WO2022204663A1 - Couches de nitrure de titane conformes et lisses et procédés pour leur formation - Google Patents

Couches de nitrure de titane conformes et lisses et procédés pour leur formation Download PDF

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Publication number
WO2022204663A1
WO2022204663A1 PCT/US2022/071227 US2022071227W WO2022204663A1 WO 2022204663 A1 WO2022204663 A1 WO 2022204663A1 US 2022071227 W US2022071227 W US 2022071227W WO 2022204663 A1 WO2022204663 A1 WO 2022204663A1
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Prior art keywords
thin film
precursor
tin
exposure
flow rate
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PCT/US2022/071227
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English (en)
Inventor
Hyunchol Cho
Hae Young Kim
Bunsen B. Nie
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Eugenus, Inc.
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Priority claimed from US17/547,086 external-priority patent/US20220172988A1/en
Application filed by Eugenus, Inc. filed Critical Eugenus, Inc.
Priority to JP2023557327A priority Critical patent/JP2024511050A/ja
Priority to CN202280036418.0A priority patent/CN117355631A/zh
Priority to KR1020237035868A priority patent/KR20230172494A/ko
Publication of WO2022204663A1 publication Critical patent/WO2022204663A1/fr

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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
    • C23C16/44—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
    • C23C16/45557—Pulsed pressure or control pressure
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—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
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • 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
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
    • 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
    • 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]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
    • H01L21/28562—Selective deposition
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric

Definitions

  • the disclosed technology generally relates to forming a titanium nitride layer, and more particularly to a conformal and smooth titanium nitride layer.
  • Titanium nitride has been widely used in fabrication of various structures in integrated circuits (ICs). For example, TiN has been used in diffusion barriers, various electrodes and metallization structures. Such wide usage of TiN in IC fabrication can be attributed to its structural, thermal and electrical properties. As the dimensions of various IC structures shrink, TiN is formed on features having increasingly smaller dimensions and complex topologies. For example, as the technology node scales to 10 nm node and beyond, there is a need for TiN layers, e.g., as diffusion barriers, that can conformally line high aspect ratio trenches and vias having dimensions as small as few nanometers.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the techniques described herein relate to a method of depositing a thin film including titanium nitride (TiN) by cyclical vapor deposition, the method including: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each including an exposure to a Ti precursor and an exposure to ammonia (NFb) at a first NFb flow rate; and after forming the TiN thin film, subjecting the semiconductor substrate, without deposition of an additional TiN thin film on the thin film, to a post-deposition exposure to NH3 at a second NH3 flow rate, wherein the second NH3 flow rate is lower than the first NH3 flow rate by at least a factor of two.
  • TiN titanium nitride
  • the techniques described herein relate to a method, wherein the method is carried out in a thin film deposition system wherein, relative to a thin TiN film deposited in the same thin film deposition system using the method except for subjecting the semiconductor substrate to the post deposition exposure to NH3, a number of particles on or embedded in the TiN thin film having a size greater than 0.1 pm is reduced by 50% or more.
  • the techniques described herein relate to a method, wherein forming the TiN thin film and subjecting the semiconductor substrate to a post deposition exposure are performed at the same semiconductor substrate temperature.
  • the techniques described herein relate to a method, wherein the first NH3 flow rate is 1000-3000 seem, and the second NH3 flow rate is 200-1000 seem.
  • the techniques described herein relate to a method, wherein a ratio of the first NH3 flow rate to the Ti precursor flow rate is 3 to 100. In some embodiments, the techniques described herein relate to a method, wherein the Ti precursor flow rate is 100 seem - 5000 seem and lower than the first NH3 flow rate. In some embodiments, the techniques described herein relate to a method, wherein a duration of each of the one or more cyclic vapor deposition cycles is less than 2.0 sec.
  • the techniques described herein relate to a method of depositing a thin film including titanium nitride (TiN) by cyclical vapor deposition, the method including: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each including an exposure to a Ti precursor and an exposure to ammonia (NH3) for a first NH3 exposure duration; and after forming the TiN thin film, subjecting the semiconductor substrate, without deposition of an additional TiN thin film, to a post-deposition exposure of NH3 for a second NH3 exposure duration, wherein the second NH3 exposure duration is greater than the first NH3 exposure duration by at least a factor of five.
  • TiN titanium nitride
  • the techniques described herein relate to a method, wherein the method is carried out in a thin film deposition system wherein, relative to a TiN thin film deposited in the same thin film deposition system using the method except for subjecting the semiconductor substrate to the post deposition exposure to NH3, a number of particles on or embedded in the TiN thin film having a size greater than 0.1 pm is reduced by 50% or more.
  • the techniques described herein relate to a method, wherein forming the TiN thin film and subjecting the formed TiN thin film to a post-deposition exposure are performed at the same semiconductor substrate temperature.
  • the techniques described herein relate to a method, wherein the first NH3 exposure duration is 0.1-0.6 sec., and the second NH3 exposure duration exceeds 1 sec.
  • the techniques described herein relate to a method of depositing a thin film including titanium nitride (TiN) by cyclical vapor deposition process, the method including: subjecting a thin film deposition chamber without a substrate disposed therein to a pre-deposition chamber purge with ammonia (NH3) at a first NH3 purge flow rate; transferring a semiconductor substrate into the thin film deposition chamber; and forming on the semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each including an exposure to a Ti precursor and an exposure to NH3.
  • NH3 titanium nitride
  • the techniques described herein relate to a method, wherein the method is carried out in the thin film deposition system wherein, relative to a TiN thin film deposited in the same thin film deposition system using the method except for subjecting the thin film deposition chamber to the pre-deposition NH3 purge, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 pm is reduced by 50% or more.
  • the techniques described herein relate to a method, wherein the first NH3 purge flow rate exceeds 200 seem.
  • the techniques described herein relate to a method, wherein the pre-deposition chamber purge is performed for a duration exceeding 1 sec.
  • the techniques described herein relate to a method, wherein the method is carried out in a process station of a thin film deposition system, wherein the thin film deposition system includes a plurality of process stations each configured to carry out the method.
  • the techniques described herein relate to a method, wherein forming the TiN thin film includes exposing the semiconductor substrate to NH3 at a second NH3 flow rate of 500-10,000 seem.
  • the techniques described herein relate to a method, wherein the one or more cyclical vapor deposition cycles includes exposure to the Ti precursor at a Ti precursor flow rate and exposure to ammonia (NH3) at a second NH3 flow rate such that a flow rate ratio of the second NH3 flow rate to the Ti precursor flow rate is 3 to 100.
  • NH3 ammonia
  • the techniques described herein relate to a method, wherein forming the TiN thin film includes exposing the semiconductor substrate to the Ti precursor at the Ti precursor flow rate of 100 seem - 5000 seem and lower than the second NH3 flow rate. In some embodiments, the techniques described herein relate to a method, wherein a duration each of the one or more cyclical vapor deposition cycles is less than 2.0 sec.
  • FIGS. 1A-1D schematically illustrate nucleation and growth mechanisms of thin films under different growth modes.
  • FIG. 2 is a cross-sectional transmission electron micrograph of a TiN layer grown on an oxide-coated silicon substrate by thermal atomic layer deposition.
  • FIG. 3A is a flow chart schematically illustrating an atomic layer deposition method of forming a TiN layer by exposing a substrate to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 3B schematically illustrates a cross-sectional view of a semiconductor structure comprising a TiN layer formed by an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 4 schematically illustrates pressure traces of different cycles of an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 5 schematically illustrates a cross-sectional view of a via lined with a TiN layer having different thicknesses at different portions of the via.
  • FIG. 6 is a graph showing experimentally measured surface roughness and step coverage trends as functions of thickness for TiN layers formed by an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 7A is a cross-sectional transmission electron micrograph of high aspect ratio vias lined with a TiN layer formed by an atomic layer deposition method in which a substrate is exposed to ALD cycles performed at the same precursor exposure pressure.
  • FIG. 7B is a cross-sectional transmission electron micrograph an upper region of the high aspect ratio vias shown in FIG. 7 A.
  • FIG. 7C is a cross-sectional transmission electron micrograph of a lower region of the high aspect ratio vias shown in FIG. 7 A.
  • FIG. 8A is a cross-sectional transmission electron micrograph of a TiN layer formed at an upper region of a high aspect ratio via similar to that shown in FIG. 7A by an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 8B is a cross-sectional transmission electron micrograph of a TiN layer formed at a lower region of the high aspect ratio via trench shown in FIG. 8A.
  • FIG. 9 is a graph showing statistical comparison of measured step coverages between a TiN layer formed by atomic layer deposition at a single exposure pressure and a TiN layer formed by atomic layer deposition at a plurality of exposure pressures, according to embodiments.
  • FIG. 10 schematically illustrates a cross-sectional view of a via lined with a TiN layer formed by an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 11 is a flow chart schematically illustrating an atomic layer deposition method of forming a TiN layer having high (111) crystalline texture by exposing a substrate to a relatively high N precursor flow rate, according to embodiments.
  • FIG. 12A illustrates experimental X-ray diffraction spectra of TiN thin films having varying degrees of (111) crystalline texture, according to embodiments.
  • FIG. 12B is a graph illustrating the experimental ratios of a peak height of an X-ray diffraction peak corresponding to a (111) crystal orientation of TiN to a peak height of an X-ray diffraction peak corresponding to a (200) crystal orientation of TiN obtained from the X-ray diffraction spectra of FIG. 12A.
  • FIG. 13 is a graph of experimental thickness and resistivity measurements of TiN thin films having increased (111) crystalline texture, according to embodiments.
  • FIG. 14 is a graph of experimental hardness and modulus measurements of TiN thin films having increased (111) crystalline texture, according to embodiments.
  • FIG. 15 is a graph of experimental hardness measurements of TiN thin films having increased (111) crystalline texture, according to embodiments.
  • FIG. 16 illustrates experimental X-ray diffraction spectra of TiN thin films formed at different exposure pressures and having increased (111) crystalline texture, according to embodiments.
  • FIG. 17 illustrates chlorine concentration depth profiles of TiN thin films having increased (111) crystalline texture, according to embodiments.
  • FIG. 18 schematically illustrates a thin film deposition system including a thin film deposition chamber and a precursor delivery system, according to embodiments.
  • FIG. 19 shows a perspective view of a lid of a process chamber comprising multiple processing stations, according to embodiments.
  • FIG. 20 schematically illustrates a precursor delivery sequence for forming TiN thin films, according to embodiments.
  • FIG. 21 is a flow chart schematically illustrating a method of forming a TiN layer by cyclical vapor deposition process with reduced particle generation, according to some embodiments.
  • FIG. 22 shows an experimental measurement of the number of particles on a 300 mm wafer after forming a TiN layer using the method illustrated in FIG. 21.
  • FIG. 23 is a flow chart schematically illustrating a method of forming a TiN layer by cyclical vapor deposition process with reduced particle generation, according to some other embodiments.
  • FIG. 24A shows an experimental measurement of the number of particles on a 300 mm wafer after forming a TiN layer using the method illustrated in FIG. 23.
  • FIG. 24B shows an experimental measurement of the number of particles on a 300 mm wafer after forming a TiN layer using the method illustrated in FIG. 23.
  • FIG. 25 is a flow chart schematically illustrating a method of forming a TiN layer by cyclical vapor deposition process with reduced particle generation, according to some other embodiments.
  • FIG. 26 shows an experimental measurement of the number of particles on a 300 mm wafer after forming a TiN layer using the method illustrated in FIG. 25.
  • a smooth and conformal thin film comprising TiN and a cyclical vapor deposition method of forming the thin film, which displays the conformality characteristic of a film deposited by cyclical vapor deposition processes, while also having electrical and physical properties that are superior or matching those of TiN films formed by existing physical vapor deposition (PVD) and chemical vapor deposition (CVD) methods.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • a method of forming a thin film comprising titanium nitride comprises forming on a semiconductor substrate a first portion of the thin film by exposing the semiconductor substrate to one or more first cyclical vapor deposition cycles each comprising an exposure to a first Ti precursor and an exposure to a first N precursor.
  • the method additionally comprises forming on the first portion of the thin film a second portion of the thin film by exposing the semiconductor substrate to one or more second cyclical vapor deposition cycles each comprising an exposure to a second Ti precursor and an exposure to a second N precursor.
  • the exposures to one or both of the second Ti precursor and the second N precursor during the one or more second cyclical vapor deposition cycles are different compared to corresponding exposures to one or both of the first Ti precursor and the first N precursor during the one or more first cyclical vapor deposition cycles.
  • the cyclical vapor deposition processes disclosed herein are sometimes referred to as atomic layer deposition (ALD).
  • atomic layer deposition ALD
  • cyclical vapor deposition processes are not limited to atomic layer deposition processes.
  • the precursors may partly or substantially saturate a reaction surface in various embodiments described herein.
  • the initial film growth may proceed substantially in a layer-by-layer growth mode, which advantageously results in an average grain size that lower and a surface roughness that is lower relative to a comparable TiN film that is deposited by exposing the substrate to the Ti and/or N precursors at higher pressures, e.g., greater than 3 torr or 5 torr.
  • the latter portion of the film growth advantageously results in a degree of conformality or a step coverage that is higher relative to a comparable TiN film that is deposited by exposing the substrate to the Ti and/or N precursors at the relatively low pressures, e.g., less than 3 torr or less than 1 torr.
  • the second portion of the thin film may continue to grow, using the first portion as a template, in a layer-by-layer mode compared to a comparable thin film grown starting with exposures to the Ti and/or N precursors at relatively higher pressures.
  • the thin film comprising the first and second portions deposited by depositing at two different corresponding exposure pressures for one or both of the Ti precursor and the N precursor according to methods disclosed herein advantageously has a combination of surface roughness and conformality that is superior relative to a thin film layer formed on the same surface using a single pressure.
  • the thin film has a relatively low electrical resistivity compared to TiN layers formed by some existing methods.
  • titanium nitride shall be understood to encompass all possible stoichiometric and nonstoichiometric compositions of titanium nitride that can be expressed by a general formula Ti x N, where x>0, including TiN, ⁇ 3 N 4 , T1 4 N 3 , TieNs, TEN and T1N 2 as well as other non- stoichiometric compositions of Ti and N.
  • TiN titanium nitride
  • IC integrated circuit
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • PE-ALD plasma enhanced atomic layer deposition
  • plasma-enhanced processes such as plasma enhanced atomic layer deposition (PE-ALD) may be effective in forming conformal films on surfaces having relatively low aspect ratios
  • such processes may not be effective in depositing films inside vias and cavities having relative high aspect ratios.
  • PE-ALD plasma enhanced atomic layer deposition
  • one possible reason for this is that a plasma or its actives species may not reach deeper portions of high aspect ratio vias under some circumstances. In these circumstances, different portions of vias may be exposed to different amounts of the plasma or its active species, leading to undesirable structural effects of non-uniform deposition, such as thicker films being deposited near the opening of the via compared to deeper portions (sometimes called cusping or keyhole formation).
  • thermal ALD may be more advantageous, because thermal ALD does not depend on the ability of the plasma or its active species to reach portions of the surface being deposited on.
  • thermal ALD techniques may be suitable for forming relatively conformal TiN films on topography, particularly topography with relatively high aspect ratios (e.g., over 1:1)
  • the inventors have recognized that TiN films formed by thermal ALD can be inferior to TiN films formed by PVD or CVD in some respects, e.g., film roughness and electrical resistivity.
  • the inventors have discovered that some electrical properties and/or physical properties of ALD-grown TiN-based films can be affected by the mode of growth.
  • the inventors have discovered that, while it may be desirable to grow the TiN-based films in a two-dimensional layer-by-layer growth mode in ALD, such layer-by-layer growth mode may not be easily achieved under some circumstances.
  • the inventors have further discovered that growing TiN-based films by ALD in a layer-by- layer growth mode poses a particular challenge in IC fabrication where the TiN-based films are formed on non-metal surfaces, such as insulating surfaces, such as oxide and nitride surfaces or semiconductor surfaces such as doped and undoped silicon surfaces.
  • the inventors have recognized that the degree to which the TiN-based films may be grown in a layer-by- layer growth mode may in turn be dependent on the initial growth mode that is dependent on the type of surface, as described herein without being bound to any theory, in reference to FIGS. 1A-1D.
  • FIG. 1A schematically illustrates nucleation of a TiN layer and FIGS. IB ID illustrate different growth modes of the TiN layer on different surfaces.
  • precursor molecules 104 once precursor molecules 104 reach the surface of a substrate 100, they become physically adsorbed thereon. Some of the adsorbed molecules 104 may diffuse along the surface of the substrate 100 until they reach an energetically favorable position to be chemisorbed. The surface diffusion is governed by, among other things, the substrate temperature, the substrate material and kinetic energy of the adsorbed molecules.
  • a nuclei formed by chemisorbed molecules exceeds a certain size (sometimes referred to as “critical size”) determined by the trade-off between volume free energy and surface energy, the nuclei may become energetically stable, and start to grow in size. Thus formed layer 108 of stable nuclei continue to grow by incorporating additional precursor molecules 104. Subsequent film growth can be classified according to different growth modes, schematically illustrated in FIGS. 1B-1D.
  • FIG. IB schematically illustrates a three-dimensional island growth mode, sometimes referred to as Volmer-Weber growth mode, which results in the formation of a layer 112 of three-dimensional islands.
  • the island growth mode can dominate when the net surface free energy associated with three-dimensional islands is positive, indicating that deposited atoms are more strongly bound to each other than to the substrate. It will be appreciated that the energetics of ALD growth of TiN layers can favor the island growth mode, e.g., when the metallic TiN layers are deposited on some semiconductor and/or insulating material surfaces.
  • FIG. 1C illustrates a layer-by-layer growth mode, sometimes referred to as Frank-van der Merwe growth mode, which results in the formation of a relatively smooth two- dimensional layer 116.
  • the layer-by-layer growth mode can dominate when the deposited atoms are more strongly bound to the substrate than to each other, such that a stable two-dimensional layer 116 is energetically favored.
  • the layer-by-layer growth mode can be sustained when there is a continuous decrease in bonding energy between the layers from the first monolayer to the bulk-crystal value of the TiN layer.
  • FIGS. IB and 1C are two different possible growth modes of thin films, it will be appreciated that, under some circumstances, a growth mode that is intermediate between a layer-by-layer growth mode and a three-dimensional growth mode is possible.
  • FIG. ID illustrates an example of an intermediate growth mode known as Stranski-Krastanov (SK) growth mode.
  • the SK growth may occur in thin film growth that commences in a layer-by-layer mode.
  • an island growth mode starts to dominate over a layer-by-layer growth mode, resulting in thin film structure 120 in which three dimensional islands are formed on a two-dimensional initial layer.
  • the SK growth mode can occur as a strain relaxation mechanism (strain-induced roughening).
  • other factors such as the substrate temperature, reactor pressure and deposition rate can significantly affect the nucleation and early growth processes, which in turn affects the final nanostructure or micro structure of the resulting thin film.
  • deposition conditions that enhance surface diffusion e.g., relatively high substrate temperatures, relatively low pressures and/or low deposition rates may promote the growth in a layer-by-layer mode.
  • the initial film growth may proceed substantially in a layer-by-layer growth mode.
  • ALD growth initializes in a three-dimensional island growth mode or a SK growth mode.
  • ALD growth of TiN on substrate surfaces including doped and undoped Si, S1O 2 , S1 3 N 4 and other high K or low K materials, may proceed in an island growth mode or the SK growth mode.
  • the inventors have discovered that, in part owing to the initial growth mode of either an island or SK growth mode, subsequent growth of TiN by ALD often results in a film morphology that is undesirable for various applications of ultrathin conformal TiN for high aspect ratio structures, as illustrated in FIG. 2.
  • FIG. 2 is a cross-sectional transmission electron micrograph of a TiN layer grown by thermal ALD on a Si substrate coated with native oxide.
  • the ALD growth of TiN is often characterized by a competitive growth of adjacent crystals with different orientations, resulting, under some circumstances, in V-shaped grains close to the nucleation layer and culminating in a columnar morphology at higher film thicknesses.
  • the resulting film morphology includes facetted column tops that give rise to a significant surface roughness and column boundaries having lower density relative to the grains. It will be appreciated that the column boundaries can have significantly worse diffusion barrier properties relative to the grains themselves, and may serve as paths of least resistance for transportation of undesirable contaminant through the TiN layer.
  • the inventors have discovered that, when an initial portion of a TiN layer is formed on the non-metal surface by exposing the substrate to Ti and/or N precursors at relatively low pressures, e.g., less than 1 torr, an initial three-dimensional or SK growth mode can be suppressed and a layer-by-layer growth mode can be promoted in an initial stage, e.g., a nucleation stage, of the TiN deposition.
  • this may be because the local diffusion of adsorbed Ti and N precursor molecules have more time to locally diffuse and wet the substrate surface, especially a non-metal surface, with relatively low contact angles.
  • the TiN layer grown at relatively low exposure pressures results in a layer that uniformly covers large areas of the non-metal surface without substantially forming islands, such that, the initial stages of growth tend more to favor a layer-by-layer growth mode on substrate surfaces on which ALD TiN would normally favor a three-dimensional island or SK growth mode as described above.
  • the resulting initial layer may grow in a layer-by-layer mode, e.g., in the nucleation stage.
  • a subsequent bulk stage of growth which may proceed by exposing the substrate to the Ti and/or N precursors at the relatively high precursor exposure pressures, e.g., greater than 3 torr, may continue to proceed in a layer-by-layer mode.
  • some of the drawbacks of conventional ALD of TiN may be avoided, particularly when the TiN layer is formed by ALD directly on some semiconductor and/or insulating materials, particularly inorganic layers comprising Si, S1O 2 and/or S1 3 N 4 , which may ordinarily be associated with an initial growth characterized by an island or SK growth mode followed by a columnar growth as described above.
  • FIG. 3A is a flow chart schematically illustrating an atomic layer deposition method 300 of forming a TiN layer by exposing a substrate to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • the resulting film may have at least two regions formed at different corresponding exposure pressures.
  • FIG. 3B schematically illustrates a cross-sectional view of a semiconductor structure 350 comprising a TiN layer formed by an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures, according to the method illustrated in FIG. 3A. Referring to FIG.
  • the method 300 includes providing 310 a substrate comprising a non-metal surface in a reaction chamber configured for ALD, e.g., thermal ALD.
  • the method 300 additionally comprises an initial stage, e.g., a nucleation stage, that includes forming 320 on the substrate a first portion of the thin film by exposing the semiconductor substrate to one or more first ALD cycles each comprising an exposure to a first Ti precursor and a first N precursor at first respective exposure pressures.
  • the method 300 further comprises latter stage, e.g., a bulk deposition stage, including forming 330 on the first portion of the thin film a second portion of the thin film by exposing the semiconductor substrate to one or more second ALD cycles each comprising an exposure to a second Ti precursor and a second N precursor at second respective exposures.
  • the exposures to one or both of the Ti precursor and the N precursor during the one or more second ALD cycles are at higher pressures relative to corresponding exposures to one or both of the Ti precursor and the N precursor during the one or more first ALD cycles.
  • FIG. 3B a cross-sectional view of a semiconductor thin film structure 350 comprising a substrate 360, which in turn comprises a non-metal surface, e.g., a dielectric and/or a semiconductor surface.
  • a first a first portion 370 of a thin film comprising TiN is formed on the substrate 360, and a second portion 380 of the thin film is formed on the first portion 370.
  • the first and second portions 370, 380 are formed by an atomic layer deposition method illustrated in FIG. 3A, in which the substrate 360 is exposed to first and second cycles with different corresponding precursor exposure pressures.
  • the first portion 370 may be grown in a layer-by-layer growth mode in the initial stage, e.g., a nucleation stage as discussed above, at least the first portion 370 or both the first and second portions 370, 380 may be substantially free of adjacent crystals having different orientations characterized by columnar growth of V-shaped grains and the relatively high (e.g., 10% of the thickness) surface roughness.
  • the resulting TiN layer has superior properties including one or more of relatively high conformality or step coverage, lower surface roughness, smaller average grain size, higher electrical conductivity and/or barrier characteristics relative to a comparable thin film layer formed at a single pressure during nucleation and bulk deposition stages.
  • the semiconductor substrate on which the TiN thin films according to embodiments can be implemented in a variety of substrates, including, but not limited to, a doped semiconductor substrate, which can be formed of an elemental Group IV material (e.g., Si, Ge, C or Sn) or an alloy formed of Group IV materials (e.g., SiGe, SiGeC, SiC, SiSn, SiSnC, GeSn, etc.); Group III-V compound semiconductor materials (e.g., GaAs, GaN, InAs, etc.) or an alloy formed of Group III-V materials; Group II- VI semiconductor materials (CdSe, CdS, ZnSe, etc.) or an alloy formed of Group II- VI materials.
  • an elemental Group IV material e.g., Si, Ge, C or Sn
  • Group III-V compound semiconductor materials e.g., GaAs, GaN, InAs, etc.
  • Group II- VI semiconductor materials CdSe, CdS, ZnSe, etc.
  • the substrate can also be implemented as a semiconductor on insulator, such as silicon on insulator (SOI), substrate.
  • SOI substrate typically includes a silicon-insulator- silicon structure in which the various structures described above are isolated from a support substrate using an insulator layer such as a buried S1O2 layer.
  • an insulator layer such as a buried S1O2 layer.
  • the various structures described herein can be at least partially formed in an epitaxial layer formed at or near a surface region.
  • the substrate can include a variety of structures formed thereon, e.g., diffusion regions, isolation regions, electrodes, vias and lines to name a few, on which any structure comprising the TiN layer according to embodiments may be formed, including topological features such as vias, cavities, holes or trenches having one or more semiconductor or dielectric surfaces.
  • structures formed thereon e.g., diffusion regions, isolation regions, electrodes, vias and lines to name a few, on which any structure comprising the TiN layer according to embodiments may be formed, including topological features such as vias, cavities, holes or trenches having one or more semiconductor or dielectric surfaces.
  • the non-metal surface on which the TiN layer according to embodiments is formed can include a semiconductor surface, e.g., a doped or undoped Si surface, and/or a dielectric surface, e.g., an interlayer dielectric (ILD) surface, a mask or a hard mask surface or a gate dielectric surface, to name a few, which can include an inorganic insulator, an oxide, a nitride, a high K dielectric, a low K dielectric, or carbon, to name a few dielectric materials.
  • a semiconductor surface e.g., a doped or undoped Si surface
  • a dielectric surface e.g., an interlayer dielectric (ILD) surface
  • ILD interlayer dielectric
  • a reactor chamber refers to any reaction chamber including a single wafer processing reaction chamber or a batch wafer processing reaction chamber that is suitably configured for thermal atomic layer deposition (ALD).
  • ALD thermal atomic layer deposition
  • the substrate may be placed on a suitable substrate holder, such as a susceptor or a carrier boat.
  • the substrate may be directly heated by conduction through a heated susceptor, or indirectly heated by radiation from a radiation source such as a lamp or by convection through a heated chamber wall.
  • reactants or precursors e.g., oxidizing and reducing reactants
  • a reaction chamber having disposed therein a substrate.
  • the introduction of one or more reactants or precursors may be in turn be alternated with a purge and/or a pump out process for removing excess reactants or precursors from the reaction chamber.
  • the reactants may be introduced into the reaction chamber under a condition over a suitable period of time such that the surface of the substrate becomes at least partly saturated with the precursors or reactants and/or a reaction product of the reactants. Excess or residual precursors or reactants may then be removed from the substrate, such as by being purged and/or pumped out of the reaction chamber.
  • a pump out process may be performed by a suitable vacuum pumping process and a purge step may be performed by introducing a non-reactive or an inert gas, e.g., nitrogen or a noble gas, into the reaction chamber.
  • a non-reactive or an inert gas e.g., nitrogen or a noble gas
  • example implementations of the method 300 (FIG. 3A) of forming by AFD e.g., thermal AFD, a thin film comprising TiN having at least two regions formed by exposing a substrate to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • the method 300 proceeds to forming 320 by atomic layer deposition (AFD), e.g., thermal AFD, on the non-metal surface a first portion of the thin film by exposing the semiconductor substrate to one or more first AFD cycles, followed by a second portion of the thin film by exposing the semiconductor substrate to one or more second AFD cycles.
  • AFD atomic layer deposition
  • exposure pressures applied during the first and second AFD cycles are described diagrammatically.
  • FIG. 4 diagrammatically illustrates pressure traces corresponding to exposures of the substrate to Ti and N precursors during a first cycle 400A or stage, e.g., a nucleation stage, for forming the first portion 370 (FIG. 3B) of the thin film and the second cycle 400B or stage, e.g., a bulk growth stage, for forming the second portion 380 (FIG. 3B) of the thin film, according to various embodiments.
  • a first cycle 400A or stage e.g., a nucleation stage
  • the second cycle 400B or stage e.g., a bulk growth stage
  • a first portion of the thin film is formed by exposing the semiconductor substrate to one or more first AFD cycles 400A each comprising one or more exposures 404 or exposure pulses to a partial pressure of a first Ti precursor and one or more exposures 408 or exposure pulses to a partial pressure of a first N precursor.
  • a second portion of the thin film is formed by exposing the semiconductor substrate to one or more second ALD cycles 400B each comprising one or more exposures 412 or exposure pulses to a partial pressure of a second Ti precursor and one or more exposures 416 or exposure pulses to a partial pressure of second N precursor.
  • each of the exposures 404 to a first Ti precursor, 408 to a first N precursor, 412 to a second Ti precursor and 416 to a second N precursor may have different partial pressure regimes, including a corresponding partial pressure rise regime 404A, 408A, 412A and 416A, a main exposure regime 404B, 408B, 412B and 416B, and a partial pressure fall regime 404C, 408C, 412C and 416C.
  • Each of the partial pressure rise regimes 404A, 408 A, 412A and 416A may correspond, for example, the respective precursor being introduced into the reaction chamber.
  • Each of the main exposure regimes 404B, 408B, 412B and 416B may correspond to a period during which the amount of the respective precursor in the reaction chamber is relatively constant.
  • the relative constant amount of the respective precursor may be maintained, e.g., using a pressure transducer or a throttle valve.
  • Each of the partial pressure fall regime 404C, 408C, 412C and 416C may correspond, for example, to a regime when the respective precursor is being purged or pumped out of the reaction chamber.
  • the precursors may be pumped out and/or purged out after each exposure.
  • the reaction chamber pressure may be substantially represented by the partial pressures of the respective precursors, and the pressures traces of the exposures 404, 408, 412 and 416 may substantially represent the reaction chamber pressures or the precursor partial pressures during the respective exposures.
  • the reaction chamber pressure may be represented by total reaction chamber pressures 404P, 408P, 412P and 416P corresponding to the exposures 404, 408, 412 and 416, where the total reaction chamber pressures result from a mixture of the respective precursors and an inert gas.
  • the substrate may be subjected to partial pressures of the first Ti precursor, the first N precursor, the second Ti precursor and the second N precursor, while measuring total pressures 404P, 408P, 412P and 416P including during purging and pumping.
  • the total chamber pressure may be kept relatively constant throughout a given precursor exposure or exposure pulse while pumping power is adjusted using a pressure transducer and replacing the removed precursor with an inert gas.
  • one or more second ALD cycles 400B for forming the second portion may each comprise one or more exposures 412 to a partial pressure of a second Ti precursor (while the measured parameter may be a total pressure 412P) and one or more exposures 416 to a partial pressure of a second N precursor (while the measured parameter may be a total pressure 416P).
  • the measured total reaction chamber pressure may be proportional to the partial pressure of the precursor.
  • the total pressures 412P and 416P that are higher relative total pressures 404P and 408P, respectively correspond to higher partial pressures of the second Ti precursor and the second N precursor relative to partial pressures of the first Ti precursor and the first N precursor, respectively.
  • the total pressures 412P and 416P that are higher relative total pressures 404P and 408P, respectively may correspond to the same or lower partial pressures of the second Ti precursor and the second N precursor relative to partial pressures of the first Ti precursor and the first N precursor, respectively.
  • one or both of exposure pressures of the second Ti precursor and the second N precursor during one or more second ALD cycles of the latter, e.g., a bulk deposition phase are higher relative to corresponding one or both of exposure pressures of the first Ti precursor and the first N precursor during one or more first ALD cycles of the initial, e.g., a nucleation phase.
  • the exposure pressures may be partial pressures of the precursors or total pressures of the reaction chambers.
  • one or both of the exposure 412 to the second Ti precursor and the exposure 416 to the second N precursor may be at higher partial pressures and/or a higher total reaction chamber pressures relative to the corresponding one or both of the exposure 404 to a the first Ti precursor and the exposure 408 to the first N precursor, respectively.
  • the corresponding partial or total pressures between corresponding exposures to Ti and N precursors during the first and second cycles 400A and 400B may be corresponding partial or total pressures during any one of partial pressure rise regimes 404A, 408A, 412A and 416A, main exposure regimes 404B, 408B, 412B and 416B, and partial pressure fall regimes 404C, 408C, 412C and 416C.
  • the exposures 412, 416 to one or both of the second Ti precursor and the second N precursor during the main exposure regimes 412B and 416B, respectively, during the second ALD cycle 400B may be at higher total or partial pressures relative to the exposures 404, 408 to one or both of the first Ti precursor and the first N precursor during the main exposure regimes 404B and 408B, respectively, during the first ALD cycle 400A.
  • the corresponding partial or total pressures between corresponding exposures to Ti and N precursors during the first and second cycles 400A and 400B may be corresponding average, mean or peak partial or total pressures during the exposures 404, 408, 412 and 416.
  • the total and/or partial pressures during the exposure 404 to the first Ti precursor and the exposure 408 to the first N precursor are different, and the total and/or partial pressures during the exposure 412 to the second Ti precursor and the exposure 416 to the second N precursor are different.
  • the total and/or partial pressures during the exposure 404 to the first Ti precursor and the exposure 408 to the first N precursor may be kept constant, and/or the total and/or partial pressures during the exposure 412 to the second Ti precursor and the exposure 416 to the second N precursor may be kept constant.
  • each of the total pressures during the exposure 404 to the first Ti precursor and the exposure 408 to the first N precursor may be 0.01-0.2 torr, 0.2-0.4 torr, 0.4-0.6 torr, 0.6-0.8 torr, 0.8-1.0 torr, 1.0-1.5 torr, 1.5-2.0 torr, 2.0-2.5 torr, 2.5-3.0 torr, or a pressure in range defined by any of these values.
  • Each of the total pressures during the exposure 412 to the second Ti precursor and the exposure 416 to the second N precursor may be 3.0-4.0 torr, 4.0- 5.0 torr, 5.0-6.0 torr, 6.0-7.0 torr, 7.0-8.0 torr, 8.0-9.0 torr, 9.0-10.0 torr, 10.0-11.0 torr, 11.0- 12.0 torr, or a pressure in range defined by any of these values.
  • a ratio of the total pressure (measured in torr) of the reaction chamber during the exposure 412 to the second Ti precursor and the exposure 404 to the first Ti precursor may be 2-5, 5-10, 10-20, 20-50, 50-100, or in a range defined by any of these values.
  • a ratio of the total pressure of the reaction chamber during the exposure 416 to the second N precursor and the exposure 408 to the first N precursor may be 2-5, 5-10, 10-20, 20-50, 50-100, or in a range defined by any of these values.
  • the respective Ti or N precursor can make up 1-2%, 2-5%, 5-10%, 10-20%, 20-50%, 50-100% of the total amount of gas molecules in the reaction chamber, or a percentage in a range defined by any of these values.
  • the total pressure or the partial pressure during the exposure 404 to the first Ti precursor and the exposure 408 to the first N precursor are controlled such that the deposition rate during the first cycle 400A or stage is between 0.10-0.20 A/cycle, 0.20-0.30 A/cycle, 0.30-0.40 A/cycle, 0.40-0.50 A/cycle, 0.50-0.60 A/cycle or a value in a range defined by any of these values, per cycle including an exposure 404 to the first Ti precursor and an exposure 408 to the first N precursor.
  • the total pressure or the partial pressure during the exposure 412 to the second Ti precursor and the exposure 416 to the second N precursor, in conjunction with the flow rates of the respective precursors and an inert gas and the pumping power of the reaction chamber are controlled such that the deposition rate during the second cycle 400B or stage is 0.20-0.30 A/cycle, 0.30-0.40 A/cycle, 0.40-0.50 A/cycle, 0.50-0.60 A/cycle, 0.60-0.70 A/cycle, 0.60-0.70 A/cycle, 0.70-0.80 A/cycle or a value in a range defined by any of these values, per cycle including an exposure 404 to the first Ti precursor and an exposure 408 to the first N precursor.
  • a ratio of the deposition rate per cycle during the second cycle 400B to the deposition rate per cycle during the first cycle 400A may be 1-1.5, 1.5-2.0, 2.5-3.0, or a ratio in a range defined by any of these values.
  • each of forming 320 (FIG. 3A) the first portion 370 (FIG. 3B) and forming 330 (FIG. 3A) the second portion 380 (FIG. 3B) of the thin film comprising TiN comprises exposing a semiconductor substrate to 1-25 cycles, 26-50 cycles, 50-100 cycles, 100-200 cycles, 200-300 cycles, 300-400 cycles, 400-500 cycles, 500-600 cycles, or a value in a range defined by any of these values, of the first cycles 400A (FIG. 4) and second cycles 400B (FIG. 4), respectively.
  • a ratio of the number of second cycles to the number of first cycles can be greater than 1, 2, 5 or 10 or a ratio in a range defined by any of these values, or smaller than 1, 0.5, 0.1 or 0.1 or a ratio in a range defined by any of these values.
  • the overall thickness of the thin film comprising TiN including the first portion 370 (FIG. 3B) and the second portion 380 (FIG. 3B) can have a combined stack thickness that does not exceed about 25 nm, 20 nm, 15 nm, 10 nm, 7 nm, 4 nm, 2 nm, or having a value in a range defined by any of these values.
  • a thickness ratio between the first portion 370 (FIG.
  • first portion 370 may be relatively thinner, e.g., when higher conformality may be more important compared to lower film roughness
  • second portion 380 may be relatively thinner, e.g., when lower film roughness may be more important compared to higher conformality.
  • each of the exposure 404 of the substrate to the first Ti precursor and the exposure 412 of the substrate to the second Ti precursor is such that the surface of the substrate is substantially or partly saturated with the first Ti precursor or the second Ti precursor, respectively.
  • excess or residual first and/or second Ti precursors or their reaction products that do not remain adsorbed or chemisorbed on the surface of the substrate may be pumped and/or purged out.
  • each of the exposure 408 of the substrate to the first N precursor and the exposure 416 of the substrate to the second N precursor is such that the substrate is substantially or partly saturated with the first N precursor or the second N precursor, respectively.
  • excess or residual first and/or second N precursors or their reaction products that do not remain adsorbed or chemisorbed on the surface of the substrate may be pumped and/or purged out.
  • Subjecting the substrate to one or more exposures to the first Ti precursor and one or more exposures to the first N precursor may form about a monolayer or less per cycle of TiN.
  • subjecting the substrate to one or more exposures to the second Ti precursor and one or more exposures to the second N precursor may form about a monolayer or less per cycle of TiN.
  • the exposure 404 to the first Ti precursor, the exposure 408 to the first N precursor, the exposure 412 to the second Ti precursor and/or the exposure 416 to the second N precursor may be performed a plurality of times in sequence prior to introduction of the other precursor.
  • exposing the substrate to a Ti precursor and/or a N precursor more than once may result in a higher level of surface saturation e.g., when substantial stearic hindrance effect exists.
  • the relative order of exposures to a first Ti precursor and to a first N precursor may be selected depending on competing circumstances.
  • the first Ti precursor may advantageously be the first precursor the substrate surface is exposed to.
  • one or more direct exposures of a Si surface to the first Ti precursor may lead to formation of one or more monolayers of TiSi and prevent formation of SiN, which may in turn be advantageous for lowering contact resistance between the underlying Si and the TiN layer formed thereover.
  • the first N precursor may advantageously be the first precursor the substrate is exposed to.
  • one or more monolayers of SiN may be intentionally formed, which may be advantageous for improving barrier characteristics of the stack.
  • the frequency and repetition of the exposures of the substrate to the first Ti reactant and/or the first N precursor in each of the first cycles 408 A, and to the second Ti reactant and/or the second N precursor in each of the second cycles 408B may be varied to obtain a desired thickness and stoichiometry, based on various considerations including susceptibility to stearic hindrance effects of the precursors.
  • non-limiting examples of the first and second Ti precursors which may be the same or different for forming first and second portions of a TiN layer according to embodiments, include titanium tetrachloride (TiCU), tetrakis(dimethylamino)titanium (TDMAT) or tetrakis(diethylamino)titanium (TDEAT).
  • TiCU titanium tetrachloride
  • TDMAT tetrakis(dimethylamino)titanium
  • TDEAT tetrakis(diethylamino)titanium
  • non-limiting examples of the first and second N precursors which may be the same or different for forming first and second portions of a TiN layer according to embodiments, include ammonia (NH3), hydrazine (N2H4) or monomethylhydrazine (CH3(NH)NH2, “MMH”).
  • NH3 ammonia
  • N2H4 hydrazine
  • CH3(NH)NH2 monomethylhydrazine
  • Having same precursors for the first and second portions of the TiN may be advantageous for, e.g., being lower in cost and/or easier for process design.
  • having different precursors for the first and second portions of the TiN may be advantageous for, e.g., different deposition characteristics or film quality.
  • non-limiting examples of the inert gas for purging may include nitrogen N2 or a noble gas such as Ar or He.
  • first and second portions 370, 380 (FIG. 3B) of the thin film comprising TiN are formed at a substrate temperature of 350°C to 800°C, 450°C to 750°C, 500°C to 700°C, 550°C to 650°C, or in a range defined by any of these values, for instance about 600°C, according to embodiments.
  • a substrate temperature 350°C to 800°C, 450°C to 750°C, 500°C to 700°C, 550°C to 650°C, or in a range defined by any of these values, for instance about 600°C, according to embodiments.
  • Keeping the temperature the same during growth of the first and second portions 370, 380 may be advantageous for throughput an ease of process control, as temperature adjustments during process may take long time.
  • the exposure times or pulse times of each of the first and second Ti precursors and first and second N precursors can be in the range of about 0.1-1 sec., 1-10 sec., 10-30 sec., 30-60 sec., or a duration in a range defined by any of these values.
  • the TiN layer is formed using an atomic layer deposition method in which a substrate is exposed to a plurality of cycles with different corresponding precursor exposure pressures according to various embodiments
  • one or both of the surface roughness and electrical resistivity can be substantially reduced to conventional TiN films including TiN films formed using other ALD processes with a single pressure setpoint.
  • the thin film comprising TiN having the above-indicated thicknesses and thickness ratios between the first and second portions 370, 380 can have an RMS surface roughness value that is less than 2.5 nm, 2 nm, 1.5 nm, 1.0 nm, 0.5 nm, or a value in a range defined by any of these values.
  • the thin film comprising TiN formed according to the methods described herein and having the above-indicated thickness and thickness ratios between the first and second portions 370, 380 can have an electrical resistivity of ⁇ 70 mW-cm, 70-100 mW-cm, 100-130 mW-cm, 130-160 mW-cm, 160-190 mW-cm, 190-220 mW- cm, 220-250 mW-cm, 250-280 mW-cm, 280-310 mW-cm, or greater than 310 mW-cm, or a value in a range defined by any of these values, for instance less than about 200 mW-cm.
  • the thin film comprising TiN formed according to the methods disclosed herein has high conformality when deposited in high aspect ratio structures.
  • One measure of conformality in the context of high aspect ratio structures is referred to herein as step coverage.
  • a high aspect ratio structure may be, e.g., a via, a hole, a trench, a cavity or a similar structure.
  • FIG. 5 schematically illustrates a semiconductor structure 500 having an example high aspect ratio structure 516 formed therein, to illustrate some example metrics of defining and/or measuring conformality of thin films formed on high aspect ratio structures.
  • the illustrated high aspect ratio structure 516 is lined with a TiN layer 512 having different thicknesses at different portions thereof.
  • a high aspect ratio structure has an aspect ratio, e.g., a ratio defined as a depth or height (H) divided by a width (W) at the opening region of the high aspect ratio structure 516, that exceeds 1.
  • the high aspect ratio structure 516 is a via formed through a dielectric layer 508, e.g., an intermetal dielectric (ILD) layer, formed on a semiconductor substrate 504, such that a bottom surface of the high aspect ratio structure 516 exposes the underlying semiconductor 504.
  • the TiN layer 512 can coat different surfaces of the high aspect ratio structure 516 with different thicknesses.
  • a step coverage may be defined as a ratio between a thickness of a thin film at a lower or bottom region of a high aspect ratio structure and a thickness of the thin film at an upper or top region of the high aspect ratio structure.
  • the upper or top region may be a region of the high aspect ratio structure at a relatively small depth at, e.g., 0-10% or 0-25% of the H measured from the top of the opening.
  • the lower or bottom region may be a region of the high aspect ratio structure at a relatively high depth at, e.g., 90-100% or 75-100% of the H measured from the top of the opening.
  • a step coverage may be defined or measured by a ratio of thicknesses of the thin film 512A formed at a bottom surface to the thin film 512C formed at upper or top sidewall surfaces of the high aspect ratio structure.
  • a step coverage may be more consistently defined or measured by a ratio of thicknesses of the thin film 512B formed at a lower or bottom sidewall surface to the thin film 512C formed at an upper or top sidewall surfaces of the high aspect ratio structure.
  • the thin film comprising TiN formed according to the methods disclosed herein results in a reduced surface roughness and electrical resistivity, while also providing high conformality in high aspect ratio structures.
  • high aspect ratio structures having an aspect ratio exceeding 1, 2, 5, 10, 20, 50, 100, 200 or a value in a range defined by any of these values may be conformally coated with TiN films according to embodiments with a step coverage as defined herein that exceeds 70%, 80%, 90%, 95%, or has a value in a range defined by any of these values.
  • FIG. 6 is a graph illustrating experimentally measured root mean square (RMS) surface roughness trend 604 and step coverage trend 608 as functions of the number of first cycles of exposures to Ti and N precursors at a relatively low chamber pressure of 0.5 torr, out of a total of 600 combined first cycles (e.g., nucleation stage) and second cycles (e.g., bulk deposition stage).
  • the second cycles of exposures to Ti and N precursors were at a relatively high chamber pressure of 5 torr.
  • Each experimental data point in FIG. 6 was taken from a TiN film grown on a native Si0 2 -coated Si substrate for surface roughness measurements, and a TiN film grown in a via formed in S1O2 and having about 40:1 aspect ratio.
  • the measured deposition rates of the first and second cycles were 0.28 A/cycle and 0.38 A/cycle, respectively.
  • the experimental data were measured on four different TiN films grown with 0 first cycles (0 A) / 600 second cycles (228 A), 50 first cycles (14 A) / 550 second cycles (209 A), 200 first cycles (56 A) / 400 second cycles (152 A), and 600 first cycles (168 A) / 0 second cycles (0 A).
  • the four TiN films had total thicknesses of about 228 A, 223 A, 208 A and 168 A, respectively.
  • the measured surface roughness values of the TiN films decrease with increasing relative number of first cycles including exposures at the relatively lower pressure.
  • the measured surface roughness values for thin films grown with 0 first cycles / 600 second cycles, 50 first cycles / 550 second cycles and 200 first cycles / 400 second cycles were about 21 A, 17.5 A and 12.5 A, respectively, corresponding to about 9%, 8% and 6% on the basis of the total thickness of the respective TiN films.
  • the measured step coverage values of the TiN films were higher for the thin film grown with 0 first cycles / 600 second cycles relative to the film grown with 600 first cycles / 0 second cycles.
  • forming the first portion of the TiN film comprises altematingly exposing the semiconductor substrate to 1 to 50 cycles each comprising an exposure to a first Ti precursor and an exposure to a first N precursor at a relatively low exposure pressure of less than about 3 torr.
  • FIGS. 7A-9 illustrate further experimental comparisons between a TiN film grown by exposing a substrate to cycles with the same precursor exposure pressures and a TiN film grown by exposing a substrate to a plurality of cycles with different corresponding precursor exposure pressures, according to embodiments.
  • FIG. 7A is a cross-sectional transmission electron micrograph of high aspect ratio vias lined with a TiN layer formed by an atomic layer deposition method in which a substrate is exposed to ALD cycles at the same precursor exposure pressure corresponding to second cycles.
  • FIGS. 7B and 7C are transmission electron micrographs (TEMs) of a TiN film grown using only second cycles of exposures to Ti and N precursors at a relatively high chamber pressure of 5 torr.
  • TEMs transmission electron micrographs
  • FIGS. 8A and 8B are transmission electron micrographs (TEMs) of a TiN film grown using a combination of first and second cycles of exposures to Ti and N precursors at a relatively low (0.5 torr) and high (5 torr) chamber pressures, according to embodiments.
  • the TEMs are images of a via formed in S1O2 having about 40:1 aspect ratio, taken at upper (FIG. 8A) and lower (FIG. 8B) regions of the via.
  • FIG. 9 is a graph illustrating an experimental statistical comparison between measured step coverages 904 measured from TEM micrographs shown in FIGS. 7A-7C and measured step coverages 908 measured from TEM micrographs shown in FIGS. 8A-8B.
  • the data points in FIG. 9 represents a ratio taken from different locations within a lower region of the via and different locations within an upper region of the via. While not readily apparent from the TEM images, the statistical comparison in FIG. 9 clearly illustrate a higher median step coverage of 93% for the TiN film deposited according to embodiments and 87% for the TiN film deposited using a single exposure pressure.
  • the statistical spread of measured step coverage for the TiN film deposited according to embodiments is substantially smaller than that for the TiN film deposited using a single exposure pressure, indicating that the film roughness is significantly higher for the latter.
  • TiN as disclosed herein have a face-centered cubic, NaCl-type lattice structure. As such, the surface atom density is highest when the surface has a (111) orientation, relative to (200) orientation. The fraction of the surface having a certain crystal orientation for TiN can be highly deposition condition-dependent.
  • the TiN films may need to be extremely thin, e.g., less than 30 nm, while simultaneously meeting a combination of stringent electrical and mechanical properties.
  • stringent electrical properties e.g., relatively high density, hardness and modulus
  • a TiN film grown by atomic layer deposition can have grains that have different crystal orientations including (111) and (200) orientations at the surface, among other orientations.
  • the inventors have discovered that TiN thin films that are textured to have certain crystalline texture can have superior mechanical properties, in addition to having a desirably low electrical resistivity and conformality as described above.
  • ultrathin TiN films having relatively high (111) crystalline texture can have a relatively high density, hardness and modulus.
  • the increased (111) crystalline texture can reduce columnar growth, thereby providing superior diffusion barrier properties.
  • these advantageous properties of the TiN thin films having relatively high (111) crystalline texture may be associated with one of the highest surface atom packing density in a direction parallel to the growth surface, as well as grain boundary arrangements that favor the superior physical properties.
  • the inventors have further discovered that the texture of TiN thin films can be controlled by controlling certain conditions of the cyclical vapor deposition cycles, as described herein.
  • the inventors have discovered that cyclical vapor deposition cycles in which the substrate is subjected to a relatively high flow rate of the N precursor can cause a TiN thin film to grow with a relatively high (111) crystalline texture, as described herein.
  • FIG. 11 is a flow chart schematically illustrating an atomic layer deposition method 1100 of forming a TiN layer having a relatively high (111) crystalline texture by exposing a substrate to a relatively high N precursor flow rate, according to embodiments.
  • the method 1100 includes providing 1110 a semiconductor substrate.
  • the method 1100 additionally includes exposing 1120 the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to a N precursor at a N precursor flow rate.
  • the method 1100 forms a TiN film having a relatively high (111) crystalline texture by exposing 1120 the semiconductor substrate to one or more cyclical vapor deposition cycles in which a ratio of the N precursor flow rate to the Ti precursor flow rate (N/Ti flow ratio) and/or the flow rate of the N precursor are substantially high compared to conventional methods.
  • a ratio of the N precursor flow rate to the Ti precursor flow rate (N/Ti flow ratio) exceeds 3.
  • the N precursor flow rate exceeds 500 seem. It will be appreciated that the exposing 1120 and forming 1130 are not necessarily ordered as shown. Various implementations of the method 1100 are described herein.
  • Providing 1110 the semiconductor substrate can be similar to providing 310 a semiconductor substrate according to various examples described above with respect to FIGS. 3A and 3B, the details of which are not repeated herein for brevity.
  • the substrate can be patterned or non-patterned, and can have one or both of insulating and conducting surfaces as described above.
  • Exposing 1120 the semiconductor substrate can be similar to exposing the semiconductor substrate to one or more first or second thermal ALD cycles as described above with respect to respect to FIGS. 3 A, 3B and 4, the details of which is not repeated herein for brevity.
  • the exposure to a Ti precursor at a Ti precursor flow rate can be in accordance with the exposure 404 (FIG. 4) to the first Ti precursor or the exposure 412 (FIG. 4) to the second Ti precursor.
  • the exposure to a N precursor at a N precursor flow rate can be in accordance with the exposure 408 (FIG. 4) to the first N precursor or the exposure 416 (FIG. 4) to the second N precursor.
  • exposing 1120 is such that a TiN thin film having a high (111) crystalline texture is formed, as described herein.
  • the Ti precursor and the N precursor can be any of the precursors described above.
  • the Ti precursor can be titanium tetrachloride (TiCU) and the N precursor can be ammonia (NFb).
  • exposing 1120 is such that a ratio of the N precursor flow rate to the Ti precursor flow rate (N/Ti flow ratio) exceeds 2.
  • the ratio can exceed 2, 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or have a value in a range defined by any of these values.
  • exposing 1120 is such that the N precursor flow rate exceeds 200 seem.
  • the N precursor flow rate can exceed 200 seem, 500 sccm, 1000 seem, 2000 seem, 3000 seem. 4000 seem, 5000 seem, 6000 seem, 7000 seem, 8000 seem, 9000 seem, 10000 seem, or have a value in a range defined by any of these values.
  • exposing 1120 is such that the Ti precursor flow rate exceeds 100 seem but does not exceed the flow rate of the N precursor, in accordance with the N/Ti flow ratio described above.
  • the Ti precursor flow rate can exceed 100 seem, 200 seem, 500 seem, 1000 seem, 2000 seem, 3000 seem. 4000 seem, 5000 seem, or have a value in a range defined by any of these values.
  • FIG. 12A illustrates experimental X-ray diffraction spectra of the resulting TiN thin films having a relatively high (111) crystalline texture, according to embodiments.
  • the X-ray diffraction spectra were taken on Examples 1-4 shown in TABLE 1 below.
  • FIG. 12B is a graph illustrating the experimental ratios of a peak height of an X-ray diffraction peak corresponding to a (111) crystal orientation of TiN to a peak height of an X-ray diffraction peak corresponding to a (200) crystal orientation of TiN obtained from the X-ray diffraction spectra of FIG. 12A.
  • the illustrated TiN thin films are shown as examples only, and the embodiments are not so limited.
  • the N precursor flow rate range and the Ti precursor flow rate range are such that the TiN thin film has a relatively high (111) crystalline texture relative to a comparable thin film (e.g., a TiN having a similar thickness) formed by exposing the semiconductor substrate to cyclical vapor deposition cycles each comprising an exposure to a different Ti precursor flow rate range outside of the Ti precursor flow rate range described above and an exposure to a different N precursor flow rate range outside of the N precursor flow rate range described above.
  • the degree of the increased (111) texture can be measured using, e.g., X-ray diffraction.
  • the relative intensities of different X-ray peaks can provide at least a semi-quantitative indication of the degree of texturing.
  • the TiN thin films formed according to embodiments advantageously have a relatively high (111) crystalline texture such that an X-ray spectrum of the thin film has a ratio of a peak height or an intensity of an X-ray diffraction peak corresponding to (111) crystal orientation to a peak height or an intensity of an X-ray diffraction peak corresponding to (200) crystal orientation that exceeds 0.4.
  • this ratio can exceed 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, or a value in a range defined by any of these values.
  • Selected experimental precursor flow conditions and the corresponding measurements of the ratios are summarized in TABLE 1. [0110] FIG.
  • FIG. 13 is a graph of experimental thickness and resistivity measurements of TiN thin films having relatively high (111) crystalline texture, according to embodiments.
  • Examples 1-4 listed in TABLE 1 increasing the N/Ti flow ratio decreases the thickness for the same number of cycles.
  • increasing the N/Ti flow ratio which in turn decreases the thickness, decreases a resistivity of the TiN thin film.
  • decreasing thickness had been associated with increasing resistivity, which had been correlated to relatively higher amounts of chlorine in relatively thin TiN thin films formed with TiCL.
  • the illustrated TiN thin films are shown as examples only, and the embodiments are not so limited.
  • the resistivity of the TiN films formed according to embodiments is less than about 200 mW-cm or any value described above. Selected experimental precursor flow conditions and the corresponding measurements of the thickness and resistivity are summarized in TABLE 1.
  • FIG. 14 is a graph of experimental hardness and modulus measurements of TiN thin films having substantially the same thicknesses and a preferential (111) crystalline texture, according to embodiments.
  • FIG. 15 is a graph of experimental hardness measurements of TiN thin films having a relatively high (111) crystalline texture for two different thicknesses, according to embodiments. According to embodiments, increasing the N/Ti flow ratio, which in turn decreases the thickness, increases a Young’s modulus and a hardness of the TiN thin film.
  • the illustrated TiN thin films are shown as examples only, and the embodiments are not so limited.
  • the hardness of the TiN films formed according to embodiments exceeds 6 GPa.
  • the hardness can exceed 6 Gpa, 10 Gpa, 14 Gpa, 18 Gpa, 22 Gpa, 25 Gpa, or have a value in a range defined by any of these values.
  • the elastic or Young’s modulus of the TiN films formed according to embodiments exceeds 150 Gpa.
  • the Young’s modulus can exceed 150 Gpa, 170 Gpa, 190 Gpa, 210 GPa, 230 GPa, 250 GPa, 270 GPa, 300 GPa, or have a value in a range defined by any of these values.
  • decreasing a deposition pressure increases the ratio of the peak height or the intensity of the X-ray diffraction peak corresponding to the (111) crystal orientation of TiN to the peak height or the intensity of the X-ray diffraction peak corresponding to the (200) crystal orientation of TiN.
  • FIG. 16 illustrates experimental X-ray spectra of TiN thin films formed at different exposure pressures and having a preferential (111) crystalline texture, according to embodiments.
  • the illustrated TiN thin films are shown as examples only, and the embodiments are not so limited.
  • the X-ray diffraction profiles were taken for TiN films having the same thickness but formed at two different exposure pressures, namely 5 torr and 3 torr.
  • the results show that lower pressure can lead to further increase in the (111) crystalline texture.
  • the inventors have recognized, however, that under some circumstances, lower exposure pressure can lead to compromised step coverage. Accordingly, in these circumstances, according to embodiments, after forming 1130 (FIG. 11) the TiN thin film having a relatively high (111) crystalline texture, the method 1100 (FIG.
  • 11) can further include forming on the TiN thin film a second TiN thin film by exposing the semiconductor substrate to one or more second cyclical vapor deposition cycles each comprising an exposure to a second Ti precursor and an exposure to a second N precursor, wherein exposures to one or both of the second Ti precursor and the second N precursor during the one or more second cyclical vapor deposition cycles are at higher pressures relative to corresponding exposures to one or both of the Ti precursor and the N precursor during the one or more first cyclical vapor deposition cycles.
  • Other exposure conditions corresponding to forming 1130 (FIG. 11) the TiN thin film and forming the second TiN thin film can be according to any of the exposure conditions described above with respect to FIGS. 3 A, 3B and 4.
  • FIG. 17 illustrates chlorine concentration depth profiles of TiN thin films having increased (111) crystalline texture, according to embodiments.
  • the depth profiles are obtained using secondary ion mass spectrometry.
  • the measured thin films correspond to Examples 1-4 listed in TABLE 1.
  • increasing the N/Ti flow ratio decreases the thickness for the same number of cycles.
  • increasing the N/Ti flow ratio which in turn decreases the thickness, decreases a resistivity of the TiN thin film.
  • FIG. 17 illustrates that this unexpected trend of decreasing resistivity with decreasing thickness correlates to decreasing chlorine concentration.
  • the amount of chlorine can decrease by more than 50%.
  • the chlorine concentration was measured to be 7.2xl0 20 /cm 3 , 6.1xl0 20 /cm 3 , 5.1xl0 20 /cm 3 and 3.5xl0 20 /cm 3 , respectively.
  • decreasing thickness had been associated with increasing chlorine content, which had been correlated to relatively higher resistivity.
  • high N/Ti flow ratios, high N precursor flow rate and/or low deposition pressure may increase the (111) texture of the resulting TiN thin film.
  • high (111) texture may provide various advantages in a similar manner to low pressure-deposited (e.g., less than 5 torr) TiN thin films as described above. Such advantages include improvements in resistivity, hardness, modulus and roughness to name a few.
  • the high N/Ti flow ratios may result in relatively low step coverage under some circumstances, in a similar manner as described above with respect to low pressure-deposited TiN thin films. To compensate, it may be desirable to have a dual or multiple layer process in which a second TiN thin film is grown on a first TiN thin film having a high (111) texture.
  • the method comprises forming on a semiconductor substrate a TiN thin film by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to a N precursor at a N precursor flow rate.
  • the method additionally comprises forming on the TiN thin film a second TiN thin film by exposing the semiconductor substrate to one or more second cyclical vapor deposition cycles each comprising an exposure to a second Ti precursor at a second Ti precursor flow rate and an exposure to a second N precursor at a second N precursor flow rate.
  • the method is such that one or both of the TiN thin film and the second TiN thin film have high (111) crystalline texture such that X-ray spectra of the one or both of the TiN thin film and the second TiN thin film have a ratio of a peak height or an intensity of an X-ray diffraction peak corresponding to a (111) crystal orientation of TiN to a peak height or an intensity of an X-ray diffraction peak corresponding to a (200) crystal orientation of TiN that exceeds 0.4.
  • a method of forming a thin film comprising titanium nitride (TiN) by a cyclical vapor deposition process comprises forming on a semiconductor substrate a first TiN thin film at a first pressure by exposing the semiconductor substrate to one or more first cyclical vapor deposition cycles each comprising an exposure to a first Ti precursor at a first Ti precursor flow rate and an exposure to a first N precursor at a first N precursor flow rate.
  • the first TiN thin film has a crystalline texture such that an X-ray spectrum of the TiN thin film has a ratio of a peak height or an intensity of an X- ray diffraction peak corresponding to a (111) crystal orientation of TiN to a peak height or an intensity of an X-ray diffraction peak corresponding to a (200) crystal orientation of TiN that exceeds 0.4.
  • the method additionally comprises forming on the first TiN thin film a second TiN thin film at a second pressure higher than the first pressure by exposing the semiconductor substrate to one or more second cyclical vapor deposition cycles each comprising an exposure to a second Ti precursor at a second Ti precursor flow rate and an exposure to a second N precursor at a second N precursor flow rate.
  • the second TiN thin film can be formed according to any first or second TiN thin film formed as part of a dual or multiple layer TiN thin film process described above, e.g., those described above with respect to FIGS. 3A, 3B and 4.
  • the resulting TiN thin film comprises a lower portion and an upper portion, where the lower and upper portions can have different crystalline textures.
  • At least the lower portion of the thin film has a crystalline texture such that an X-ray diffraction profile of the thin film has a ratio of a peak height or an intensity of an X-ray diffraction peak corresponding to (111) crystal orientation to a peak height or an intensity of an X-ray diffraction peak corresponding to (200) crystal orientation exceeds 0.4.
  • the upper portion can have similar or lower degree of (111) texture, depending on the deposition condition and the desired final film characteristics, as described herein.
  • the second TiN thin film grown on the TiN thin film can benefit from a high (111) texture of the underlying first TiN thin film.
  • the second TiN thin film can also have relatively high (111) texture despite that fact that, if grown on another surface that does not have the high (111) TiN texture of the underlying first TiN thin film, the second TiN thin film may not have a relatively high (111) texture.
  • a material other than TiN or TiN that does not have a relatively high (111) texture such as an insulating film such as S1O2, Si or other materials
  • the second TiN thin film may not have a relatively high (111) texture.
  • the second TiN layer may have a crystalline texture such that an X-ray spectrum of the TiN thin film has a ratio of a peak height or an intensity of an X- ray diffraction peak corresponding to a (111) crystal orientation of TiN to a peak height or an intensity of an X-ray diffraction peak corresponding to a (200) crystal orientation of TiN that is substantially less than 0.4, e.g., 0.3, 0.2, 0.1 or a value in a range defined by any of these values.
  • the textured surface of the underlying TiN thin film can serve as a template for the second or subsequent TiN thin film.
  • the second or subsequent TiN thin film is not necessarily formed under high (111) texturing condition
  • the second or subsequent TiN thin film can be formed under conditions that improve the overall performance of the combined TiN thin film.
  • the second or subsequent TiN thin film can be grown under conditions that increase the step coverage, e.g., at high pressure, as described above with respect to various two-step deposition processes.
  • the second TiN thin film can be formed at a high pressure, e.g., greater than 3 or 5 torr, as described above, e.g., according to various two step processes described with respect to FIGS. 3 A and 3B, with or without the high N precursor flow rate and/or N/Ti precursor flow ratio.
  • a high pressure e.g., greater than 3 or 5 torr
  • the initial film growth may proceed substantially in a (111) texture-favorable mode, which advantageously results in improved mechanical properties and electrical resistivity as described above.
  • the latter portion of the thin film, or the second TiN thin film can advantageously grow with a degree of conformality or a step coverage that is higher relative to a the first TiN thin film having a relatively high (111) texture, or relative to a TiN thin film that is deposited by exposing the substrate to the Ti and/or N precursors at the relatively low pressures, e.g., less than 3 torr or less than 1 torr.
  • the second portion of the thin film which may continue to grow in a layer by layer fashion, using the first portion as a template.
  • the second TiN thin film can have a lower or comparable (111) texture relative the underlying first TiN thin film.
  • the thickness ratio between first and second TiN thin films can be 10%, 25%, 50%, 25%, 90% or a value in a range defined by any of these values, depending on the final film characteristics desired.
  • the first TiN thin film may be 50% or greater in thickness relative to the overall thickness
  • the second TiN thin film may be 50% or greater in thickness.
  • the resulting TiN thin film can have (111) texture that is any fraction of the (111) texture value of the first TiN thin film, e.g., 10%, 25%, 50%, 25%, 90% or a value in a range defined by any of these values.
  • the resulting Young’ s modulus and/or hardness can also have a value defined by these values.
  • the resulting TiN thin film can have a conformality value that is any fraction of the conformality value of the second TiN thin film without the underlying first TiN thin film, e.g., 10%, 25%, 50%, 25%, 90% or a value in a range defined by any of these values thereof.
  • the thin film comprising the first and second portions deposited by depositing a relatively highly (111) textured first TiN thin film followed by a second TiN thin film according to methods disclosed herein advantageously has a combination of surface roughness and conformality that is superior relative to a thin film layer formed on the same surface using a single step.
  • the thin film has a relatively low electrical resistivity compared to TiN layers formed by some existing methods.
  • FIG. 18 schematically illustrates a thin film deposition system including a thin film deposition chamber and a precursor delivery system configured for forming TiN layers according to embodiments.
  • the illustrated thin film deposition chamber is configured to process a substrate on a support, e.g., a susceptor, under a process condition.
  • the process chamber includes a gas distribution plate, also referred to as a showerhead, configured to diffuse the precursor(s) over a substrate on the susceptor.
  • the thin film deposition system additionally includes a precursor delivery system configured to deliver a plurality of precursors from precursor sources and one or more purge gases, e.g., inert gases, from inert gas sources into the process chamber.
  • purge gases e.g., inert gases
  • Each of the precursors and purge gases is connected to the process chamber by a respective gas delivery line.
  • the gas delivery lines additionally include mass flow controllers (MFCs) and respective precursor valves for introducing respective precursors into the thin film deposition chamber, which can be atomic layer deposition (ALD) valves.
  • MFCs mass flow controllers
  • ALD atomic layer deposition
  • the gas delivery lines are connected to the thin film deposition chamber through a showerhead.
  • the illustrated precursor delivery system is configured to deliver precursors including TiCU and NFF, as a Ti precursor and a N precursor, respectively, into the process chamber from respective precursor sources through respective precursor delivery lines.
  • the precursor delivery system is additionally configured to deliver Ar as a purge gas into the process chamber from Ar sources through purge gas delivery lines.
  • the purge gas may be delivered as a continuous purge (CP) gas and/or a rapid purge (RP) gas.
  • the illustrated precursor delivery system is configured to deliver Ar as both CP and RP gases into the process chamber from the Ar sources through respective gas delivery lines. While the illustrated thin film deposition system includes one process station for single wafer processing, embodiments are not so limited. In some embodiments, the thin film deposition system can advantageously include multiple processing stations for increased throughout among other advantages, as described below with respect to FIG. 19.
  • FIG. 19 shows a perspective view of a lid of a process chamber comprising multiple processing stations each configured to introduce precursors to a substrate for TiN deposition.
  • Each of the multiple processing stations has a lid portion 112-1, 112-2, 112-3, 112- 4 that is configured to introduce precursors through precursor delivery lines as shown in FIG. 18, according to embodiments.
  • the lid illustrated in FIG. 19 corresponds to a process chamber having four processing stations each configured to process a substrate on a support, e.g., a susceptor, under a process condition.
  • Each of the processing stations is configured to independently process a substrate under a process condition, including a process temperature and a process pressure.
  • the processing stations can be, e.g., single substrate processing stations each configured to deliver precursors through respective precursor delivery lines, as shown in FIG. 18.
  • the illustrated lid portions 112-1, 112-2, 112-3 and 112-4 are physically outside the process chamber. Inside the process chamber, the lid portion can include or be attached to a gas distribution plate (not shown), or a showerhead, configured to diffuse the precursor(s) over a substrate on the susceptor.
  • Each of the process chamber lids illustrated in FIG. 19 is equipped with a precursor delivery system for delivering a plurality of precursors and one or more purge gases.
  • Each of the precursors and purge gases is connected to the process chamber by a respective gas delivery line.
  • Each of the delivery lines is connected to the respective gas source on the one end as described above with respect to the thin film deposition system illustrated in FIG. 19.
  • the delivery line is split into four local delivery lines connected to valve assembly blocks 250-1, 250-2, 250-3 and 250-4 (not shown) each including multiple ALD valves.
  • the ALD valves are in turn connected to showerheads of each of the processing stations, in a similar manner as shown in FIG. 18.
  • a method of depositing a thin film comprises alternatingly exposing a substrate in a thin film deposition chamber to a plurality of precursors. Exposing the substrate comprises introducing the precursors into the thin film deposition chamber through valves (e.g., atomic layer deposition (ALD) valves) each configured to supply one of the precursors.
  • ALD atomic layer deposition
  • each of the precursor valves can be configured as a three-port valve configured to simultaneously flow a carrier gas and a precursor gas.
  • a carrier gas e.g., Ar or N2
  • a precursor gas enters through a third port, which is a small, precise orifice that delivers a relatively small chemical volume.
  • This three-port configuration can deliver a steady flow of carrier gas into the process station while pulsing a precursor gas, as shown.
  • the carrier gas serves to facilitate the movement the precursor into the deposition chamber, and to control the overall process pressure during deposition.
  • FIG. 20 illustrates, by way of example only, an example precursor delivery sequence for delivering two precursors, according to some embodiments.
  • a first precursor 2010 is delivered through a first precursor inlet connected to a first valve (e.g., an ALD valve) and a second precursor 2020 is delivered through a second precursor inlet connected to a second valve (e.g., an ALD valve).
  • a deposition cycle 2006 (e.g., an ALD cycle) comprises a first subcycle 2002 for exposing a substrate to the first precursor 2010, e.g., a first one of Ti and N precursors, and a second subcycle 2004 for exposing the substrate to the second precursor 2020, e.g., the other of the Ti and N precursors.
  • Each of the precursor valves can be configured as a three-port valve, and in some implementations, a continuous purge gas 2008, e.g., an inert gas, may be provided through the valves while the substrate is exposed to the first precursor 2010 and/or the second precursor 2020.
  • a continuous purge gas 2008 e.g., an inert gas
  • one or both of the first 2002 and second 2004 subcycles further comprise respective rapid purges 2012, 2022 using an inert gas following the exposures to one or both of the first 2010 and second 2020 precursors, respectively.
  • the rapid purges 2012, 2022 may be performed using a purge valve.
  • the rapid purge 2012 is higher in magnitude, e.g. has a higher flow rate, than the continuous purge 2008.
  • first 2010 and second 2020 precursors may be introduced into the thin film deposition chamber through respective valves.
  • the first precursor 2010 can be, e.g., one of a Ti precursor such as TiCL and a N precursor such as NFL
  • the second precursor 2020 can be, e.g., the other of the Ti precursor and the N precursor.
  • the exposure time of one or both of the first 2010 and second 2020 precursors can be less than 1.0 sec., 0.8 sec., 0.6 sec, 0.4 sec, 0.2 sec., 0.1 sec., or a value in a ranged defined by any of these values.
  • the thin film deposition system is configured to introduce one or both of the first 2010 and second 2020 precursors through respective ones of the valves at respective flow rates such that a surface of the substrate substantially reaches a saturation level, e.g., a saturation level greater than 40%, 60%, 80% or a value in a range defined by any of these values, within the respective exposure times.
  • a saturation level e.g., a saturation level greater than 40%, 60%, 80% or a value in a range defined by any of these values, within the respective exposure times.
  • durations of one or both of the first 2002 and second 2004 subcycles, including the precursor exposure and the rapid purge can be less than 1.0 sec., 0.8 sec., 0.6 sec, 0.4 sec, 0.2 sec., 0.1 sec., or a value in a ranged defined by any of these values.
  • a duration of the overall cycle 2006 including the first 2002 and second 2004 subcycles may be less than 2.0 sec., 1.5 sec, 1.0 sec., 0.5 sec., or a value in a range defined by any of these values.
  • NH3 when used as a nitrogen precursor or as a purge gas according to embodiments disclosed herein, can provide a significant reduction in particles that are deposited on a substrate directly or indirectly as a result of depositing the TiN layer.
  • FIG.21 is a flow chart schematically illustrating a method 2100 of forming a TiN layer by cyclical vapor deposition process with reduced particles generated therefrom, according to some embodiments.
  • the method includes providing 2110 a semiconductor substrate and forming 2120 on the semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to NH3 at a NH3 flow rate.
  • Exposing 2130 the semiconductor substrate includes subjecting the semiconductor substrate to one or more exposure conditions including: a ratio of the NH3 flow rate to the Ti precursor flow rate exceeding 3; the NH3 flow rate exceeding 300 seem; and/or a NH3 exposure duration of 0.1-0.6 sec.
  • the method 2100 can be implemented on a thin film deposition system similar to those described above with respect to FIGS. 18 and 19, and using a precursor delivery sequence similar to that described above with respect to FIG. 20.
  • the first precursor 2010 can be a Ti precursor, e.g., TiCU
  • the second precursor 2020 can be a N precursor, e.g., NH3
  • the exposures to each of the first 2010 and second 2020 precursors can be followed by a rapid purge 2012, 2022 using, e.g., N2 or Ar.
  • the exposures to each of the first 2010 and second 2020 precursors can be accompanied by a continuous purge 2008 through a three-port ALD valve described above.
  • subjecting 2130 the semiconductor substrate to one or more exposure conditions is such that a ratio of the NH3 flow rate to the Ti precursor flow rate exceeds 2.
  • the ratio can exceed 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or have a value in a range defined by any of these values.
  • subjecting 2130 the semiconductor substrate to one or more exposure conditions is such that the NH3 flow rate can exceed 200 seem, 500 seem, 1000 seem, 2000 seem, 3000 seem. 4000 seem, 5000 seem, 6000 seem, 7000 seem, 8000 seem, 9000 seem, 10000 seem, or have a value in a range defined by any of these values.
  • subjecting 2130 the semiconductor substrate to one or more exposure conditions is such that the Ti precursor flow rate exceeds 100 seem but does not exceed the flow rate of NH3.
  • the Ti precursor flow rate can exceed 100 seem, 200 seem, 500 seem, 1000 seem, 2000 seem, 3000 seem., 4000 seem, 5000 seem, or have a value in a range defined by any of these values.
  • the flow rates disclosed herein can represent a flow rate per processing station, and one or more stations can be in operation at the same time.
  • the total flow rates described herein can be lx, 2x, 3x or 4x depending on how many processing stations are operated at a given moment.
  • FIG. 22 shows an experimental measurement of the number of particles on a 300 mm wafer after forming TiN layers using the method illustrated in FIG. 21.
  • the y-axis represents the total number of particles detected as having a size of about 0.100-0.700 mhi, as measured using KLA-Tencor SP1/SP2.
  • the x-axis represents the duration of the exposure of the substrate to NH3 as part of the process that can be represented by the exposure sequence illustrated in FIG. 20.
  • the number of particles was measured after subjecting a substrate to a plurality of cycles each including an exposure to TiCU and an exposure to NH3, where the exposures to each of the precursors is followed by a rapid purge using Ar.
  • the TiCU flow rate and NH3 flow rate were 100 seem and 2000 seem, respectively, per processing station for each of the four processing stations as illustrated in FIG. 19, or a combined flow of 400 seem and 8000 seem, respectively.
  • the TiCU exposure duration, post-TiCU exposure purge duration, NH3 exposure duration and post-NFU exposure purge duration were 0.1 sec., 0.2 sec., 0.1-0.6 sec as shown and 0.3 sec., respectively.
  • the chamber pressure during deposition was 5 Torr and the substrate temperature was about 550°C during the deposition of the TiN layer.
  • the inventors have found that the NH3 exposure duration less than 0.6 sec, or more particularly a duration of 0.1-0.6 sec., 0.1-0.2 sec, 0.2-0.3 sec., 0.3-0.4 sec., 0.4-0.5 sec, 0.5-0.6 sec., or 0.3-0.6 sec, can be critical in obtaining an expected reduction in the number of particles on or embedded in the thin film having a size greater than about 0.1 mhi by 50% or more.
  • NH3 may, alone or in combination of any of the chemical species present on the substrate or in the chamber, chemically or physically interact or react with some types of particles.
  • the interaction may be, e.g., a chemical reaction that volatilizes the particles, thereby reducing the particles that may have formed on the substrate.
  • the interaction may be, e.g., a physical interaction where the high relatively high flow rate physically removes the particles that may have formed on the substrate.
  • FIG. 23 is a flow chart schematically illustrating a method 2300 of forming a TiN layer by cyclical vapor deposition process with reduced particle generation, according to some other embodiments. Unlike the method 2100 described above with respect to FIG. 21, the method 2300 includes subjecting the semiconductor substrate to NH3 after forming the TiN thin film.
  • the method 2300 includes providing 2310 a semiconductor substrate and forming 2320 on the semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to NH3 at a first NH3 flow rate for a NH3 exposure duration.
  • the method 2300 additionally includes, after forming the TiN film, subjecting 2330 the semiconductor substrate, e.g., in situ and without further deposition of the TiN film to a post-deposition exposure to NH3 under a condition including one or both of: a second NH3 flow rate lower than the first NH3 flow rate by at least a factor of two; and a second NH3 exposure duration exceeding the NH3 exposure duration by at least a factor of five.
  • the post-deposition exposure may be the last exposure step prior to removing the substrate from the chamber.
  • the method 2300 can be implemented in a thin film deposition system similar to those described above with respect to FIGS. 18 and 19.
  • forming 2320 the TiN thin film can be implemented using a precursor delivery sequence similar to that described above with respect to FIG. 20.
  • Various process parameters including the substrate temperature, chamber pressure, flow rates and exposure times during deposition, can be in accordance with various process parameters described above, the details of which are not repeated herein for brevity.
  • the illustrated method 2300 additionally includes, after forming the TiN thin film, subjecting 2330 the substrate having a TiN thin film formed thereon to a post-deposition exposure to NH3.
  • subjecting 2330 the semiconductor substrate, without further depositing the TiN film, to a post-deposition exposure to NH3 includes exposing the semiconductor substrate to a second NH3 flow rate that is different, e.g., lower than the NH3 flow rate during the deposition of the TiN by at least a factor of 2, 4, 6, 8, 10, or a value in a range defined by any of these values.
  • the second NH3 flow rate can exceed 100 seem, 250 seem, 500 seem, 1000 seem, 1500 seem, 2000 seem, 2500 seem, 3000 seem, 3500 seem, 4000 seem, 4500 seem, 5000 seem, or have a value in a range defined by any of these values, for instance 500 seem.
  • subjecting 2330 the semiconductor substrate, without further depositing the TiN film, to a post-deposition exposure to NH3 includes exposing the semiconductor substrate to a second NH3 exposure for a duration exceeding the NH3 exposure duration during the deposition of the TiN by at least a factor of 5, 10, 20, 50, 100, 200, 500 or a value in a range defined by any of these values.
  • the second NH3 exposure duration can exceed 1 sec., 5 sec., 10 sec, 20 sec, 50 sec., 100 sec., 200 sec., 500 sec, 1000 sec., or have a value in a range defined by any of these values, for instance 120 sec.
  • subjecting 2330 the semiconductor substrate to a post deposition exposure can be performed at a first temperature. In some embodiments, subjecting 2330 the semiconductor substrate to a post deposition exposure can be performed at the same temperature as forming 2320 on the semiconductor substrate a TiN thin film without aid of plasma. In some other embodiments, subjecting 2330 the semiconductor substrate to a post deposition exposure can be performed at a different temperature than forming 2320 on the semiconductor substrate a TiN thin film without aid of plasma.
  • FIGS. 24A and 24B show experimental measurements of the number of particles on a 300 mm wafer after forming a TiN layer using the method illustrated in FIG. 23. In FIG.
  • the y-axis of the graph represents the total number of particles detected as having a size of about 0.100-0.700 mhi, as measured using KLA-Tencor SP1/SP2.
  • the x-axis of the graph shows two different post-deposition exposure times, namely 20 sec. (left bar graphs) and 120 sec. (right bar graphs), for exposing the substrate to NFF. For each exposure times, measurements were made on two different stations (Stnl, Stn4) in a multi-station chamber such that described above with respect to FIG. 19. The number of particles was measured after subjecting a substrate to a TiN deposition and to the post-deposition NFb purge, according to embodiments.
  • the process condition for depositing the TiN thin film was the same as that described above with respect to FIG. 22 with an NFb exposure time of 0.3 sec.
  • the NFF purge was performed at a flow rate of 500 seem per processing station for each of the four processing stations as illustrated in FIG. 19, or a combined flow of 2000 seem.
  • the post-deposition NFb exposure durations for the two experimental conditions were 20 sec. and 120 sec.
  • the chamber pressure during the TiN deposition and during the post-deposition NFF exposure was kept constant at 5 Torr and the substrate temperature was kept constant at about 550°C during the TiN deposition and during the post-deposition NFb exposure.
  • FIG. 25 is a flow chart schematically illustrating a method 2500 of forming a TiN layer by cyclical vapor deposition process with reduced particle generation, according to some other embodiments.
  • the method 2500 includes, prior to deposition, subjecting 2510 a thin film deposition chamber without a substrate disposed therein to a pre-deposition chamber purge under a NFb purge flow rate, which can be the same, higher or lower than a NFb flow rate during a TiN thin film deposition condition by at least a factor of two. Subsequently, the method 2500 includes transferring 2520 a semiconductor substrate into the thin film deposition chamber.
  • the method 2500 additionally includes forming 2530 on the semiconductor substrate a TiN thin film under the thin film deposition condition in the thin film deposition chamber without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to ammonia (NH3) at a NH3 flow rate.
  • a TiN thin film under the thin film deposition condition in the thin film deposition chamber without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to ammonia (NH3) at a NH3 flow rate.
  • the method 2500 can be implemented in a thin film deposition system described above with respect to FIGS. 18 and 19.
  • forming 2530 the TiN thin film can be implemented using a precursor delivery sequence similar to that described above with respect to FIG. 20.
  • Various process parameters including the substrate temperature, chamber pressure, flow rates and exposure times during deposition can be in accordance with various process parameters described above, the details of which are not repeated herein for brevity.
  • the illustrated method 2500 additionally includes, before and/or after forming the TiN thin film, subjecting 2530 the thin film deposition chamber without having a substrate disposed therein to an idle purge using NH3.
  • subjecting 2510 the thin film deposition chamber to a NH3 purge includes flowing NH3 at a second NH3 flow rate that can be the same or different compared to the NH3 flow rate during the deposition of the TiN.
  • the NH3 purge flow rate can exceed 200 seem, 500 seem, 1000 seem, 2000 seem, 3000 seem, 4000 seem, 5000 seem, 6000 seem, 7000 seem, 8000 seem, 9000 seem, 10,000 seem, or have a value in a range defined by any of these values, or have a value in a range defined by any of these values, for instance 2000 seem.
  • the NH3 purge can be accompanied by a nitrogen (N2) purge at a flow rate similar to any of the above NH3 flow rates.
  • subjecting 2510 the thin film deposition chamber to a NH3 purge includes flowing the NH3 for a duration exceeding that of a deposition cycle duration.
  • the purge duration can exceed 1 sec., 100 sec., 1000 sec., 10,000 sec., or have a value in a range defined by any of these values, for instance 2 hours.
  • a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% or more.
  • FIG. 26 shows experimental measurements of the number of particles on a 300 mm wafer after subjecting the thin film deposition to the pre-deposition chamber purge under a NH 3 purge according to the method illustrated in FIG. 25.
  • the y- axis represents the total number of particles detected as having a size of about 0.100-0.700 mhi, as measured using KLA-Tencor SP1/SP2.
  • the x-axis shows the conditions the chamber has been subjected to prior to inserting a virgin test wafer for particle detection, namely before the TiN deposition, after 5000 TiN deposition wafer cycles and after 2 hours of idle purge under NH 3 .
  • the process condition for TiN deposition cycles was the same as that described above with respect to FIG.
  • the thin films comprising TiN formed using different exposure pressures can be used in a variety of applications, particularly where the substrate comprises a relatively high aspect ratio structure and/or a non- metal surface that can benefit from various advantageous characteristics of the TiN layer as disclosed herein.
  • Example applications include deposition a via, a hole, a trench, a cavity or a similar structure having an aspect ratio, e.g., a ratio defined as a depth divided by a top width, that exceeds 1, 2, 5, 10, 20, 50, 100, 200 or a value in a range defined by any of these values.
  • FIG. 10 schematically illustrates an application in the context of a diffusion barrier for a contact structure, e.g., a source or drain contact, formed on an active semiconductor substrate region that may be heavily doped.
  • a portion of a semiconductor device 1000 is illustrated, which includes a substrate 1004 on which a dielectric layer 1008, e.g., an interlayer or intermetal dielectric (ILD) layer comprising a dielectric material such as an oxide or nitride is formed.
  • a via or a trench may be formed through the dielectric layer 1008.
  • the via or the trench may expose various non-metal surfaces, e.g., an exposed bottom surface comprising a substrate surface, e.g., a silicon substrate surface, as well as dielectric sidewalls of the vias.
  • the bottom and side surfaces of the via can be conformally coated with a first portion (corresponding to the first portion 370 in FIG. 3B) of the TiN layer, followed by a second portion (corresponding to the second portion 380 in FIG. 3B) formed according to various embodiments described herein.
  • a conformal first portion may first be formed directly on inner surfaces of the via, followed by formation of a conformal second TiN layer, according to various embodiments disclosed herein.
  • the lined via may be filled with a metal, e.g., W, A1 or Cu, to form a contact plug 1016.
  • a metal e.g., W, A1 or Cu
  • the via may be filled with tungsten by CVD using, e.g., WF 6 .
  • the barrier layer 1012 formed according to embodiments can be advantageous for various reasons.
  • the propensity for a pinching off during the subsequent metal fill process may be substantially reduced.
  • the barrier layer 1012 can provide effective hindrance of material transport thereacross, e.g., dopant (B, P) out-diffusion from the substrate 1004, as well as in-diffusion of reactants, etchants and metals (e.g., F, Cl, W or Cu) from the contact plug formation process.
  • the barrier effect may be enhanced by reduced surface roughness and increased step coverage.
  • a layer-by-layer growth mode may reduce the overall contact resistance of the barrier layer 1012. Furthermore, due to the reduced film roughness, a relatively thinner barrier layer 1012 may be formed while still accomplishing its desired barrier function, leading to further reduction in contact resistance.
  • TiN layers formed according to various embodiments disclosed herein include conductive structures formed in recessed substrates (e.g., buried electrodes or lines), electrodes (e.g., DRAM capacitor electrodes or gate electrodes), metallization barriers for higher metal levels (e.g., barriers in vias/trenches for Cu contacts/lines), high aspect ratio vertical rod electrodes or vias for three-dimensional memory and through-silicon vias (TSVs), to name a few.
  • recessed substrates e.g., buried electrodes or lines
  • electrodes e.g., DRAM capacitor electrodes or gate electrodes
  • metallization barriers for higher metal levels e.g., barriers in vias/trenches for Cu contacts/lines
  • TSVs through-silicon vias
  • a method of forming a thin film comprising titanium nitride (TiN) by a cyclical vapor deposition process comprising: forming on a semiconductor substrate a TiN thin film by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to a N precursor at a N precursor flow rate, wherein a ratio of the N precursor flow rate to the Ti precursor flow rate exceeds 3.
  • a method of forming a thin film comprising titanium nitride (TiN) by a cyclical vapor deposition process comprising: forming on a semiconductor substrate a TiN thin film by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to a first N precursor at a first N precursor flow rate, wherein the N precursor flow rate exceeds 200 seem.
  • a method of forming a thin film comprising titanium nitride (TiN) by a cyclical vapor deposition process comprising: forming on a semiconductor substrate a TiN thin film by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate within a Ti precursor flow rate range and an exposure to a N precursor at a N precursor flow rate within a N precursor flow rate range, wherein the N precursor flow range and the Ti precursor flow range are such that the TiN thin film has a preferential (111) crystalline texture relative to another TiN thin film formed by exposing the semiconductor substrate to cyclical vapor deposition cycles each comprising an exposure to the Ti precursor within a different Ti precursor flow rate range outside of the Ti precursor flow rate range and an exposure to the N precursor within a different N precursor flow rate range outside of the N precursor flow rate range.
  • forming the TiN thin film comprises depositing at a first deposition rate less than 0.3 A per one of the cyclical vapor deposition cycles comprising an exposure of the semiconductor substrate to the Ti precursor and an exposure to the N precursor, and wherein forming the second TiN thin film comprises depositing at a second deposition rate greater than 0.3 A per one of the second cyclical vapor deposition cycles comprising an exposure of the semiconductor substrate to the second Ti precursor and an exposure to the second N precursor.
  • the semiconductor substrate comprises a trench or a via comprising an inner surface comprising a non-metallic sidewall surface in a trench or a via having an aspect ratio exceeding 1, and wherein forming the thin film comprises conformally lining the inner surface, wherein a ratio of thicknesses of the thin film formed on lower 25% of a height of the trench or the via and upper 25% of the height of the trench or the via exceeds 0.9.
  • an electrical resistivity of the thin film is less than about 200 mW-cm.
  • any of Embodiments 1-9 comprising: providing the semiconductor substrate comprising a trench or a via having an aspect ratio exceeding 1 ; forming the thin film in the trench or the via by exposing the semiconductor substrate to the one or more cyclical vapor deposition to form the TiN thin film in the trench or the via; and further exposing the semiconductor substrate to one or more second cyclical vapor deposition cycles each comprising an exposure to a second Ti precursor and an exposure to a second N precursor to form a second TiN thin film on the TiN thin film, wherein exposures to one or both of the Ti precursor and the N precursor during the one or more cyclical vapor deposition cycles are at different pressures relative to corresponding exposures to one or both of the second Ti precursor and the second N precursor during the one or more second cyclical vapor deposition cycles.
  • forming the TiN layer comprises forming by thermal cyclical vapor deposition at a temperature between 400°C and 600°C.
  • a semiconductor structure comprising: a semiconductor substrate comprising a non-metallic sidewall surface in a trench or a via having an aspect ratio exceeding 5; and a thin film comprising TiN conformally lining the non-metallic sidewall surface, wherein the thin film has a preferential (111) crystalline texture such that an X- ray spectrum of the thin film has a ratio of a peak height or an intensity of an X-ray diffraction peak corresponding to (111) crystal orientation to a peak height or an intensity of an X-ray diffraction peak corresponding to (200) crystal orientation exceeds 0.4.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition comprising: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to ammonia (NH3) at a NH3 flow rate exceeding 200 seem, wherein a NH3 exposure duration is 0.1 to 0.6 sec.
  • Embodiment 2 The method of Embodiment 1, wherein the method is carried out in a thin film deposition system wherein, relative to a TiN thin film deposited in the same thin film deposition system using a method having the same process parameters except for one or both of the NH3 flow rate and the NH3 exposure duration, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% of more. 3.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition comprising: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to ammonia (N3 ⁇ 4) at a N3 ⁇ 4 flow rate such that a flow rate ratio of the N3 ⁇ 4 flow rate to the Ti precursor flow rate exceeds 3, wherein a N3 ⁇ 4 exposure duration is 0.1 to 0.6 sec.
  • Embodiment 4 The method of Embodiment 3, wherein the method is carried out in a thin film deposition system wherein, relative to a TiN thin film deposited in the same thin film deposition system using a method having the same process parameters except for one or both of the flow rate ratio and the N3 ⁇ 4 exposure duration, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% of more.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition comprising: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to ammonia (N3 ⁇ 4) at a N3 ⁇ 4 flow rate for a N3 ⁇ 4 exposure duration; and after forming the TiN thin film, subjecting the semiconductor substrate without further deposition of the TiN thin film to a post-deposition exposure to N3 ⁇ 4 under a condition including a second N3 ⁇ 4 flow rate lower than the N3 ⁇ 4 flow rate by at least a factor of two.
  • TiN titanium nitride
  • Embodiment 6 The method of Embodiment 5, wherein the method is carried out in a thin film deposition system wherein, relative to a thin TiN film deposited in the same thin film deposition system using a method having the same process parameters except for subjecting the substrate to the post deposition exposure to N3 ⁇ 4, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% of more.
  • Embodiments 5 or 6 wherein forming the TiN thin film and subjecting the TiN thin film to a post-deposition exposure are performed at the same substrate temperature.
  • the N3 ⁇ 4 flow rate is 1000- 3000 seem, and the second NH3 flow rate is 200-1000 seem.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition comprising: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor at a Ti precursor flow rate and an exposure to ammonia (NH3) at a NH3 flow rate for a NH3 exposure duration; and after forming the TiN thin film, subjecting the semiconductor substrate without further deposition of the TiN thin film to a post-deposition exposure to NH3 under a condition including a second NH3 exposure duration exceeding the NH3 exposure duration by at least a factor of five.
  • TiN titanium nitride
  • Embodiment 10 The method of Embodiment 9, wherein the method is carried out in a thin film deposition system wherein, relative to a TiN thin film deposited in the same thin film deposition system using a method having the same process parameters except for subjecting the substrate to the post deposition exposure to NH3, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% of more.
  • Embodiments 9 or 10 wherein forming the TiN thin film and subjecting the TiN thin film to a post-deposition exposure are performed at the same substrate temperature.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition process comprising: subjecting a thin film deposition chamber without a substrate disposed therein to a pre-deposition chamber purge with ammonia (NH3) at a NH3 purge flow rate; transferring a semiconductor substrate into the thin film deposition chamber; and forming on the semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor flow rate and an exposure to NH3. 14.
  • NH3 ammonia
  • Embodiment 13 wherein the method is carried out in the thin film deposition system wherein, relative to a TiN thin film deposited in the same thin film deposition system using a method having the same process parameters except for subjecting the thin film deposition chamber to the pre-deposition N3 ⁇ 4 purge, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% of more.
  • the one or more cyclical vapor deposition cycles comprises the exposure to the Ti precursor at a Ti precursor flow rate and the exposure to ammonia (N3 ⁇ 4) at a N3 ⁇ 4 flow rate such that a flow rate ratio of the N3 ⁇ 4 flow rate to the Ti precursor flow rate is 3-100.
  • forming the TiN thin comprises exposing the semiconductor substrate to the Ti precursor and N3 ⁇ 4 for respective durations such that a duration of a cycle of the cyclical vapor deposition cycles is less than 2.0 sec.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition comprising: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor and an exposure to ammonia (NH3) at a first NH3 flow rate; and after forming the TiN thin film, subjecting the semiconductor substrate, without deposition of an additional TiN thin film on the TiN thin film, to a post-deposition exposure to NH3 at a second NH3 flow rate, wherein the second NH3 flow rate is lower than the first NH3 flow rate by at least a factor of two.
  • TiN titanium nitride
  • Embodiment 2 The method of Embodiment 1, wherein the method is carried out in a thin film deposition system wherein, relative to a reference TiN thin film deposited in the same thin film deposition system using a reference method that is the same as the method of Claim 1 except for subjecting the semiconductor substrate to the post-deposition exposure to NH3, a number of particles on or embedded in the TiN thin film having a size greater than 0.1 mhi is reduced by 50% or more.
  • Embodiments 1 or 2 wherein forming the TiN thin film and subjecting the semiconductor substrate to the post-deposition exposure are performed at the same semiconductor substrate temperature.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition comprising: forming on a semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor and an exposure to ammonia (N3 ⁇ 4) for a first NH3 exposure duration; and after forming the TiN thin film, subjecting the semiconductor substrate, without deposition of an additional TiN thin film on the TiN thin film, to a post-deposition exposure to NH3 for a second NH3 exposure duration, wherein the second NH3 exposure duration is greater than the first NH3 exposure duration by at least a factor of five.
  • TiN titanium nitride
  • Embodiment 11 The method of Embodiment 10, wherein the method is carried out in a thin film deposition system wherein, relative to a reference TiN thin film deposited in the same thin film deposition system using reference a method that is the same as the method of Claim 10 except for subjecting the semiconductor substrate to the post-deposition exposure to NH3, a number of particles on or embedded in the TiN thin film having a size greater than 0.1 mhi is reduced by 50% or more.
  • a method of depositing a thin film comprising titanium nitride (TiN) by cyclical vapor deposition process comprising: subjecting a thin film deposition chamber without a substrate disposed therein to a pre-deposition chamber purge with ammonia (NH3) at a first NH3 purge flow rate; transferring a semiconductor substrate into the thin film deposition chamber; and forming on the semiconductor substrate a TiN thin film without aid of plasma by exposing the semiconductor substrate to one or more cyclical vapor deposition cycles each comprising an exposure to a Ti precursor and an exposure to NH3.
  • NH3 ammonia
  • Embodiment 16 wherein the method is carried out in the thin film deposition system wherein, relative to a reference TiN thin film deposited in the same thin film deposition system using reference method that is the same as the method of Claim 16 except for subjecting the thin film deposition chamber to the pre-deposition chamber purge, a number of particles on or embedded in the TiN thin film having a size greater than about 0.1 mhi is reduced by 50% or more.
  • the words “comprise,” “comprising,” “include,” “including” and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to.”
  • the word “coupled”, as generally used herein, refers to two or more elements that may be either directly connected, or connected by way of one or more intermediate elements.
  • the word “connected”, as generally used herein, refers to two or more elements that may be either directly connected, or connected by way of one or more intermediate elements.
  • conditional language used herein such as, among others, “can,” “could,” “might,” “may,” “e.g.,” “for example,” “such as” and the like, unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or states.
  • conditional language is not generally intended to imply that features, elements and/or states are in any way required for one or more embodiments or whether these features, elements and/or states are included or are to be performed in any particular embodiment.

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Abstract

De manière générale, la technologie de l'invention divulgue la formation d'un film mince comprenant du nitrure de titane (TiN), et plus particulièrement la formation par un traitement de dépôt en phase vapeur cyclique du film mince comprenant du TiN. Selon un aspect, un procédé de formation d'un film mince comprenant du nitrure de titane (TiN) par un traitement de dépôt en phase vapeur cyclique consiste à former sur un substrat semi-conducteur un film mince de TiN par exposition du substrat semi-conducteur à un ou plusieurs cycles de dépôt en phase vapeur comprenant chacun une exposition à un précurseur de Ti à un débit de précurseur de Ti et une exposition à un précurseur de NH3 à un débit de précurseur de NH3, après la formation du film de TiN, à soumettre le substrat semi-conducteur, sans dépôt supplémentaire du film mince de TiN, à une exposition post-dépôt de NH3 à un second débit de NH3.
PCT/US2022/071227 2021-03-22 2022-03-18 Couches de nitrure de titane conformes et lisses et procédés pour leur formation WO2022204663A1 (fr)

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