WO2004095563A1 - Procede de modification de surface et appareil de modification de surface destine a un film isolant intercouche - Google Patents

Procede de modification de surface et appareil de modification de surface destine a un film isolant intercouche Download PDF

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Publication number
WO2004095563A1
WO2004095563A1 PCT/JP2004/005641 JP2004005641W WO2004095563A1 WO 2004095563 A1 WO2004095563 A1 WO 2004095563A1 JP 2004005641 W JP2004005641 W JP 2004005641W WO 2004095563 A1 WO2004095563 A1 WO 2004095563A1
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Prior art keywords
interlayer insulating
insulating film
modifying
oxygen
oxidizing
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PCT/JP2004/005641
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English (en)
Japanese (ja)
Inventor
Shingo Hishiya
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Tokyo Electron Limited
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Application filed by Tokyo Electron Limited filed Critical Tokyo Electron Limited
Priority to US10/554,086 priority Critical patent/US20070026642A1/en
Priority to KR1020057016680A priority patent/KR101048949B1/ko
Publication of WO2004095563A1 publication Critical patent/WO2004095563A1/fr

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    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • 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
    • C23C16/56—After-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • 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
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Definitions

  • the present invention relates to a method and a device for modifying the surface of an interlayer insulating film, and more particularly to a method and a device for modifying the surface of an interlayer insulating film having a low dielectric constant.
  • an interlayer insulating film having a low dielectric constant for example, a coating liquid made of a material having a low dielectric constant is spin-coated on a semiconductor wafer as a substrate, and a coating film (SOD (Spin On Dielectrics)) is formed. Film) and baking the coating film.
  • SOD Spin On Dielectrics
  • the CVD (Chemical Vapor Deposition) film required for building multilayer wiring called a hard mask
  • Adhesion with a film formed on the interlayer insulating film is required.
  • the contact area between the two films becomes smaller and the aspect ratio increases, so that good adhesion cannot be obtained with an interlayer insulating film that is simply baked on a coating film. This is because there are cases.
  • CMP Chemical Mechanical Polishing
  • the surface of the formed interlayer insulating film is modified, for example, by irradiating the surface of the formed interlayer insulating film with plasma, and the adhesion between the interlayer insulating film and the film formed thereon is improved.
  • the film characteristics of the interlayer insulating film may be deteriorated.
  • the dielectric constant of the interlayer insulating film increases or the surface of the interlayer insulating film becomes rough.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a method and apparatus for modifying the surface of an interlayer insulating film, which can prevent deterioration of film properties and improve adhesion. Aim.
  • Another object of the present invention is to provide a method and apparatus for modifying the surface of an interlayer insulating film that can improve the adhesion while maintaining the dielectric constant.
  • the present invention relates to a method for modifying the surface of an interlayer insulating film formed by baking a coating film formed by applying a coating solution on a substrate at a predetermined temperature, wherein the reaction chamber accommodating the substrate is provided with a predetermined pressure.
  • the adhesion can be improved while maintaining the dielectric constant of the interlayer insulating film. . Further, deterioration of the film characteristics of the interlayer insulating film is also prevented.
  • the oxidizing active gas is any one of ozone, water vapor, oxygen, and a mixed gas of hydrogen and oxygen.
  • the predetermined temperature is 250 ° C. to 600 ° C.
  • the oxidizing active gas is ozone.
  • the predetermined temperature is 250 ° C. to 600 ° C.
  • the oxidizing active gas is a mixed gas of hydrogen and oxygen.
  • the surface of the interlayer insulating film is modified so that the surface energy of the interlayer insulating film is at least 8 Om NZm. Is preferred.
  • the surface of the interlayer insulating film is modified so that the surface contact angle of water on the surface of the interlayer insulating film becomes smaller than 40 °. It is preferred that it is so.
  • the interlayer insulating film is a low dielectric constant interlayer insulating film.
  • the low dielectric constant interlayer insulating film is formed from a coating solution containing polysiloxane having an organic functional group. Can be done.
  • the present invention is a device for modifying the surface of an interlayer insulating film formed by baking a coating film formed by applying a coating liquid on a substrate at a predetermined temperature, wherein the reaction device for accommodating the substrate is provided. Chamber; heating means for heating the reaction chamber to a predetermined temperature; oxidizing gas supply means for supplying an oxidizing gas into the reaction chamber; and control means for controlling the heating means and the oxidizing gas supply means.
  • a surface reforming apparatus for an interlayer insulating film comprising: .
  • the adhesion can be improved while maintaining the dielectric constant of the interlayer insulating film. . Further, deterioration of the film characteristics of the interlayer insulating film is also prevented.
  • the oxidizing active gas is any one of ozone, water vapor, oxygen, and a mixed gas of hydrogen and oxygen.
  • the predetermined temperature is 250 ° C. to 600 ° C.
  • the oxidizing active gas is ozone.
  • the predetermined temperature is 250 ° C. ( ⁇ 600 ° C.)
  • the oxidizing active gas is a mixed gas of hydrogen and oxygen.
  • control unit controls the heating unit and the oxidizing gas supply unit so that the surface energy of the interlayer insulating film is at least 8 OmN / m.
  • control means may control the heating means and the oxidizing active gas supply means such that a surface contact angle of water on the surface of the interlayer insulating film becomes smaller than 40 °. preferable.
  • the interlayer insulating film is a low dielectric constant interlayer insulating film.
  • the low dielectric constant interlayer insulating film can be formed from a coating solution containing polysiloxane having an organic functional group.
  • FIG. 1 is a diagram showing a thin film forming apparatus according to one embodiment of the present invention.
  • Figure 2A shows the relationship between the contact angle of pure water and the surface energy of the interlayer insulating film. It is rough.
  • FIG. 2B is a graph showing the relationship between the contact angle of pure water and the energy of the polar component in the surface energy of the interlayer insulating film.
  • FIG. 3A is a table showing conditions for surface modification of an interlayer insulating film by ozone.
  • FIG. 3B is a graph showing the contact angle of the surface-modified interlayer insulating film with pure water according to the table of FIG. 3A.
  • FIG. 4A is a table showing conditions for modifying the surface of the interlayer insulating film with water vapor.
  • FIG. 4B is a graph showing the contact angle of the surface-modified interlayer insulating film with pure water according to the table of FIG. 4A.
  • FIG. 5A is a table showing conditions for surface modification of an interlayer insulating film by hydrogen and oxygen.
  • FIG. 5B is a graph showing the contact angle of the surface-modified interlayer insulating film with pure water according to the table of FIG. 5A.
  • FIG. 6A is a table showing conditions for surface modification of an interlayer insulating film by oxygen.
  • FIG. 6B shows the contact angle of the surface-modified interlayer insulating film with pure water according to the table of FIG. 6A.
  • FIG. 7A is a table showing conditions for surface modification of an interlayer insulating film by ultraviolet rays.
  • FIG. 7B shows the contact angle of the surface-modified interlayer insulating film with pure water according to the table of FIG. 7A.
  • FIG. 8 is a graph showing the measurement results of the dielectric constant of an interlayer insulating film surface-modified according to the present invention and an interlayer insulating film not surface-modified.
  • FIG. 9 is a diagram showing a heat treatment apparatus for modifying the surface of an interlayer insulating film by irradiation with ultraviolet rays.
  • FIG. 1 shows a heat treatment apparatus for modifying the surface of an interlayer insulating film with an oxidizing active gas.
  • the heat treatment apparatus 1 includes a substantially cylindrical reaction tube 2 whose longitudinal direction is directed vertically.
  • the reaction tube 2 includes the inner tube 3 and the inner tube 3 while covering the inner tube 3.
  • an outer pipe 4 having a ceiling formed to have a certain interval.
  • the inner tube 3 and the outer tube 4 are made of a heat-resistant material, for example, quartz o
  • a manifold 5 made of stainless steel (SUS) formed in a cylindrical shape is arranged below the outer tube 4.
  • the manifold 5 is air-tightly connected to the lower end of the outer tube 4.
  • the inner pipe 3 is supported by a support ring 6 formed so as to protrude from the inner wall of the manifold 5.
  • a lid 7 is disposed below the manifold 5.
  • the lid 7 is configured to be able to move up and down by the boat elevator 8. When the lid 7 is raised by the boat elevator 8, the lower side of the manifold 5 is closed.
  • a wafer boat 9 made of, for example, quartz is placed on the lid 7.
  • the wafer boat 9 is provided with a semiconductor wafer 10 (substrate) on which a low dielectric constant insulating film such as an insulating film made of, for example, polysiloxane having an organic functional group is formed as an interlayer insulating film.
  • a low dielectric constant insulating film such as an insulating film made of, for example, polysiloxane having an organic functional group
  • a plurality of sheets can be stored at intervals.
  • the interlayer color film is formed, for example, by spin-coating a coating solution containing polysiloxane having an organic functional group to form a coating film on the semiconductor wafer 10 and firing the coating film to form a semiconductor. It is formed on the wafer 10.
  • a heat insulator 11 is provided around the reaction tube 2 so as to surround the reaction tube 2.
  • a heating heater 12 made of a resistance heating element is provided on the inner wall surface of the heat insulator 11.
  • the inside of the reaction tube 2 is heated to a predetermined temperature by the heater 12 for heating, and as a result, the semiconductor wafer 10 is heated to the predetermined temperature.
  • An oxidizing gas introduction pipe 13 for introducing an oxidizing gas is passed through a side surface of the manifold 5.
  • only one oxidation active gas introduction pipe 13 is drawn.
  • the oxidation active gas introduction pipe 13 is inserted below the support ring 6 so as to face the inside of the inner pipe 3.
  • the oxidizing gas introduction pipe 13 is connected to a predetermined oxidizing gas supply source (not shown) via a mask opening controller (not shown) or the like.
  • the oxidizing gas include ozone, water vapor, oxygen, and a mixed gas of hydrogen and oxygen.
  • the oxidation active gas is a mixed gas of hydrogen and oxygen
  • the mixed gas of hydrogen and oxygen is a common gas. It is supplied from the oxidation active gas introduction pipe 13.
  • hydrogen and oxygen may be separately supplied from separate oxidation active gas introduction tubes 13 and mixed in the reaction tube 2.
  • the oxidizing gas introduction pipe 13 is not provided.
  • a plurality of ultraviolet lamps are provided on the inner wall of the heat insulator 11.
  • Ultraviolet irradiation device is provided.
  • the interlayer insulating film of the semiconductor wafer 10 is irradiated with the ultraviolet light from the ultraviolet lamp.
  • a discharge port 14 is provided on the side of the manifold 5.
  • the discharge port 14 is provided above the support ring 6 and communicates with a space formed between the inner tube 3 and the outer tube 4 in the reaction tube 2. Then, exhaust gas and the like generated in the inner pipe 3 pass through the space between the inner pipe 3 and the outer pipe 4 and are exhausted to the exhaust port 14.
  • a purge gas supply pipe 15 for supplying nitrogen gas as a purge gas is inserted below the exhaust port 14 on the side surface of the manifold 5.
  • An exhaust pipe 16 is hermetically connected to the outlet 14.
  • a valve 17 and a vacuum pump 18 are interposed in the exhaust pipe 16 from the upstream side.
  • the valve 1 # controls the pressure in the reaction tube 2 to a predetermined pressure by adjusting the opening of the exhaust pipe 16.
  • the vacuum pump 18 exhausts the gas in the reaction tube 2 via the exhaust tube 16 and adjusts the pressure in the reaction tube 2.
  • the exhaust pipe 16 is provided with a trap, a scrubber and the like (not shown), and the exhaust gas exhausted from the reaction pipe 2 is detoxified and then exhausted outside the heat treatment apparatus 1. ing.
  • a control unit 19 is connected to the boat elevator 8, the heating heater 12, the oxidation active gas introduction pipe 13, the source gas supply pipe 15, the valve 17, and the vacuum pump 18. ing.
  • the control unit 19 is composed of a microprocessor, a process controller, etc., measures the temperature, pressure, etc. of each part of the heat treatment apparatus 1, outputs a control signal or the like to each of the above parts based on the measured data, and Each part of 1 is controlled according to a prescribed recipe (time sequence).
  • the semiconductor wafer 10 on which the interlayer insulating film is formed is housed, while the inside of the reaction tube 2 is heated to a predetermined temperature and the oxidizing gas is supplied into the reaction tube 2. Yes (or By irradiating the interlayer insulating film of the semiconductor wafer 10 with ultraviolet rays, the surface of the interlayer insulating film is modified.
  • a method of modifying the surface of the interlayer insulating film using the heat treatment apparatus 1 configured as described above will be described. In the following description, the operation of each unit constituting the heat treatment apparatus 1 is controlled by the control unit 19.
  • the inside of the reaction tube 2 is heated to a predetermined temperature by the heating heater 12.
  • the preferable range of the temperature depends on the type of the oxidizing gas used, as described later.
  • the inside of the reaction tube 2 is heated to an optimum temperature according to the type of the oxidizing active gas used.
  • a wafer boat 9 containing the semiconductor wafer 10 on which the interlayer insulating film has been formed is placed on the lid 7. Then, the lid 7 is raised by the boat elevator 8. Thereby, the semiconductor wafer 10 is accommodated in the reaction chamber.
  • the coating film is baked in the heat treatment apparatus 1 (when the calcination of the coating film and the surface modification are continuously performed in one heat treatment apparatus 1), the loading step is unnecessary.
  • the interlayer insulating film is formed, for example, by spin-coating a coating solution containing polysiloxane having an organic functional group to form a coating film on the semiconductor wafer 10 and baking the coating film. Formed as 0.
  • the coating solution containing a polysiloxane having an organic functional group is, for example, a solution in which a polysiloxane having an organic functional group is dissolved in an organic solvent.
  • Optional components such as a surfactant can be added to this solution.
  • As an interlayer insulating film formed in this way there is porous-methylsilsesquioxane (Porous-Methyl Silsesquioxane). For example, pores having a molecular or atomic size of 20 nm or less are formed in the interlayer insulating film.
  • the inside of the reaction tube 2 is maintained at a predetermined pressure according to the type of the oxidizing active gas used. Then, a predetermined amount of an oxidizing gas is supplied into the inner tube 3 from the oxidizing gas introducing pipe 13.
  • the oxidizing gas is supplied into the inner tube 3
  • the polar component energy in the surface energy of the interlayer insulating film increases.
  • the surface energy of the interlayer insulating film increases.
  • the reason why the polar component energy in the surface energy of the interlayer insulating film is increased is that a part of (S i — CH 3 ) of the porous MSQ that constitutes the interlayer insulating film is (S i — CH 3 ) by the oxidizing active gas.
  • ultraviolet light is applied to the interlayer insulating film of the semiconductor wafer 10 from an ultraviolet lamp (not shown) provided inside the heat treatment apparatus 1. You. This increases the surface energy of the interlayer insulating film.
  • the vacuum pump 18 is driven while controlling the opening of the valve 17, and the gas in the reaction tube 2 is exhausted to the exhaust tube 16. Further, the pressure in the reaction tube 2 is returned to normal pressure, and the semiconductor wafer 10 is unloaded by lowering the lid 7 by the boat elevator 8.
  • the semiconductor wafer 10 on which the interlayer insulating film made of porous MSQ was formed was heated to a predetermined temperature by the heat treatment apparatus 1 (reaction tube 2).
  • the heat treatment apparatus 1 (reaction tube 2).
  • ozone, water vapor, oxygen, or hydrogen and oxygen as an oxidizing active gas were supplied to modify the surface of the interlayer insulating film.
  • the same semiconductor wafer 10 was irradiated with ultraviolet rays to modify the surface of the interlayer insulating film. And the measurement about the adhesiveness and surface energy of each interlayer insulating film was performed.
  • the surface energy of the interlayer insulating film after the modification treatment was measured using a contact angle method.
  • the contact angle method is a method in which a liquid is dropped on an interlayer insulating film and the contact angle between a ball (drop) of the liquid and the surface of the interlayer insulating film is measured.
  • Figure 2A shows the relationship between the contact angle of pure water and the surface energy of the interlayer insulating film.
  • FIG. 2B shows the relationship between the contact angle of pure water and the polar component energy in the surface energy of the interlayer insulating film.
  • the surface energy of the interlayer insulating film was calculated by referring to the solid surface free energy (surface energy) calculation method by the Owens-Wendt method.
  • the contact angle of each liquid is measured using liquids with different surface tensions
  • the dispersion component, the polar component, and the hydrogen bond component are calculated from the Dupre-Young equation
  • the extended Fowkes equation is calculated.
  • the surface energy (surface tension) is derived from the dispersion component, the polar component, and the hydrogen bond component. This time, pure water and ethylene glycol were used as liquids with different surface tensions. Recall and jode methane were used.
  • the correlation between the contact angle of pure water and the surface energy of the interlayer insulating film As shown in FIG. 2A, as for the correlation between the contact angle of pure water and the surface energy of the interlayer insulating film, as the surface energy increases, the contact angle of pure water decreases. As shown in Fig. 2B, the correlation between the contact angle due to pure water and the energy of the polar component in the surface energy of the interlayer insulating film-the greater the polar component energy, the smaller the contact angle due to pure water. . The correlation in FIG. 2B leads to the correlation in FIG. 2A. In addition, a hard mask was formed on the interlayer insulating film, and a CMP (Chemical Mechanical Polishing) test was performed. The surface energy of the interlayer insulating film, which would prevent film peeling, was determined.
  • CMP Chemical Mechanical Polishing
  • the surface energy was preferably 80 mNZm or more, and more preferably 10 OmNZm or more. Therefore, in order to improve the adhesion performance of the interlayer insulating film, that is, the adhesiveness with a film formed thereon, for example, a hard mask, it is necessary to modify the contact angle with pure water to be 40 ° or less. It is more preferable to carry out the modification so as to be 20 ° or less.
  • the following describes the surface modification of the interlayer insulating film with ozone, the surface modification of the interlayer insulating film with water vapor, the surface modification of the interlayer insulating film with hydrogen and oxygen, the surface modification of the interlayer insulating film with oxygen, and the surface modification with ultraviolet light. It will be described in order.
  • the ozone supply time of 1 minute from the oxidation activity gas introduction pipe 13 the pressure is 133 Pa in the reaction tube 2 (l T orr), the amount of ozone is a 25 g / Nm 3, in the reaction tube 2 Temperatures of 200 ° C (Comparative Example 2), 250 ° C (Example 1), and 300 ° C
  • FIG. 3A shows conditions for surface modification of the interlayer insulating film by ozone.
  • FIG. 3B shows the contact angle of the surface-modified interlayer insulating film with pure water.
  • a hard mask was formed on each interlayer insulating film after the surface modification, and a CMP test was performed.
  • the results are shown in FIG. 3A (“ ⁇ ” when film peeling does not occur and has adhesiveness, and “x” when film peeling occurs and there is no adhesiveness) in FIG. 3A.
  • the contact angle of the interlayer insulating film with pure water was measured and a CMP test was performed. And in Figure 3B.
  • the contact angle of the interlayer insulating film with pure water is 40 ° or less
  • the results of the CMP test were also good.
  • the temperature in the reaction tube 2 was 300 ° C. (Example 2)
  • the contact angle of the interlayer insulating film with pure water was reduced to 20 ° or less, and the result of the CMP test was good. For this reason, it was confirmed that the adhesion property of the interlayer insulating film was improved by the surface modification of the interlayer insulating film with ozone, and the adhesiveness with the hard mask was improved.
  • the ozone concentration is set to 25 gZNm 3 or more, or the treatment time is set to 1 minute or more. It is considered that it is possible to obtain sufficient surface modification (improve surface energy).
  • the temperature in the reaction tube 2 is preferably 600 ° C. or lower, more preferably 400 ° C. or lower.
  • the Phoenix degree in the reaction tube 2 in the surface modification of the interlayer insulating film with ozone is also preferably 60 CTC or less, more preferably 200 ° C. to 400 ° C.
  • the pressure in the reaction tube 2 during the surface modification treatment of the interlayer insulating film with ozone is preferably 0.3 Pa (0.003 To rr) to: LO lkPa (normal pressure). , 0.3 Pa (0.003 Torr) to 6.65 kPa (50 Torr).
  • LO lkPa normal pressure
  • 0.3 Pa 0.003 Torr
  • 6.65 kPa 50 Torr
  • the minimum pressure of the heat treatment apparatus 1 is 0.3 Pa, while ozone tends to be deactivated on the high pressure side. This tendency becomes more pronounced at higher processing temperatures.
  • the temperature inside the reaction tube 2 is 300 ° C
  • it is preferably at most 6.65 kPa (50 Torr).
  • the ozone supply time during the surface modification treatment of the interlayer insulating film with ozone is preferably 60 minutes or less, more preferably 30 minutes or less, and most preferably 10 minutes or less.
  • the general baking time of the film in the device generation using the porous MSQ is 30 minutes to 60 minutes, taking into account the actual productivity.
  • O Zon amount of surface modification of the interlayer insulating film by ozone is preferably 2 0 0 g / N m 3 or less, and more preferably l OO gZN m 3 or less.
  • the pressure in the reaction tube 2 is set to normal pressure
  • the temperature in the reaction tube 2 is set to 500 ° C.
  • the steam supply time from the oxidation active gas introduction tube 13 is set to 30 minutes.
  • Example 3 and the case where the temperature in the reaction tube 2 was set at 400 ° C. and the steam supply time from the oxidation active gas introduction tube .13 was set to 15 minutes
  • FIG. 4A shows the conditions for modifying the surface of the interlayer insulating film with water vapor.
  • FIG. 4B shows the contact angle of the surface-modified interlayer insulating film with pure water.
  • the pressure in the reaction tube 2 is set to 13 3 Pa (1 Torr)
  • the supply time of hydrogen and oxygen from the oxidizing active gas introduction pipe 13, and the ratio of hydrogen (hydrogen mixture ratio) were changed as shown in FIG. 5A (Examples 4 to 10)
  • the surface of the interlayer insulating film was modified with hydrogen and oxygen.
  • the contact angle of each interlayer insulating film with pure water was measured.
  • oxygen and hydrogen were separately supplied into the reaction tube 2 through separate oxidation active gas introduction tubes 13 and mixed in the reaction tube 2.
  • FIG. 5A shows the conditions for the surface modification of the interlayer insulating film by hydrogen and oxygen.
  • the temperature in the reaction tube 2 is 360 ° C. to 400 ° C.
  • the supply time of hydrogen and oxygen from the oxidation active gas introduction tube 13 is 1 minute to 10 minutes
  • the contact angle of the interlayer insulating film with pure water became sufficiently small. Therefore, it is considered that the surface modification of the interlayer insulating film with hydrogen and oxygen improves the adhesion performance of the interlayer insulating film and improves the adhesion with the hard mask.
  • the same surface modification was performed when the temperature in the reaction tube 2 was set to 250 ° C. Also in this case, the contact angle of the interlayer insulating film with pure water was sufficiently small. For this reason, the temperature in the reaction tube 2 in the surface modification of the interlayer insulating film with hydrogen and oxygen is preferably 600 ° C. or less, more preferably 250 ° C. to 400 ° C.
  • the pressure in the reaction tube 2 during the surface modification treatment of the interlayer insulating film with hydrogen and oxygen is preferably ⁇ 0.3 Pa (0.003 Torr) to: LO lkPa (normal pressure).
  • the pressure is more preferably 0.3 Pa (0.003 Torr) to 0.3 kPa (3 Torr). This is because the minimum pressure of the heat treatment apparatus 1 is about 0.3 Pa, while the oxidizing power of hydrogen and oxygen becomes weak at a high pressure of 0.3 kPa or more.
  • the gas supply time during the surface modification treatment of the interlayer insulating film with hydrogen and oxygen is preferably 60 minutes or less, more preferably 30 minutes or less, and most preferably 10 minutes or less.
  • the typical baking time for the film in the device generation using the porous MSQ is 30 minutes to 60 minutes, considering the actual productivity.
  • the mixing ratio of hydrogen is preferably 0.001% to 99%, and more preferably 5% to 66%. For adding trace amounts of hydrogen This is because radicals are generated during the treatment, and the radicals enable the surface modification treatment.
  • the pressure in the reaction tube 2 was set to normal pressure
  • the oxygen supply time from the oxidizing active gas introduction tube 13 was set to 30 minutes
  • the temperature in the reaction tube 2 was set to 300 ° C (Comparative Example 4).
  • C. Comparative Example 5
  • 500.degree. C. Example 11
  • 600.degree. C. Example 12
  • the surface of the interlayer insulating film was modified with oxygen.
  • the contact angle of each interlayer insulating film with pure water was measured.
  • FIG. 6A shows the conditions for modifying the surface of the interlayer insulating film with oxygen.
  • FIG. 6B shows the contact angle of the surface-modified interlayer insulating film with pure water.
  • the irradiation time of the ultraviolet light on the interlayer insulating film is set to 10 seconds (Example 13) and 30 seconds (Example 14) at room temperature (about 25 ° C.) in an air atmosphere.
  • Surface modification of the interlayer insulating film was performed.
  • the contact angle of each interlayer insulating film with pure water was measured.
  • FIG. 7A shows the conditions for surface modification of the interlayer insulating film by ultraviolet rays.
  • FIG. 7B shows the contact angle of the surface-modified interlayer insulating film with pure water. As shown in FIGS.
  • the ultraviolet irradiation time is 10 seconds or more (Examples 13 and 14)
  • the contact angle of the interlayer insulating film with pure water became 40 ° or less.
  • the contact angle of the interlayer insulating film with pure water was reduced to 20 ° or less. Therefore, the surface of the interlayer insulating film due to ultraviolet rays It is thought that the modification improves the adhesion performance of the interlayer insulating film and improves the adhesion with the hard mask.
  • the ultraviolet irradiation time is preferably at least 10 seconds, more preferably at least 30 seconds.
  • the treatment atmosphere in the surface modification treatment of the interlayer insulating film with ultraviolet rays is preferably air or an atmosphere containing oxygen. This is because in such a processing atmosphere, oxygen radicals or ozone can be generated by ultraviolet irradiation.
  • the temperature in the reaction tube 2 when the surface of the interlayer insulating film is modified by ultraviolet rays is preferably 60 CTC or less, more preferably 400 C or less.
  • the pressure in the reaction tube 2 in the surface modification of the interlayer insulating film by ultraviolet rays should be 0.3 Pa (0.003 Torr) to: L 0 1 kPa (normal pressure). Is preferred.
  • FIG. 8 shows the measurement results of the dielectric constant of the interlayer insulating film of which the surface was modified in Example 1 and the interlayer insulating film of Comparative Example 1 in which the surface was not modified.
  • the dielectric constant of the interlayer insulating film hardly changes. Therefore, it was confirmed that the surface modification of the interlayer insulating film according to the present invention can improve the adhesion while maintaining the dielectric constant of the interlayer insulating film.
  • the surface modification of the present invention can prevent the deterioration of the film characteristics and improve the adhesion.
  • Adhesion can be improved while maintaining the dielectric constant of the interlayer insulating film. Further, the adhesion can be improved while preventing the deterioration of the film characteristics.
  • an interlayer insulating film formed by spin-coating a coating solution containing polysiloxane having an organic functional group to form a coating film on a semiconductor wafer 10 and baking the coating film is used.
  • a membrane has been described.
  • the book The present invention is not limited to this, but can be applied to various interlayer insulating films.
  • the film formed on the upper surface is liable to peel off, and therefore the present invention is particularly effective for a low-dielectric-constant interlayer insulating film.
  • the low dielectric constant interlayer insulating film is not limited to the porous-MSQ, but includes other various low dielectric constant interlayer insulating films.
  • the coating liquid containing the polysiloxane having an organic functional group is spin-coated to form a coating film on the semiconductor wafer 10, and the interlayer formed by firing the coating film is formed.
  • An insulating film has been described.
  • the batch vertical heat treatment apparatus 1 having a double-tube structure in which the reaction tube 2 is composed of the inner tube 3 and the outer tube 4 has been described, but the present invention is not limited to this. Not something.
  • the present invention can be applied to a batch heat treatment apparatus having a single pipe structure without the inner pipe 3.
  • the surface reforming apparatus of the present invention is not limited to a batch-type heat treatment apparatus, and may be, for example, a single-wafer heat treatment apparatus as shown in FIG.
  • FIG. 9 shows a heat treatment apparatus 51 for modifying the surface of an interlayer insulating film by ultraviolet irradiation.
  • a semiconductor wafer 53 on which an interlayer insulating film ′ is formed is placed on a placement section 52 in the heat treatment apparatus 51.
  • the semiconductor wafer 53 is maintained at a predetermined temperature by the heater 54 disposed in the receiver 52.
  • An ultraviolet irradiation unit 55 including a plurality of ultraviolet lamps is provided at an upper part of the heat treatment apparatus 51, and the semiconductor wafer 53 is irradiated with ultraviolet light from the ultraviolet irradiation unit 55.
  • the surface of the interlayer insulating film formed on the semiconductor wafer 53 is modified by the ultraviolet rays, and the adhesion is improved while maintaining the dielectric constant.
  • the oxidizing active gas may be any gas that can increase the polar component energy in the surface energy of the interlayer insulating film.

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Abstract

La présente invention concerne un procédé de modification de surface et un appareil de modification de surface destiné à des films isolants intercouche qui permettent d'améliorer les propriétés d'adhésion d'un film isolant intercouche sans en changer la constante diélectrique. On forme un film isolant intercouche sur une plaquette (10) semiconductrice en cuisant un film de revêtement. La surface de ce film isolant intercouche est modifiée par le chauffage de l'intérieur d'un tube de réaction (2), dans lequel la plaquette semiconductrice (10) est placée, à une certaine température avec une alimentation simultanée d'un gaz à activité oxydante dans ce tube de réaction (2). Le gaz à activité oxydante est de l'ozone, de la vapeur d'eau, de l'oxygène ou un gaz mélangé hydrogène et oxygène.
PCT/JP2004/005641 2003-04-23 2004-04-20 Procede de modification de surface et appareil de modification de surface destine a un film isolant intercouche WO2004095563A1 (fr)

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JP4607613B2 (ja) 2005-02-09 2011-01-05 株式会社東芝 半導体装置の製造方法
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JP5522979B2 (ja) 2009-06-16 2014-06-18 国立大学法人東北大学 成膜方法及び処理システム
JP6928764B2 (ja) * 2016-01-28 2021-09-01 東京エレクトロン株式会社 金属酸化物のスピンオン堆積の方法

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Publication number Priority date Publication date Assignee Title
JPH07201843A (ja) * 1993-12-28 1995-08-04 Tokyo Electron Ltd Ｓｏｇ膜の形成方法
JPH08213383A (ja) * 1995-02-08 1996-08-20 Nec Corp スピンオングラス膜の形成方法

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JPH10135327A (ja) * 1996-10-29 1998-05-22 Hitachi Ltd 半導体集積回路装置およびその製造方法
JPH10163206A (ja) * 1996-12-02 1998-06-19 Yamaha Corp 配線形成法
KR100239731B1 (ko) * 1997-05-17 2000-01-15 김영환 반도체 제조공정에서의 무기층 형성방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07201843A (ja) * 1993-12-28 1995-08-04 Tokyo Electron Ltd Ｓｏｇ膜の形成方法
JPH08213383A (ja) * 1995-02-08 1996-08-20 Nec Corp スピンオングラス膜の形成方法

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TW200504865A (en) 2005-02-01
TWI339859B (fr) 2011-04-01

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