WO2019132113A1 - Method of manufacturing a cobalt containing thin film - Google Patents

Method of manufacturing a cobalt containing thin film Download PDF

Info

Publication number
WO2019132113A1
WO2019132113A1 PCT/KR2018/002428 KR2018002428W WO2019132113A1 WO 2019132113 A1 WO2019132113 A1 WO 2019132113A1 KR 2018002428 W KR2018002428 W KR 2018002428W WO 2019132113 A1 WO2019132113 A1 WO 2019132113A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
containing thin
cobalt
plasma
hydrogen
Prior art date
Application number
PCT/KR2018/002428
Other languages
French (fr)
Inventor
Myong Woon Kim
Sang Ick Lee
Sung Woo Cho
Kang Yong Lee
Original Assignee
Dnf Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dnf Co., Ltd. filed Critical Dnf Co., Ltd.
Publication of WO2019132113A1 publication Critical patent/WO2019132113A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/45542—Plasma being used non-continuously during the ALD reactions
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • 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
    • H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01027—Cobalt [Co]

Definitions

  • the present invention relates to a method of manufacturing a cobalt containing thin film.
  • the aluminum-based metal wiring has started to have limitations in terms of resistance, a deposition rate, stability, or the like. For this reason, a wiring technology using copper as metal which may have low resistance and excellent interfacial characteristics to replace the aluminum-based metal wiring is being developed rapidly.
  • the copper has high conductivity and thus may have a tolerance even if the amount of electrons flowing in a lead increases due to the increase in the speed of the semiconductor element.
  • the copper is more difficult to be etched than aluminum, there is a problem in that the copper wiring cannot be formed by a photolithography process unlike the aluminum-based metal wiring.
  • a method of forming a copper wiring generally, a single damascene method of forming the desired predetermined copper wiring by previously forming a long extended trench corresponding to a circuit wiring on an insulating layer on which a copper wiring is to be located, buryingcopper in the trench, and then performing a chemical mechanical polishing (CMP) process to remove copper formed in locations other than the trench may be used.
  • CMP chemical mechanical polishing
  • a dual damascene method of penetrating through an insulating layer to connect between a lower conductive layer and an upper conductive layer which are vertically separated from each other by the insulating layer, forming a via hole through which the lower conductive layer is exposed and a trench together, burying copper in these via hole and trench together, and then performing a CMP process to remove unnecessary copper may be used.
  • an interlayer insulating layer is formed on a semiconductor substrate on which predetermined lower patterns are formed and then a trench defining a metal wiring forming area including the via hole for the metal wiring is formed within the interlayer insulating layer.
  • a anti-diffusion layer is deposited on an inner wall of the via hole and the trench and the interlayer insulating layer and then a copper film is deposited to completely bury the trench and the via hole on the anti-diffusion layer
  • the copper film and the anti-diffusion layer are polished by the chemical mechanical polishing process to expose the interlayer insulating layer, thereby forming the copper wiring in the via hole and the trench.
  • a capping film is formed between the copper wiring and the interlayer insulating layer to prevent copper from being diffused in an upward direction of the copper wiring.
  • the capping film is deposited and then the photoresist is applied thereon, the exposure and development phenomenon is performed on the photoresist to form an opening on a photoresist pattern and then an etching process needs to be performed using the opening as an etch mask, which is an increasing factor of process cost and tact time.
  • the present applicant has studied capping layer material and process conditions for suppressing the occurrence of metal diffusion, deformation and de-weighting of metal crystalline structure and the like caused from a metal wiring in a semiconductor device including the metal wiring to find that a method of manufacturing a high-density, high-purity cobalt containing thin film which can be deposited on the metal wiring at a high deposition rate and can implement remarkably improved step coverage and gap fill characteristics when satisfying the predetermined material and process conditions, thereby completing the present invention.
  • An object of the present invention is to provide a method of manufacturing a high-purity cobalt containing thin film for forming a cobalt capping layer on a metal wiring.
  • Another object of the present invention is to provide a method of manufacturing a high-density, high-purity cobalt containing thin film capable of implementing improved step coverage and gap fill characteristics.
  • Still another object of the present invention is to provide a method of manufacturing a cobalt containing thin film capable of selectively forming a cobalt capping layer on a metal wiring by being selectively deposited only on a conductive layer on a substrate on which the conductive layer and an insulating layer exist.
  • a method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition includes: a first step of adsorbing a cobalt precursor compound onto a substrate and then providing purgegas; and a second step of providing hydrogen plasma onto the substrate to form a deposition film, wherein the hydrogen plasma satisfies the following conditions.
  • P H is a hydrogen plasma irradiation dose
  • T H is a supply time of hydrogen plasma
  • the cobalt precursor compound may be at least one selected from the following Chemical Formulae 1 and 2.
  • R 1 and R 2 each may independently be hydrogen or (C1-C5) alkyl
  • R 3 and R 4 each may independently be hydrogen, (C1-C7) alkyl, amino (-NH 2 ) or silyl (-SiH 3 );
  • o may be an integer of 0 to 2;
  • p may be an integer of 0 or 1, except the case when o and p are 0 at the same time]
  • the R 1 may be hydrogen
  • the o may be an integer of 2;
  • the R 3 may be hydrogen
  • R 2 and R 4 each may independently be hydrogen or (C1-C5) alkyl
  • the p is an integer of 1.
  • the cobalt precursor compound of the Chemical Formula 1 may be adsorbed onto the substrate ranging from 250 to 350 °C and then purge gas may be provided.
  • the cobalt precursor compound of the Chemical Formula 2 may be adsorbed onto the substrate ranging from 350 to 500 °C and then the purge gas may be provided.
  • the second step of providing the hydrogen plasma to form the deposition film may be performed.
  • the hydrogen plasma may satisfy the above conditions.
  • the method may further include: a third step of performing gap fill by providing argon plasma onto the substrate on which the deposition film is formed.
  • the argon plasma may satisfy the following conditions.
  • P Ar may be an argon plasma irradiation dose
  • T Ar may be a supply time of the argon plasma
  • a unit cycle sequentially including the first to third steps may be performed at least twice or more.
  • the cobalt containing thin film may be selectively deposited only on the conductive layer.
  • the conductive layer and the insulating layer on the substrate may be disposed on the same layer.
  • the conductive layer may include metal selected from the group consisting of gold (Au), silver (Ag), copper (Cu), tin (Sn), aluminum (Al), nickel (Ni), tungsten(W), chromium (Cr), zinc (Zn), platinum (Pt), molybdenum (Mo), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), manganese (Mn), ruthenium(Ru), iridium (Ir), rhenium (Re), and ruthenium(Ru).
  • the insulating layer may include silicon oxide, silicon nitride, or silicon oxynitride.
  • the capping layer which is deposited on the metal wiring at the high deposition rate and planarized without deforming the shape of the cavity or the shape of the metal wiring due to the high aspect ratio in the highly integrated semiconductor device.
  • the occurrence of the metal diffusion, the deformation and de-weighting of the metal crystalline structure or the like which are caused from the metal wiring in the semiconductor device including the metal wiring can be effectively suppressed by providing the high-density, high-purity cobalt containing thin film by remarkably improving the gap fill characteristics, thereby improving the reliability of the metal wiring.
  • the high-density, high-purity cobalt containing thin film as the capping layer can be selectively formed on the metal wiring of the highly integrated semiconductor device, thereby eliminating the need for the patterning process for the formation of the capping layer.
  • FIG. 1 is a diagram showing results of checking a gap fill characteristics of a cobalt containing thin film manufactured in Examples and Comparative Examples of the present invention, in which a cross section of the cobalt containing thin film was manufactured by focused ion beam (FIB) processing and the cross section is observed by SEM (125,000 times magnification).
  • FIB focused ion beam
  • FIG. 2 is a diagram showing results of checking gap fill characteristics of the cobalt containing thin film manufactured in Example 1 of the present invention, in which the cross section of the cobalt containing thin film is observed by TEM (49,000 times magnification).
  • FIG. 3 is a diagram showing the cross section of the cobalt containing thin film manufactured in Example 5 of the present invention which is observed by the TEM (29,500 times magnification).
  • FIG. 4 is a diagram showing the cross section of the cobalt containing thin film manufactured in Example 7 of the present invention which is observed by the SEM (125,000 times magnification).
  • FIG. 5 is a diagram showing the cross sections of the cobalt containing thin films manufactured in Examples 7 to 9 of the present invention which is observed by the TEM (29,500 times magnification).
  • FIG. 6 is a diagram showing the SEM observation (150,000 times magnification) of results of selection ratios of the cobalt containing thin films manufactured in Examples 6 and 11 of the present invention.
  • alkyl used in the present specification includes both linear and branched forms.
  • the alkyl according to the exemplary embodiment of the present invention may have 1 to 7 carbon atoms, specifically, 1 to 5 carbon atoms, more specifically, 1 to 3 carbon atoms.
  • a "first unit cycle” means a process unit of a first step.
  • second unit cycle used in the present specification means a process unit in which first to third steps are sequentially performed, in which the first unit cycle may be repeated once or more and then the second and third steps may be sequentially performed.
  • the second unit cycle also has the same meaning as the term “loop" usedin the present specification.
  • a barrier layer containing tantalum, tantalum nitride, tin, aluminum, an alloy of manganese and copper or the like is provided in a copper wiring, or an adhesion improving agent between copper and other materials is provided.
  • suchattempts are either costly or only partially effective.
  • the present inventors selected a cobalt precursor compound as a capping layer material for suppressing the occurrence of the copper diffusion, the deformation and de-weighting of the copper crystalline structure or the like which are caused from the copper wiring, and performed the study on the process conditions.
  • the present inventors devised a method of manufacturing a high-purity cobalt containing thin film capable of implementing remarkably improved step coverage without impurities by adjusting hydrogen plasma in a step of forming a deposition film during a plasma enhanced chemical vapor deposition process.
  • the cobalt precursor compound has a disadvantage in that it is thermally unstable or has a relatively high deposition temperature and carbon contamination is serious due to decomposition characteristics of ligand.
  • PECVD plasma enhanced chemical vapor deposition
  • impurities such as carbon exist in the thin film by 20 atom % or more. Therefore, a heat treatment process for removing the impurities should be necessarily involved.
  • a high-purity cobalt containing thin film may be provided without the heat treatment process for removing the impurities such as carbon.
  • the present invention provides a method of manufacturing a cobalt containing thin film for forming a planarized capping layer without deforming a shape of a cavity or a shape of a metal wiring dueto a high aspect ratio. That is, the method of manufacturing a cobalt containing thin film according to the exemplary embodiment of the present invention is excellent in the step coverage.
  • the method of manufacturing a cobalt containing thin film according to an exemplary embodiment of the present invention may be based on the plasma enhanced chemical vapor deposition process.
  • the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition includes a first step of adsorbing a cobalt precursor compound onto a substrate and then providing purgegas, and a second step of providing hydrogen plasma onto the substrate to form a deposition film, in which the hydrogen plasma satisfies the following conditions.
  • P H is a hydrogen plasma irradiation dose
  • T H is a supply time of hydrogen plasma
  • the hydrogen plasma power satisfies a range of 350 to 450 W.
  • the hydrogen plasma power is out of the range, it is not effective to remove impurities such as carbon in the thin film and it is difficult to implement a uniform thin film.
  • the hydrogen plasma may be provided in an irradiation dose of 0.5 W / cm 2 to 0.8 W / cm 2 , more specifically, an irradiation dose of 0.57 W / cm 2 to 0.73 W / cm 2 .
  • the hydrogen plasma may be irradiated at a power of 350 to 450 W.
  • the hydrogen plasma may be irradiated at a power of 380 to 430 W, more specifically, at a power of 390 to 420 W, and should satisfy the irradiation dose described above.
  • the hydrogen plasma may be applied from a high frequency power source, and may be based on a frequency range of RF power.
  • the hydrogen plasma may use a high frequency power source in a range of 10 to 50 MHz, specifically, in a range of 10 to 30 MHz, more specifically, in a range of 15 to 25 MHz.
  • the hydrogen plasma is provided in the above-described irradiation dose for 100 to 200 seconds (sec).
  • the hydrogen plasma irradiation dose is out of the range, the reduction action on the impurities such as carbon is not smoothed, and as a result, the purity of the cobalt containing thin film cannot be improved.
  • the planarized cobalt containing thin film is not preferable to be applied to the device having the high aspect ratio and does not smoothly react with the cobalt precursor compound adsorbed on the substrate,which is not preferable.
  • the hydrogen plasma may be provided at the power value described above for 100 to 180 seconds, and more specifically, at the power value described above for 110 to 150 seconds.
  • the cobalt precursor compound in the first step, may be adsorbed onto a substrate and then the purge gas may be provided.
  • the cobalt precursor compound may be provided onto the substrate by a bubblerscheme or vapor phase mass flow controller (MFC) scheme or may be provided onto a substrate by a liquid delivery system (LDS).
  • MFC vapor phase mass flow controller
  • LDS liquid delivery system
  • the liquid delivery system may include a direct liquid injection scheme of directly injecting the cobalt precursor compound.
  • the cobalt precursor compound may be provided by the bubblerscheme at a temperature of 60 °C or less, specifically, onto the substratefor 1 to 10 seconds through carrier gas.
  • the carrier gas may be inert gas.
  • Non-limiting examples of the carrier gas may include one or mixed gas of at least two selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon, radon (Rn) and the like.
  • the injection amount of the carrier gas is not limited. Specifically, the injection amount of the carrier gas may range from 10 sccm (50 sccm / L) to 500 sccm (2500 sccm / L), and more specifically, the injection amount of the carrier gas may range from 10 to 100 sccm.
  • the cobalt precursor compound may be thermally stable and highly adsorbed onto the substrate, the cobalt precursor compound may be at least one selected from the compounds represented by the following Chemical Formulae 1 and 2.
  • R 1 and R 2 are each independently hydrogen or (C1-C5) alkyl
  • R 3 and R 4 are each independently hydrogen, (C1-C7) alkyl, amino (-NH 2 ) or silyl (-SiH 3 );
  • o is an integer of 0 to 2;
  • p is an integer of 0 or 1, except the case when o and p are 0 at the same time]
  • the cobalt precursor compound may be at least one compound selected from the compounds in which the R 1 is hydrogen, the o is an integer of 2, the R 3 is hydrogen, the R 2 and R 4 each are independently hydrogen or (C1-C5) alkyl, and the p is an integer of 1.
  • the high-purity deposition film may be formed by the subsequent hydrogen plasma, and the improved step coverage may be implemented.
  • the cobalt precursor compound may be adsorbed onto the substrate ranging from 350 to 500 °C.
  • the cobalt precursor compound of the above Chemical Formula 1 may be adsorbed onto the substrate ranging from 250 to 350 °C, more specifically, adsorbed onto the substrate of 280 to 320 °C.
  • the cobalt precursor compound of the above Chemical Formula 2 may be adsorbed onto the substrate ranging from 350 to 500 °C, more specifically, adsorbed onto the substrate of 350 to 450 °C.
  • Non-limiting examples of the substrates may include a substrate including semiconductor materials such as Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs InP, and the like; a rigid substrate such as a silicon on insulator (SOI) substrate, a quartz substrate, or a glass substrate; a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES) and polyester, and the like, but the substrate is not limited there to.
  • the substrate may include both of a conductive layer and an insulating layer, and the cobalt containing thin film according to the exemplary embodiment of the present invention may be selectively deposited on the conductive layer of the substrate.
  • the cobalt precursor compound may be adsorbed onto the substrate and then the purge gas may be provided to remove, from the substrate, at least a portion of the rest other than the adsorbed portion onto the substrate.
  • the purge gas may be the same as or different from the purge gas, and may be one or mixed gas of at least two selected from the inert gas described above.
  • the injection amount of the purge gas is not limited. Specifically, the injection amount of the purge gas may range from 800 to 5,000 sccm, more specifically, 1,000 to 2,000 sccm.
  • the first step may be repeatedly performed until the desired film thickness according to the purpose is obtained.
  • the second step may be a step of providing the hydrogen plasma onto the substrate to form the deposition film.
  • the deposition film may be the cobalt containing thin film proposed in the present invention.
  • the step coverage of the high-purity cobalt containing thin film may be remarkably improved by appropriately adjusting the hydrogen plasma power and the supply time of the hydrogen plasma under the above conditions.
  • the hydrogen plasma according to the exemplary embodiment of the present invention is provided so as to satisfy the predetermined power value and the supply time, such that the high-purity cobalt containing thin film can be deposited at the high deposition rate by the plasma enhanced chemical vapor deposition using at least one compound selected from the compounds represented by the above Chemical Formulae 1 and 2 and the remarkably improved step coverage can be implemented.
  • the cobalt containing thin film can be selectively deposited on the conductive layer (e.g., metal wiring).
  • the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention is different from the existing direct plasma method.
  • the direct plasma method refers to a method performed by supplyingsource gas, reactive gas, and post-processing gas containing a cobalt precursor compound or the like into a processing space between the electrode and the substrate and applying electric power.
  • the film quality of the thin film formed on the side part of the step structure may be relatively lowered, such that it is difficult to implement the improved step coverage.
  • the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition is different from the direct plasma method in that it provides the hydrogen plasma after performing the step of adsorbing the cobalt precursor compound onto the substrate and then purging the cobalt precursor compound once or more, thereby forming the high-purity deposition film.
  • the remarkably improved step coverage can be implemented by controlling the conditions of the hydrogen plasma.
  • the step of adsorbing the cobalt precursor compound onto the substrate and purging the cobalt precursor compound is performed once or more and then the hydrogen plasma is provided to form the high-purity deposition film with uniform flatness, which may be applied to a spatial split method of implementing a deposition by sequentially moving a substrateinto chambers while these processes are performed continuously in the chambers while the chambers are spaced spatially as well as a time division method for implementing these processes.
  • the hydrogen plasma may be formed by injecting hydrogen gas and then applying RF power.
  • the hydrogen gas may be supplied at an injection amount in the range of 100 to 5,000 sccm, specifically, at an injection amount in the range of 1,000 to 3,000 sccm, more specifically, at the injection amount of 1,500 to 2,500 sccm, but the injection amount of the hydrogen gas is not limited thereto.
  • the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention may further include a third step of providing argon plasma onto the substrate on which the deposition film is formed to perform the gap fill.
  • the remarkable improved gap fill characteristics can be implemented by the argon plasma.
  • the exemplary embodiment of the present invention it is possible to effectively suppress the overhanging in the thin film by controlling the conditions of the hydrogen plasma upon the formation of the deposition film, and to provide the remarkably improved gap fill characteristics by additionally providing the argon plasma onto the substrateon which the deposition film is formed.
  • the argon plasma may satisfy the following conditions.
  • P Ar is an argon plasma irradiation dose
  • T Ar is a supply time of the argon plasma
  • the argon plasma can implement the remarkably improved gap fill characteristics when satisfying the above-described conditions, thereby providing the high-density, high-purity cobalt containing thin film as the capping layer. Accordingly, the reliability of the semiconductor device can be improved by employing the capping layer according to the exemplary embodiment of the present invention.
  • the argon plasma may be provided in an irradiation dose of 0.5 W / cm 2 to 0.8 W / cm 2 , more specifically, an irradiation dose of 0.57 W / cm 2 to 0.73 W / cm 2 .
  • the argon plasma may be irradiated at a power of 350 to 450 W.
  • the argon plasma may be irradiated at a power of 380 to 430 W, more specifically, at a power of 390 to 420 W, and should satisfy the irradiation dose described above.
  • the supply time of the argon plasma may be, specifically, 120 to 300 seconds, more specifically 200-300 seconds, but is not limited thereto.
  • the argon plasma may be formed by injecting argon gas and then applying RF power.
  • the argon gas may be supplied at an injection amount ranging from 10 to 5,000 sccm, but the injection amount of the argon gas is not limited thereto.
  • the argon gas may be provided at an injection amount ranging from 10 to 100 sccm.
  • the argon gas may be provided at an injection amount ranging from 1,000 to 3,000 sccm.
  • the second unit cycle sequentially including the first to third steps may be performed at least twice.
  • the carrier gas in the chamber may be continuously supplied.
  • the cobalt containing thin film according to the exemplary embodiment of the present invention may be selectively deposited only on the conductive layer on the substrate on which the conductive layer and the insulating layer are formed. That is, according to the exemplary embodiment of the present invention, the high-density, high-purity cobalt containing thin film can be selectively formed on the metal wiring as the capping layer.
  • the conductive layer may be a conductive layer including metal selected from the group consisting of gold (Au), silver (Ag), copper (Cu), tin (Sn), aluminum (Al), nickel (Ni), tungsten(W), chromium (Cr), zinc (Zn), platinum (Pt), molybdenum (Mo), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), manganese (Mn), ruthenium(Ru), iridium (Ir), rhenium (Re), ruthenium(Ru), and the like, and may be the above-described metals, alloys thereof, nitrides thereof, and the like.
  • the insulating layer may include silicon oxide, silicon nitride, silicon oxynitride, or the like, and an insulating metal oxide, an organic insulating material or the like may be one aspect of the insulating layer of the present invention.
  • the substrate may be formed with the conductive layer which is divided into two or more parts, and a part of the conductive layer may be formed with the insulating layer.
  • the substrate may have a structure in which the conductive layers are spaced apart from each other or patterned, and a part of the spaced or patterned structure may include the insulating layer.
  • the specific resistance of the cobalt containing thin film manufactured in the following Examples and Comparative Examples was measured using a 4-point probe measuring system.
  • the purityof the cobalt containing thin film manufactured in the following Examples and Comparative Examples and the content (atom %) of impurities such as carbon (C) and oxygen (O) in the thin film were measured by X-ray photoelectron spectroscopy (XPS) analysis.
  • the thicknesses of the cobalt containing thin film manufactured in the following Examples and Comparative Examples were measured by observing the cross section of the thin film using SEM or TEM.
  • the cobalt containing thin film was formed on a trench wafer having an aspect ratio of about 1: 1.
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) under the process conditions shown in Table 1 below.
  • the cobalt precursor compound (tricarbonyl allyl cobalt) was supplied in a vapor state and adsorbed onto the silicon substrate. At this time, the cobalt precursor compound was transported by 50 sccm of argon gas. After the adsorption, 1100 sccm of the argon gas was purged. This was repeatedly performed in the first unit cycle.
  • the hydrogen plasma was provided onto the substrate to form a deposition film.
  • the argon plasma was provided onto the deposition film to perform the gap fill process.
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (tricarbonyl allyl cobalt) under the process conditions shown in Table 1 below.
  • CVD plasma enhanced chemical vapor deposition
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) under the process conditions shown in Table 2 below.
  • the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) was supplied in a vapor state and adsorbed onto the silicon substrate. At this time, the cobalt precursor compound was transported by 50 sccm of argon gas. After the adsorption, 1100 sccm of the argon gas was purged. This was repeatedly performed with the first unit cycle.
  • the hydrogen plasma was provided onto the substrate to form a deposition film.
  • the argon plasma was applied onto the deposition film to perform the gap fill process.
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) under the process conditions shown in Table 2 below.
  • CVD plasma enhanced chemical vapor deposition
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (dicobalt hexacarbonyl tert-butylacetylene) under the same process conditions of the above Example 1.
  • CVD plasma enhanced chemical vapor deposition
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (tricarbonyl allyl cobalt) under the process conditions shown in Table 3 below.
  • CVD plasma enhanced chemical vapor deposition
  • the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) was supplied in a vapor state and adsorbed onto the silicon substrate. At this time, the cobalt precursor compound was transported by 100 sccm of argon gas, and 2000 sccm of hydrogen gas and a RF power of 50 W were applied for 30 seconds (process pressure: 1 torr).
  • the cobalt containing thin film manufactured in the above Comparative Example 1 was heat-treated in the hydrogen atmosphere in the chamber (see process conditions in Table 3 below).
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (tricarbonyl allyl cobalt) under the process conditions shown in Table 4 below.
  • CVD plasma enhanced chemical vapor deposition
  • the cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) under the process conditions shown in Table 4 below.
  • CVD plasma enhanced chemical vapor deposition
  • the present invention does not perform the additional heat treatment, the high specific resistance can be implemented, and at the same time, the content of the impurities is also low, suchthat the high-purity cobalt containing thin film can be provided.
  • the purecobalt containing thin film is formed without performing the additional heat treatment and the low specific resistance can be implemented.
  • FIGS. 1 to 6 showed the results of observing the step coverage and the gap fill characteristics of the cobalt containing thin film according to the exemplary embodiment of the present invention.
  • the thin film having a uniform thickness can be formed on the upper and side parts thereof even in the step structure having the high aspect ratio.
  • the further improved gap fill characteristics can be implemented when the argon plasma is provided.
  • the deposition film is uniformly formed on the upper and side parts of the cobalt containing thin film formed on the pattern substrate having an aspect ratio of about 1: 1 at a thickness of about 7 to 8 nm. That is, it was confirmed that in the case of the cobalt containing thin film according to the exemplary embodiment of the present invention, the excellent deposition film having the step coverage of 90% or more is formed.
  • the cobalt containing thin film according to the exemplary embodiment of the present invention has high selectivity at an excellent deposition rate on the conductive layer.

Landscapes

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

Abstract

The present invention relates to a method of manufacturing a cobalt containing thin film. According to the present invention, it is possible to provide a capping layer which is deposited on a metal wiring at a high deposition rate and planarized without deforming a shape of the cavity or a shape of the metal wiring due to a high aspect ratio in a highly integrated semiconductor device. Further, according to the present invention, it is possible to more improve the reliability of the metal wiring by providing a high-density, high-purity cobalt containing thin film by remarkably improving gap fill characteristics.

Description

METHOD OF MANUFACTURING A COBALT CONTAINING THIN FILM
The present invention relates to a method of manufacturing a cobalt containing thin film.
In order to more rapidly process a large amount of information in a rapidly developing information society, a highly integrated semiconductor device with a high data transmission speed is required. However, it is difficult to secure desired characteristics of a semiconductor device due to the high integration.
Conventionally, aluminum or an aluminum alloy was used as a metal wiring of a semiconductor device. However, as the width and thickness of the metal wiring are reduced due to the high integration of the semiconductor device, the increased resistance value reduces a signal transmission speed of the device, and a large current density is generated due to the reduced cross sectional area of the wiring, which more aggravates an electromigration phenomenon. In other words, the aluminum-based metal wiring has started to have limitations in terms of resistance, a deposition rate, stability, or the like. For this reason, a wiring technology using copper as metal which may have low resistance and excellent interfacial characteristics to replace the aluminum-based metal wiring is being developed rapidly.
The copper has high conductivity and thus may have a tolerance even if the amount of electrons flowing in a lead increases due to the increase in the speed of the semiconductor element. However, since the copper is more difficult to be etched than aluminum, there is a problem in that the copper wiring cannot be formed by a photolithography process unlike the aluminum-based metal wiring.
For this reason, as a method of forming a copper wiring, generally, a single damascene method of forming the desired predetermined copper wiring by previously forming a long extended trench corresponding to a circuit wiring on an insulating layer on which a copper wiring is to be located, buryingcopper in the trench, and then performing a chemical mechanical polishing (CMP) process to remove copper formed in locations other than the trench may be used. As one example of another method of forming a copper wiring, a dual damascene method of penetrating through an insulating layer to connect between a lower conductive layer and an upper conductive layer which are vertically separated from each other by the insulating layer, forming a via hole through which the lower conductive layer is exposed and a trench together, burying copper in these via hole and trench together, and then performing a CMP process to remove unnecessary copper may be used.
Describing the conventional methods of forming a copper wiring described above in detail, an interlayer insulating layer is formed on a semiconductor substrate on which predetermined lower patterns are formed and then a trench defining a metal wiring forming area including the via hole for the metal wiring is formed within the interlayer insulating layer. Next, in the state where a anti-diffusion layer is deposited on an inner wall of the via hole and the trench and the interlayer insulating layer and then a copper film is deposited to completely bury the trench and the via hole on the anti-diffusion layer, the copper film and the anti-diffusion layer are polished by the chemical mechanical polishing process to expose the interlayer insulating layer, thereby forming the copper wiring in the via hole and the trench. Then, a capping film is formed between the copper wiring and the interlayer insulating layer to prevent copper from being diffused in an upward direction of the copper wiring.
Conventionally, however, in order to form the capping film, the capping film is deposited and then the photoresist is applied thereon, the exposure and development phenomenon is performed on the photoresist to form an opening on a photoresist pattern and then an etching process needs to be performed using the opening as an etch mask, which is an increasing factor of process cost and tact time.
In view of the technical background, the present applicant has studied capping layer material and process conditions for suppressing the occurrence of metal diffusion, deformation and de-weighting of metal crystalline structure and the like caused from a metal wiring in a semiconductor device including the metal wiring to find that a method of manufacturing a high-density, high-purity cobalt containing thin film which can be deposited on the metal wiring at a high deposition rate and can implement remarkably improved step coverage and gap fill characteristics when satisfying the predetermined material and process conditions, thereby completing the present invention.
An object of the present invention is to provide a method of manufacturing a high-purity cobalt containing thin film for forming a cobalt capping layer on a metal wiring.
Another object of the present invention is to provide a method of manufacturing a high-density, high-purity cobalt containing thin film capable of implementing improved step coverage and gap fill characteristics.
Still another object of the present invention is to provide a method of manufacturing a cobalt containing thin film capable of selectively forming a cobalt capping layer on a metal wiring by being selectively deposited only on a conductive layer on a substrate on which the conductive layer and an insulating layer exist.
In one general aspect, a method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition includes: a first step of adsorbing a cobalt precursor compound onto a substrate and then providing purgegas; and a second step of providing hydrogen plasma onto the substrate to form a deposition film, wherein the hydrogen plasma satisfies the following conditions.
0.5W/cm2 ≤ PH　≤ 1.0W/cm2
100sec ≤ TH　≤ 200sec
[In the conditions,
PH is a hydrogen plasma irradiation dose, and
TH is a supply time of hydrogen plasma]
The cobalt precursor compound may be at least one selected from the following Chemical Formulae 1 and 2.
[Chemical Formula 1]
Figure PCTKR2018002428-appb-I000001
[Chemical Formula 2]
Figure PCTKR2018002428-appb-I000002
[In the above Chemical formulae 1 and 2,
R1 and R2 each may independently be hydrogen or (C1-C5) alkyl;
R3 and R4 each may independently be hydrogen, (C1-C7) alkyl, amino (-NH2) or silyl (-SiH3);
Figure PCTKR2018002428-appb-I000003
may be a single bond or a double bond;
o may be an integer of 0 to 2;
p may be an integer of 0 or 1, except the case when o and p are 0 at the same time]
In the above Chemical formulae 1 and 2,
the R1 may be hydrogen;
the o may be an integer of 2;
the R3 may be hydrogen;
the R2 and R4 each may independently be hydrogen or (C1-C5) alkyl; and
the p is an integer of 1.
In the first step, the cobalt precursor compound of the Chemical Formula 1 may be adsorbed onto the substrate ranging from 250 to 350 ℃ and then purge gas may be provided.
In the first step, the cobalt precursor compound of the Chemical Formula 2 may be adsorbed onto the substrate ranging from 350 to 500 ℃ and then the purge gas may be provided.
After the first step may be repeatedly performed until a required film thickness is obtained, the second step of providing the hydrogen plasma to form the deposition film may be performed. Specifically, in the second step, the hydrogen plasma may satisfy the above conditions.
The method may further include: a third step of performing gap fill by providing argon plasma onto the substrate on which the deposition film is formed.
The argon plasma may satisfy the following conditions.
0.5W/cm2 ≤ PAr　≤ 1.0W/cm2
100sec ≤ TAr　≤ 300sec
[In the conditions,
PAr may be an argon plasma irradiation dose, and
TAr may be a supply time of the argon plasma]
A unit cycle sequentially including the first to third steps may be performed at least twice or more.
On the substrate on which the conductive layer and the insulating layer are formed, the cobalt containing thin film may be selectively deposited only on the conductive layer.
The conductive layer and the insulating layer on the substrate may be disposed on the same layer.
The conductive layer may include metal selected from the group consisting of gold (Au), silver (Ag), copper (Cu), tin (Sn), aluminum (Al), nickel (Ni), tungsten(W), chromium (Cr), zinc (Zn), platinum (Pt), molybdenum (Mo), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), manganese (Mn), ruthenium(Ru), iridium (Ir), rhenium (Re), and ruthenium(Ru).
The insulating layer may include silicon oxide, silicon nitride, or silicon oxynitride.
According to the exemplary embodiment of the present invention, it is possible to provide the capping layer which is deposited on the metal wiring at the high deposition rate and planarized without deforming the shape of the cavity or the shape of the metal wiring due to the high aspect ratio in the highly integrated semiconductor device.
Further, according to the exemplary embodiment of the present invention, the occurrence of the metal diffusion, the deformation and de-weighting of the metal crystalline structure or the like which are caused from the metal wiring in the semiconductor device including the metal wiring can be effectively suppressed by providing the high-density, high-purity cobalt containing thin film by remarkably improving the gap fill characteristics, thereby improving the reliability of the metal wiring.
In addition, according to the exemplary embodiment of the present invention, the high-density, high-purity cobalt containing thin film as the capping layer can be selectively formed on the metal wiring of the highly integrated semiconductor device, thereby eliminating the need for the patterning process for the formation of the capping layer.
FIG. 1 is a diagram showing results of checking a gap fill characteristics of a cobalt containing thin film manufactured in Examples and Comparative Examples of the present invention, in which a cross section of the cobalt containing thin film was manufactured by focused ion beam (FIB) processing and the cross section is observed by SEM (125,000 times magnification).
FIG. 2 is a diagram showing results of checking gap fill characteristics of the cobalt containing thin film manufactured in Example 1 of the present invention, in which the cross section of the cobalt containing thin film is observed by TEM (49,000 times magnification).
FIG. 3 is a diagram showing the cross section of the cobalt containing thin film manufactured in Example 5 of the present invention which is observed by the TEM (29,500 times magnification).
FIG. 4 is a diagram showing the cross section of the cobalt containing thin film manufactured in Example 7 of the present invention which is observed by the SEM (125,000 times magnification).
FIG. 5 is a diagram showing the cross sections of the cobalt containing thin films manufactured in Examples 7 to 9 of the present invention which is observed by the TEM (29,500 times magnification).
FIG. 6 is a diagram showing the SEM observation (150,000 times magnification) of results of selection ratios of the cobalt containing thin films manufactured in Examples 6 and 11 of the present invention.
A method of manufacturing a cobalt containing thin film according to an exemplary embodiment of the present invention will be described below. In this case, technical terms and scientific terms used in the present specification have the general meaning understood by those skilled in the art to which the present invention pertains unless otherwise defined, and a description for the known function and configuration obscuring the present invention will be omitted in the following description.
The term "alkyl" used in the present specification includes both linear and branched forms. In addition, the alkyl according to the exemplary embodiment of the present invention may have 1 to 7 carbon atoms, specifically, 1 to 5 carbon atoms, more specifically, 1 to 3 carbon atoms.
Also, in the term used in the present specification, a "first unit cycle" means a process unit of a first step.
In addition, the term "second unit cycle" used in the present specification means a process unit in which first to third steps are sequentially performed, in which the first unit cycle may be repeated once or more and then the second and third steps may be sequentially performed. In addition, the second unit cycle also has the same meaning as the term "loop" usedin the present specification.
When copper is used in a metal wiring process, problems such as copper diffusion and deformation and de-weighting of a copper crystalline structure are caused, thereby increasing error possibility of the semiconductor device.
In order to solve this problem, conventionally, a barrier layer containing tantalum, tantalum nitride, tin, aluminum, an alloy of manganese and copper or the like is provided in a copper wiring, or an adhesion improving agent between copper and other materials is provided. However, suchattempts are either costly or only partially effective.
Accordingly, the present inventors selected a cobalt precursor compound as a capping layer material for suppressing the occurrence of the copper diffusion, the deformation and de-weighting of the copper crystalline structure or the like which are caused from the copper wiring, and performed the study on the process conditions. As a result, the present inventors devised a method of manufacturing a high-purity cobalt containing thin film capable of implementing remarkably improved step coverage without impurities by adjusting hydrogen plasma in a step of forming a deposition film during a plasma enhanced chemical vapor deposition process.
Generally, the cobalt precursor compound has a disadvantage in that it is thermally unstable or has a relatively high deposition temperature and carbon contamination is serious due to decomposition characteristics of ligand. In particular, when a plasma enhanced chemical vapor deposition (PECVD) process is used, impurities such as carbon exist in the thin film by 20 atom % or more. Therefore, a heat treatment process for removing the impurities should be necessarily involved.
However, according to the method of manufacturing a cobalt containing thin film using the plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, a high-purity cobalt containing thin film may be provided without the heat treatment process for removing the impurities such as carbon. In particular, according to the method of manufacturing a cobalt containing thin film using the plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, it is possible to provide the high-purity cobalt containing thin film capable of implementing the improved step coverage by adjusting the hydrogen plasma condition by employing the predetermined cobalt precursor compound.
As described above, the present invention provides a method of manufacturing a cobalt containing thin film for forming a planarized capping layer without deforming a shape of a cavity or a shape of a metal wiring dueto a high aspect ratio. That is, the method of manufacturing a cobalt containing thin film according to the exemplary embodiment of the present invention is excellent in the step coverage.
The method of manufacturing a cobalt containing thin film according to an exemplary embodiment of the present invention may be based on the plasma enhanced chemical vapor deposition process.
Specifically, the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition includes a first step of adsorbing a cobalt precursor compound onto a substrate and then providing purgegas, and a second step of providing hydrogen plasma onto the substrate to form a deposition film, in which the hydrogen plasma satisfies the following conditions.
0.5W/cm2 ≤ PH　≤ 1.0W/cm2
100sec ≤ TH　≤ 200sec
[In the conditions,
PH is a hydrogen plasma irradiation dose, and
TH is a supply time of hydrogen plasma]
According to the method of manufacturing a cobalt containing thin film according to an exemplary embodiment of the present invention, it is possible to remarkably improve the step coverage upon the deposition by appropriately adjusting the hydrogen plasma power and the supply time of the hydrogen plasma under the conditions in the step for forming the deposition film.
According to the method of manufacturing a cobalt containing thin film according to an exemplary embodiment of the present invention, the hydrogen plasma power satisfies a range of 350 to 450 W. When the hydrogen plasma power is out of the range, it is not effective to remove impurities such as carbon in the thin film and it is difficult to implement a uniform thin film. In particular, when the hydrogen plasma irradiation dose of less than 0.50 W / cm2 is provided, a reduction action on the impurities such as carbon in the thin film is not smoothed, and thus the purity of the cobalt containing thin film cannot be improved, and when the hydrogen plasma irradiation dose exceeding 1.0 W / cm2 is provided, an arching phenomenon occurs in the plasma, and thus impurities such as particles occur and it is difficult to implement the planarized cobalt containing thin film and the planarized cobalt containing thin film may not applied to the device having the high aspect ratio.
Specifically, the hydrogen plasma may be provided in an irradiation dose of 0.5 W / cm2 to 0.8 W / cm2, more specifically, an irradiation dose of 0.57 W / cm2 to 0.73 W / cm2.
For example, the hydrogen plasma may be irradiated at a power of 350 to 450 W. Specifically, the hydrogen plasma may be irradiated at a power of 380 to 430 W, more specifically, at a power of 390 to 420 W, and should satisfy the irradiation dose described above.
The hydrogen plasma may be applied from a high frequency power source, and may be based on a frequency range of RF power.
For example, the hydrogen plasma may use a high frequency power source in a range of 10 to 50 MHz, specifically, in a range of 10 to 30 MHz, more specifically, in a range of 15 to 25 MHz.
In addition, in the method of manufacturing a cobalt containing thin film according to the exemplary embodiment of the present invention, the hydrogen plasma is provided in the above-described irradiation dose for 100 to 200 seconds (sec). When the hydrogen plasma irradiation dose is out of the range, the reduction action on the impurities such as carbon is not smoothed, and as a result, the purity of the cobalt containing thin film cannot be improved. In addition, since it is difficult to implement the planarized cobalt containing thin film, the planarized cobalt containing thin film is not preferable to be applied to the device having the high aspect ratio and does not smoothly react with the cobalt precursor compound adsorbed on the substrate,which is not preferable.
Specifically, the hydrogen plasma may be provided at the power value described above for 100 to 180 seconds, and more specifically, at the power value described above for 110 to 150 seconds.
Hereinafter, a method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention will be described in detail.
In the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, in the first step, the cobalt precursor compound may be adsorbed onto a substrate and then the purge gas may be provided.
The cobalt precursor compound may be provided onto the substrate by a bubblerscheme or vapor phase mass flow controller (MFC) scheme or may be provided onto a substrate by a liquid delivery system (LDS). At this time, the liquid delivery system may include a direct liquid injection scheme of directly injecting the cobalt precursor compound.
As an example, the cobalt precursor compound may be provided by the bubblerscheme at a temperature of 60 ℃ or less, specifically, onto the substratefor 1 to 10 seconds through carrier gas.
The carrier gas may be inert gas. Non-limiting examples of the carrier gas may include one or mixed gas of at least two selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon, radon (Rn) and the like.
At this time, the injection amount of the carrier gas is not limited. Specifically, the injection amount of the carrier gas may range from 10 sccm (50 sccm / L) to 500 sccm (2500 sccm / L), and more specifically, the injection amount of the carrier gas may range from 10 to 100 sccm.
Since the cobalt precursor compound may be thermally stable and highly adsorbed onto the substrate, the cobalt precursor compound may be at least one selected from the compounds represented by the following Chemical Formulae 1 and 2.
[Chemical Formula 1]
Figure PCTKR2018002428-appb-I000004
[Chemical Formula 2]
Figure PCTKR2018002428-appb-I000005
[In the above Chemical formulae 1 and 2,
R1 and R2 are each independently hydrogen or (C1-C5) alkyl;
R3 and R4 are each independently hydrogen, (C1-C7) alkyl, amino (-NH2) or silyl (-SiH3);
Figure PCTKR2018002428-appb-I000006
is a single bond or a double bond;
o is an integer of 0 to 2;
p is an integer of 0 or 1, except the case when o and p are 0 at the same time]
Since the cobalt precursor compound implements the high adsorption onto the substrate and smoothly removes the ligand by the subsequent hydrogen plasma, the cobalt precursor compound may be at least one compound selected from the compounds in which the R1 is hydrogen, the o is an integer of 2, the R3 is hydrogen, the R2 and R4 each are independently hydrogen or (C1-C5) alkyl, and the p is an integer of 1.
In particular, when the cobalt precursor compound is used, the high-purity deposition film may be formed by the subsequent hydrogen plasma, and the improved step coverage may be implemented.
The cobalt precursor compound may be adsorbed onto the substrate ranging from 350 to 500 ℃.
For example, the cobalt precursor compound of the above Chemical Formula 1 may be adsorbed onto the substrate ranging from 250 to 350 ℃, more specifically, adsorbed onto the substrate of 280 to 320 ℃.
For example, the cobalt precursor compound of the above Chemical Formula 2 may be adsorbed onto the substrate ranging from 350 to 500 ℃, more specifically, adsorbed onto the substrate of 350 to 450 ℃.
Non-limiting examples of the substrates may include a substrate including semiconductor materials such as Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs InP, and the like; a rigid substrate such as a silicon on insulator (SOI) substrate, a quartz substrate, or a glass substrate; a flexible plastic substrate such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES) and polyester, and the like, but the substrate is not limited there to. In addition, the substrate may include both of a conductive layer and an insulating layer, and the cobalt containing thin film according to the exemplary embodiment of the present invention may be selectively deposited on the conductive layer of the substrate.
The cobalt precursor compound may be adsorbed onto the substrate and then the purge gas may be provided to remove, from the substrate, at least a portion of the rest other than the adsorbed portion onto the substrate. At this time, the purge gas may be the same as or different from the purge gas, and may be one or mixed gas of at least two selected from the inert gas described above.
The injection amount of the purge gas is not limited. Specifically, the injection amount of the purge gas may range from 800 to 5,000 sccm, more specifically, 1,000 to 2,000 sccm.
Further, in the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, the first step may be repeatedly performed until the desired film thickness according to the purpose is obtained.
In the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, the second step may be a step of providing the hydrogen plasma onto the substrate to form the deposition film. At this time, the deposition film may be the cobalt containing thin film proposed in the present invention.
In the step of forming the deposition film, the step coverage of the high-purity cobalt containing thin film may be remarkably improved by appropriately adjusting the hydrogen plasma power and the supply time of the hydrogen plasma under the above conditions.
As described above, the hydrogen plasma according to the exemplary embodiment of the present invention is provided so as to satisfy the predetermined power value and the supply time, such that the high-purity cobalt containing thin film can be deposited at the high deposition rate by the plasma enhanced chemical vapor deposition using at least one compound selected from the compounds represented by the above Chemical Formulae 1 and 2 and the remarkably improved step coverage can be implemented. In particular, the cobalt containing thin film can be selectively deposited on the conductive layer (e.g., metal wiring).
Also, the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention is different from the existing direct plasma method.
The direct plasma method refers to a method performed by supplyingsource gas, reactive gas, and post-processing gas containing a cobalt precursor compound or the like into a processing space between the electrode and the substrate and applying electric power. When the method is employed, the film quality of the thin film formed on the side part of the step structure may be relatively lowered, such that it is difficult to implement the improved step coverage.
The method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to an exemplary embodiment of the present invention is different from the direct plasma method in that it provides the hydrogen plasma after performing the step of adsorbing the cobalt precursor compound onto the substrate and then purging the cobalt precursor compound once or more, thereby forming the high-purity deposition film. At this time, according to the exemplary embodiment of the present invention, the remarkably improved step coverage can be implemented by controlling the conditions of the hydrogen plasma.
For example, the step of adsorbing the cobalt precursor compound onto the substrate and purging the cobalt precursor compound is performed once or more and then the hydrogen plasma is provided to form the high-purity deposition film with uniform flatness, which may be applied to a spatial split method of implementing a deposition by sequentially moving a substrateinto chambers while these processes are performed continuously in the chambers while the chambers are spaced spatially as well as a time division method for implementing these processes.
The hydrogen plasma may be formed by injecting hydrogen gas and then applying RF power.
The hydrogen gas may be supplied at an injection amount in the range of 100 to 5,000 sccm, specifically, at an injection amount in the range of 1,000 to 3,000 sccm, more specifically, at the injection amount of 1,500 to 2,500 sccm, but the injection amount of the hydrogen gas is not limited thereto.
The method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention may further include a third step of providing argon plasma onto the substrate on which the deposition film is formed to perform the gap fill. The remarkable improved gap fill characteristics can be implemented by the argon plasma.
In the case of the cobalt containing thin film formed by the plasma enhanced chemical vapor deposition which is the conventional method of manufacturing a cobalt containing thin film, seam or void occurs due to overhanging in the thin film, and thus the gap fill characteristics cannot be improved.
However, according to the exemplary embodiment of the present invention, it is possible to effectively suppress the overhanging in the thin film by controlling the conditions of the hydrogen plasma upon the formation of the deposition film, and to provide the remarkably improved gap fill characteristics by additionally providing the argon plasma onto the substrateon which the deposition film is formed.
The argon plasma may satisfy the following conditions.
0.5W/cm2 ≤ PAr　≤ 1.0W/cm2
100sec ≤ TAr　≤ 300sec
[In the conditions,
PAr is an argon plasma irradiation dose, and
TAr is a supply time of the argon plasma]
In the gap fill step, the argon plasma can implement the remarkably improved gap fill characteristics when satisfying the above-described conditions, thereby providing the high-density, high-purity cobalt containing thin film as the capping layer. Accordingly, the reliability of the semiconductor device can be improved by employing the capping layer according to the exemplary embodiment of the present invention.
Specifically, the argon plasma may be provided in an irradiation dose of 0.5 W / cm2 to 0.8 W / cm2, more specifically, an irradiation dose of 0.57 W / cm2 to 0.73 W / cm2.
For example, the argon plasma may be irradiated at a power of 350 to 450 W. Specifically, the argon plasma may be irradiated at a power of 380 to 430 W, more specifically, at a power of 390 to 420 W, and should satisfy the irradiation dose described above.
At this time, the supply time of the argon plasma may be, specifically, 120 to 300 seconds, more specifically 200-300 seconds, but is not limited thereto.
The argon plasma may be formed by injecting argon gas and then applying RF power.
The argon gas may be supplied at an injection amount ranging from 10 to 5,000 sccm, but the injection amount of the argon gas is not limited thereto.
For example, the argon gas may be provided at an injection amount ranging from 10 to 100 sccm.
For example, the argon gas may be provided at an injection amount ranging from 1,000 to 3,000 sccm.
In the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, the second unit cycle sequentially including the first to third steps may be performed at least twice.
Further, according to the method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition according to the exemplary embodiment of the present invention, in the whole of the deposition process, the carrier gas in the chamber may be continuously supplied.
On the other hand, the cobalt containing thin film according to the exemplary embodiment of the present invention may be selectively deposited only on the conductive layer on the substrate on which the conductive layer and the insulating layer are formed. That is, according to the exemplary embodiment of the present invention, the high-density, high-purity cobalt containing thin film can be selectively formed on the metal wiring as the capping layer.
The conductive layer may be a conductive layer including metal selected from the group consisting of gold (Au), silver (Ag), copper (Cu), tin (Sn), aluminum (Al), nickel (Ni), tungsten(W), chromium (Cr), zinc (Zn), platinum (Pt), molybdenum (Mo), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), manganese (Mn), ruthenium(Ru), iridium (Ir), rhenium (Re), ruthenium(Ru), and the like, and may be the above-described metals, alloys thereof, nitrides thereof, and the like.
The insulating layer may include silicon oxide, silicon nitride, silicon oxynitride, or the like, and an insulating metal oxide, an organic insulating material or the like may be one aspect of the insulating layer of the present invention.
For example, the substrate may be formed with the conductive layer which is divided into two or more parts, and a part of the conductive layer may be formed with the insulating layer. In addition, the substrate may have a structure in which the conductive layers are spaced apart from each other or patterned, and a part of the spaced or patterned structure may include the insulating layer. Thus, according to the exemplary embodiment of the present invention in which the cobalt containing thin film is selectively formed only on the conductive layer, the cobalt containing thin film can be formed only on the desired conductive layer without the patterning process for forming the capping layer.
Hereinafter, the present invention will be described more specifically based on Examples. Terms and words used in the present specification and claims are not to be construed as a general or dictionary meaning, but are to be construed as meaning and concepts meeting the technical ideas of the present disclosure based on a principle that the present inventors may appropriately define the concepts of terms in order to describe their disclosures in best mode.
Therefore, the configurations described in the exemplary embodiments and drawings of the present invention are merely most preferable exemplary embodiments but do not represent all of the technical spirit of the present invention. Thus, it is to be understood that the present invention has various equivalents and modifications that can be substituted at the time of filing this application.
(Evaluation on physical properties of thin film)
1. Specific resistance measurement
The specific resistance of the cobalt containing thin film manufactured in the following Examples and Comparative Examples was measured using a 4-point probe measuring system.
The results were shown in Table 5.
2. Measurement of thin film composition
The purityof the cobalt containing thin film manufactured in the following Examples and Comparative Examples and the content (atom %) of impurities such as carbon (C) and oxygen (O) in the thin film were measured by X-ray photoelectron spectroscopy (XPS) analysis.
The results were shown in Table 5.
3. Thickness measurement
The thicknesses of the cobalt containing thin film manufactured in the following Examples and Comparative Examples were measured by observing the cross section of the thin film using SEM or TEM.
4. Step coverage
In order to confirm the step coverage of the cobalt containing thin film manufactured in the following Examples and Comparative Examples, the cobalt containing thin film was formed on a trench wafer having an aspect ratio of about 1: 1.
The results are shown in FIGS. 1 to 6.
(Example 1)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) under the process conditions shown in Table 1 below.
Specifically, the cobalt precursor compound (tricarbonyl allyl cobalt) was supplied in a vapor state and adsorbed onto the silicon substrate. At this time, the cobalt precursor compound was transported by 50 sccm of argon gas. After the adsorption, 1100 sccm of the argon gas was purged. This was repeatedly performed in the first unit cycle.
The hydrogen plasma was provided onto the substrate to form a deposition film. Next, the argon plasma was provided onto the deposition film to perform the gap fill process.
All the above processes were repeated in one loop.
(Examples 2 to 6)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (tricarbonyl allyl cobalt) under the process conditions shown in Table 1 below.
Figure PCTKR2018002428-appb-T000001
(Example 7)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) under the process conditions shown in Table 2 below.
Specifically, the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) was supplied in a vapor state and adsorbed onto the silicon substrate. At this time, the cobalt precursor compound was transported by 50 sccm of argon gas. After the adsorption, 1100 sccm of the argon gas was purged. This was repeatedly performed with the first unit cycle.
The hydrogen plasma was provided onto the substrate to form a deposition film. Next, the argon plasma was applied onto the deposition film to perform the gap fill process.
All the above processes were repeated with one loop.
(Examples 8 to 11)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) under the process conditions shown in Table 2 below.
Figure PCTKR2018002428-appb-T000002
(Example 12)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (dicobalt hexacarbonyl tert-butylacetylene) under the same process conditions of the above Example 1.
(Comparative Example 1)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (tricarbonyl allyl cobalt) under the process conditions shown in Table 3 below.
Specifically, the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) was supplied in a vapor state and adsorbed onto the silicon substrate. At this time, the cobalt precursor compound was transported by 100 sccm of argon gas, and 2000 sccm of hydrogen gas and a RF power of 50 W were applied for 30 seconds (process pressure: 1 torr).
(Comparative Example 2)
The cobalt containing thin film manufactured in the above Comparative Example 1 was heat-treated in the hydrogen atmosphere in the chamber (see process conditions in Table 3 below).
Figure PCTKR2018002428-appb-T000003
(Comparative Examples 3 and 6)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (tricarbonyl allyl cobalt) under the process conditions shown in Table 4 below.
(Comparative Examples 7 and 8)
The cobalt containing thin film was manufactured by the plasma enhanced chemical vapor deposition (CVD) using the cobalt precursor compound (cyclopentadienyl(methylcyclopentadiene)cobalt) under the process conditions shown in Table 4 below.
Figure PCTKR2018002428-appb-T000004
Figure PCTKR2018002428-appb-T000005
According to the above Table 5, although the present invention does not perform the additional heat treatment, the high specific resistance can be implemented, and at the same time, the content of the impurities is also low, suchthat the high-purity cobalt containing thin film can be provided.
Specifically, as a result of thin film composition through XPS analysis, it was confirmed that the specific resistance of the cobalt containing thin film according to the exemplary embodiment of the present invention was in the range of 9.2 to 11.3 mΩcm. On the other hand, it was confirmed that the specific resistance of Comparative Example 1, which was carried out under the normal direct plasma processing conditions, was 105mΩcm. Further, since the above Comparative Example 1 does not perform the additional heat treatment process, it was confirmed that the cobalt containing thin film having a high content of impurities in which the carbon content is 30 atom % is formed.
According to the present invention, it has been confirmed that the purecobalt containing thin film is formed without performing the additional heat treatment and the low specific resistance can be implemented.
In addition, FIGS. 1 to 6 showed the results of observing the step coverage and the gap fill characteristics of the cobalt containing thin film according to the exemplary embodiment of the present invention.
Specifically, as shown in FIG. 1, it was confirmed that in the case of the cobalt containing thin film according to the exemplary embodiment of the present invention, the thin film having a uniform thickness can be formed on the upper and side parts thereof even in the step structure having the high aspect ratio. In addition, it can be confirmed that the further improved gap fill characteristics can be implemented when the argon plasma is provided.
Referring to FIG. 5, it was confirmed that the deposition film is uniformly formed on the upper and side parts of the cobalt containing thin film formed on the pattern substrate having an aspect ratio of about 1: 1 at a thickness of about 7 to 8 nm. That is, it was confirmed that in the case of the cobalt containing thin film according to the exemplary embodiment of the present invention, the excellent deposition film having the step coverage of 90% or more is formed.
Further, as shown in FIG. 6, as a result of the selection ratio at the copper substrate corresponding to the conductive layer and the silicon oxide film corresponding to the insulating layer, it was confirmed that it is deposited on the copper substrate, which is the conductive layer, at a thickness 10 times larger than the silicon oxide film. That is, the cobalt containing thin film according to the exemplary embodiment of the present invention has high selectivity at an excellent deposition rate on the conductive layer.
It will be obvious to those skilled in the art to which the present invention pertains that the present invention described above is not limited to the above-mentioned exemplary embodiments and the accompanying drawings, butmay be variously substituted, modified, and altered without departing from the scope and spirit of the present invention.

Claims (13)

  1. A method of manufacturing a cobalt containing thin film by plasma enhanced chemical vapor deposition, comprising:
    a first step of adsorbing a cobalt precursor compound onto a substrateand then providing purge gas; and
    a second step of providing hydrogen plasma onto the substrate to form a deposition film, wherein the hydrogen plasma satisfies the following conditions.
    0.5W/cm2 ≤ PH　≤ 1.0W/cm2
    100sec ≤ TH　≤ 200sec
    [In the conditions,
    PH is a hydrogen plasma irradiation dose, and
    TH is a supply time of hydrogen plasma]
  2. The method of claim 1, wherein the cobalt precursor compound is at least one selected from the following Chemical Formulae 1 and 2.
    [Chemical Formula 1]
    Figure PCTKR2018002428-appb-I000007
    [Chemical Formula 2]
    Figure PCTKR2018002428-appb-I000008
    [In the above Chemical formulae 1 and 2,
    R1 and R2 are each independently hydrogen or (C1-C5) alkyl;
    R3 and R4 are each independently hydrogen, (C1-C7) alkyl, amino (-NH2) or silyl (-SiH3);
    Figure PCTKR2018002428-appb-I000009
    is a single bond or a double bond;
    o is an integer of 0 to 2;
    p is an integer of 0 or 1, except the case when o and p are 0 at the same time]
  3. The method of claim 2, wherein in the above Chemical formulae 1 and 2,
    the R1 is hydrogen;
    the o is an integer of 2;
    the R3 is hydrogen;
    the R2 and R4 are each independently hydrogen or (C1-C5) alkyl; and
    the p is an integer of 1.
  4. The method of claim 2, wherein in the first step, the cobalt precursor compound of the Chemical Formula 1 is adsorbed onto the substrate ranging from 250 to 350 ℃ and then purge gas is provided.
  5. The method of claim 2, wherein in the first step, the cobalt precursor compound of the Chemical Formula 2 is adsorbed onto the substrate ranging from 350 to 500 ℃ and then purge gas is provided.
  6. The method of claim 1, wherein the first step is repeatedly performed until a required film thickness is obtained.
  7. The method of any one of claims 1 to 6, further comprising:
    a third step of performing gap fill by providing argon plasma onto the substrateon which the deposition film is formed.
  8. The method of claim 7, wherein the argon plasma satisfies the following conditions.
    0.5W/cm2 ≤ PAr　≤ 1.0W/cm2
    100sec ≤ TAr　≤ 300sec
    [In the conditions,
    PAr is an argon plasma irradiation dose, and
    TAr is a supply time of the argon plasma]
  9. The method of claim 7, wherein a unit cycle sequentially including the first to third steps is performed at least twice or more.
  10. The method of claim 1, wherein on the substrate on which a conductive layer and an insulating layer are formed, the cobalt containing thin film is selectively deposited only on the conductive layer.
  11. The method of claim 10, wherein the conductive layer and the insulating layer on the substrateare disposed on the same layer.
  12. The method of claim 10, wherein the conductive layer includes metal selected from the group consisting of gold (Au), silver (Ag), copper (Cu), tin (Sn), aluminum (Al), nickel (Ni), tungsten(W), chromium (Cr), zinc (Zn) platinum (Pt), molybdenum (Mo), tantalum (Ta), titanium (Ti), hafnium (Hf), zirconium (Zr), manganese (Mn), ruthenium(Ru), iridium (Ir), rhenium (Re), and ruthenium(Ru).
  13. The method of claim 10, wherein the insulating layer includes silicon oxide, silicon nitride, or silicon oxynitride.
PCT/KR2018/002428 2017-12-29 2018-02-28 Method of manufacturing a cobalt containing thin film WO2019132113A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2017-0184007 2017-12-29
KR1020170184007A KR20190081455A (en) 2017-12-29 2017-12-29 Method of manufacturing a cobalt-containing thin film

Publications (1)

Publication Number Publication Date
WO2019132113A1 true WO2019132113A1 (en) 2019-07-04

Family

ID=67067596

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/002428 WO2019132113A1 (en) 2017-12-29 2018-02-28 Method of manufacturing a cobalt containing thin film

Country Status (3)

Country Link
KR (1) KR20190081455A (en)
TW (1) TW201936984A (en)
WO (1) WO2019132113A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090029036A1 (en) * 2007-05-21 2009-01-29 Christian Dussarrat cobalt precursors for semiconductor applications
WO2011162255A1 (en) * 2010-06-22 2011-12-29 株式会社アルバック Process for production of barrier film, and process for production of metal wiring film
US20120214303A1 (en) * 2001-07-25 2012-08-23 Seshadri Ganguli Process for forming cobalt and cobalt silicide materials in tungsten contact applications
KR20150078776A (en) * 2013-12-31 2015-07-08 (주)디엔에프 method of manufacturing a cobalt-containing thin film and a cobalt-containing thin film manufactured thereby
KR20160122399A (en) * 2015-04-14 2016-10-24 (주)디엔에프 method of manufacturing a cobalt-containing thin film and a cobalt-containing thin film manufactured thereby

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120214303A1 (en) * 2001-07-25 2012-08-23 Seshadri Ganguli Process for forming cobalt and cobalt silicide materials in tungsten contact applications
US20090029036A1 (en) * 2007-05-21 2009-01-29 Christian Dussarrat cobalt precursors for semiconductor applications
WO2011162255A1 (en) * 2010-06-22 2011-12-29 株式会社アルバック Process for production of barrier film, and process for production of metal wiring film
KR20150078776A (en) * 2013-12-31 2015-07-08 (주)디엔에프 method of manufacturing a cobalt-containing thin film and a cobalt-containing thin film manufactured thereby
KR20160122399A (en) * 2015-04-14 2016-10-24 (주)디엔에프 method of manufacturing a cobalt-containing thin film and a cobalt-containing thin film manufactured thereby

Also Published As

Publication number Publication date
TW201936984A (en) 2019-09-16
KR20190081455A (en) 2019-07-09

Similar Documents

Publication Publication Date Title
WO2017188785A1 (en) Pressurization type method for manufacturing metal monoatomic layer, metal monoatomic layer structure, and pressurization type apparatus for manufacturing metal monoatomic layer
KR930011538B1 (en) Depositing method of wn film for metalization of semiconductor device
WO2021060864A1 (en) Thin film fabrication method
US4777150A (en) Process for the formation of a refractory metal silicide layer on a substrate for producing interconnection
WO2012176988A1 (en) Organometallic compound, preparing method of the same, and preparing method of thin film using the same
WO2019088722A1 (en) Method for producing ruthenium-containing thin film, and ruthenium-containing thin film produced thereby
US5281304A (en) Process for forming copper wiring
CA2004909A1 (en) Semiconductor integrated-circuit device metallization
WO2019132113A1 (en) Method of manufacturing a cobalt containing thin film
WO2023200154A1 (en) Ruthenium precursor composition, preparation method therefor, and formation method for ruthenium-containing film using same
US6492281B1 (en) Method of fabricating conductor structures with metal comb bridging avoidance
WO2023219400A1 (en) Method for forming electrode for semiconductor devices, and electrode for semiconductor devices
WO2023191360A1 (en) Step rate improver, method for forming thin film using same, and semiconductor substrate and semiconductor device manufactured therefrom
WO2023195655A1 (en) Thin film shielding agent, method for forming thin film using same, and semiconductor substrate and semiconductor device manufactured therefrom
WO2023153647A1 (en) Oxide film reaction surface control agent, method for forming oxide film by using same, and semiconductor substrate and semiconductor device manufactured therefrom
WO2023191361A1 (en) Thin film modification composition, method for forming thin film using same, and semiconductor substrate and semiconductor element, manufactured therefrom
WO2023177091A1 (en) Shielding compound, thin film forming method using same, and semiconductor substrate and semiconductor device manufactured therefrom
WO2024090846A1 (en) Vacuum-based thin film modifier, thin film modifying composition comprising same, thin film forming method using same, and semiconductor substrate and semiconductor device manufactured therefrom
WO2023195657A1 (en) Thin film modification composition, method for forming thin film by using same, semiconductor substrate manufactured thereby, and semiconductor device
WO2024112078A1 (en) Method and device for thin film process including activated proton assist plasma etching
WO2023167483A1 (en) Thin film modification composition, method for forming thin film using same, and semiconductor substrate and semiconductor element manufactured therefrom
WO2022177403A1 (en) Auxiliary precursor, thin film precursor composition, method for forming thin film, and semiconductor substrate manufactured thereby
WO2020138976A1 (en) Method for manufacturing semiconductor device
WO2023195654A1 (en) Thin film modification composition, method for forming thin film by using same, and semiconductor substrate and semiconductor element manufactured therefrom
WO2022255734A1 (en) Film forming material, film forming composition, film forming method using film forming material and film forming composition, and semiconductor device manufactured therefrom

Legal Events

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

Ref document number: 18893688

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18893688

Country of ref document: EP

Kind code of ref document: A1