.
  • the RI for the film on Si0 2 IK was -1.46 and on Si(native) was 1.33-1.35.
  • a process window exists from -75-130 °C on Si02 IK and -75-100 °C on Si(native).
  • the figure also shows that for at least some of the films, growth rate decreases with an increase in temperature. It is thought that this is due to precursor thermal desorption.
  • Si0 2 films were deposited using disiloxane and 0 2 .
  • the pulse length of disiloxane was varied, and it was flowed at a rate of 200 seem. This was followed by a purge of N 2 for 4.0 seconds at 200 seem. Next, 0 2 was flowed for 0.5 seconds at a rate of 200 seem.
  • the chamber was again purged with N 2 for 4.0 seconds at 200 seem. The chamber had a pressure of 1.5 Torr.
  • the film was deposited on Si0 2 IK and on Si(native).
  • a graph of the growth per cycle (GPC) and refractive indices (RI) versus disiloxane pulse length is shown in FIGURE 3.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne des procédés de dépôt de divers films contenant du silicium à l'aide de disiloxane ou d'un dérivé de disiloxane. Certains procédés concernent le dépôt de SixOy à l'aide d'un composé contenant de l'oxygène, de plasma ou d'un halogénosilane. Certains autres procédés concernent le dépôt d'oxydes métalliques à l'aide d'un halogénure métallique et de disiloxane. Certains autres procédés encore ont trait au dépôt de films de SiOC à l'aide de disiloxane ou de dérivés de disiloxane contenant du carbone, éventuellement avec des hydroxydes organiques.
PCT/US2014/027899 2013-03-14 2014-03-14 Dépôt de films à l'aide de précurseurs de disiloxane WO2014152826A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201361782281P 2013-03-14 2013-03-14
US61/782,281 2013-03-14
US201361792569P 2013-03-15 2013-03-15
US61/792,569 2013-03-15

Publications (1)

Publication Number Publication Date
WO2014152826A1 true WO2014152826A1 (fr) 2014-09-25

Family

ID=51581327

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/027899 WO2014152826A1 (fr) 2013-03-14 2014-03-14 Dépôt de films à l'aide de précurseurs de disiloxane

Country Status (2)

Country Link
TW (1) TW201443274A (fr)
WO (1) WO2014152826A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170114465A1 (en) * 2015-10-22 2017-04-27 Applied Materials, Inc. Methods Of Depositing Flowable Films Comprising SiO and SiN
US11584854B2 (en) 2016-09-19 2023-02-21 Versum Materials Us, Llc Compositions and methods for the deposition of silicon oxide films

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5023295A (en) * 1988-09-16 1991-06-11 Wacker-Chemie Gmbh Compositions suitable for coating the surface of electrical high-voltage insulators
US5162480A (en) * 1990-12-14 1992-11-10 Union Carbide Chemicals & Plastics Technology Corporation Self-curing ceramicizable polysiloxanes
US20010055672A1 (en) * 2000-02-08 2001-12-27 Todd Michael A. Low dielectric constant materials and processes
US20030064154A1 (en) * 2001-08-06 2003-04-03 Laxman Ravi K. Low-K dielectric thin films and chemical vapor deposition method of making same
US20090075490A1 (en) * 2007-09-18 2009-03-19 L'air Liquite Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method of forming silicon-containing films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5023295A (en) * 1988-09-16 1991-06-11 Wacker-Chemie Gmbh Compositions suitable for coating the surface of electrical high-voltage insulators
US5162480A (en) * 1990-12-14 1992-11-10 Union Carbide Chemicals & Plastics Technology Corporation Self-curing ceramicizable polysiloxanes
US20010055672A1 (en) * 2000-02-08 2001-12-27 Todd Michael A. Low dielectric constant materials and processes
US20030064154A1 (en) * 2001-08-06 2003-04-03 Laxman Ravi K. Low-K dielectric thin films and chemical vapor deposition method of making same
US20090075490A1 (en) * 2007-09-18 2009-03-19 L'air Liquite Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method of forming silicon-containing films

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170114465A1 (en) * 2015-10-22 2017-04-27 Applied Materials, Inc. Methods Of Depositing Flowable Films Comprising SiO and SiN
KR20180058232A (ko) * 2015-10-22 2018-05-31 어플라이드 머티어리얼스, 인코포레이티드 SiO 및 SiN을 포함하는 유동성 막들을 증착시키는 방법들
CN108140555A (zh) * 2015-10-22 2018-06-08 应用材料公司 沉积包含SiO及SiN 的可流动薄膜的方法
CN108140555B (zh) * 2015-10-22 2024-03-15 应用材料公司 沉积包含SiO及SiN的可流动薄膜的方法
KR102692947B1 (ko) 2015-10-22 2024-08-06 어플라이드 머티어리얼스, 인코포레이티드 SiO 및 SiN을 포함하는 유동성 막들을 증착시키는 방법들
US11584854B2 (en) 2016-09-19 2023-02-21 Versum Materials Us, Llc Compositions and methods for the deposition of silicon oxide films

Also Published As

Publication number Publication date
TW201443274A (zh) 2014-11-16

Similar Documents

Publication Publication Date Title
KR102692947B1 (ko) SiO 및 SiN을 포함하는 유동성 막들을 증착시키는 방법들
US7402534B2 (en) Pretreatment processes within a batch ALD reactor
US9984868B2 (en) PEALD of films comprising silicon nitride
US9643844B2 (en) Low temperature atomic layer deposition of films comprising SiCN or SiCON
US10790141B2 (en) Surface-selective atomic layer deposition using hydrosilylation passivation
US20070065578A1 (en) Treatment processes for a batch ALD reactor
US9382270B2 (en) Substituted silacyclopropane precursors and their use for the deposition of silicon-containing films
US20240047193A1 (en) Methods of Depositing SiCON with C, O, and N Compositional Control
JP2023507326A (ja) 炭素含有量が調整可能な炭窒化ケイ素間隙充填
US11107674B2 (en) Methods for depositing silicon nitride
WO2014152826A1 (fr) Dépôt de films à l'aide de précurseurs de disiloxane
US20160002782A1 (en) Catalytic Atomic Layer Deposition Of Films Comprising SiOC
US9200365B2 (en) Method of catalytic film deposition
JP2024524999A (ja) 新規の酸化剤及び歪環前駆体
KR20220062111A (ko) 할로겐화된 실릴아미드들을 사용하여 SiCO(N)를 원자층 증착하는 방법들
TW201316406A (zh) 用於低溫膜沉積之碳矽烷前驅物

Legal Events

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

Ref document number: 14771173

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14771173

Country of ref document: EP

Kind code of ref document: A1