WO2017132351A1 - Methods of spin-on deposition of metal oxides - Google Patents

Methods of spin-on deposition of metal oxides Download PDF

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Publication number
WO2017132351A1
WO2017132351A1 PCT/US2017/015097 US2017015097W WO2017132351A1 WO 2017132351 A1 WO2017132351 A1 WO 2017132351A1 US 2017015097 W US2017015097 W US 2017015097W WO 2017132351 A1 WO2017132351 A1 WO 2017132351A1
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WO
WIPO (PCT)
Prior art keywords
surface energy
executing
fill material
modification treatment
deposition
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2017/015097
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English (en)
French (fr)
Inventor
Nihar Mohanty
Lior HULI
Jeffrey Smith
Richard Farrell
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Tokyo Electron Ltd
Tokyo Electron US Holdings Inc
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Tokyo Electron Ltd
Tokyo Electron US Holdings Inc
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Filing date
Publication date
Application filed by Tokyo Electron Ltd, Tokyo Electron US Holdings Inc filed Critical Tokyo Electron Ltd
Priority to CN201780013847.5A priority Critical patent/CN108701587B/zh
Priority to JP2018539823A priority patent/JP6928764B2/ja
Priority to KR1020187024190A priority patent/KR102405203B1/ko
Publication of WO2017132351A1 publication Critical patent/WO2017132351A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/65Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
    • H10P14/6516Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials
    • H10P14/6546Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials to change the surface groups of the insulating materials
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326Deposition processes
    • H10P14/6342Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/455Chemical 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
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/65Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
    • H10P14/6502Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials
    • H10P14/6508Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials by exposure to a liquid
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/65Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
    • H10P14/6502Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials
    • H10P14/6512Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials by exposure to a gas or vapour
    • H10P14/6514Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials by exposure to a gas or vapour by exposure to a plasma
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/65Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
    • H10P14/6516Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials
    • H10P14/6528In-situ cleaning after layer formation, e.g. removing process residues
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/65Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
    • H10P14/6516Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials
    • H10P14/6529Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials by exposure to a gas or vapour
    • H10P14/6532Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed after formation of the materials by exposure to a gas or vapour by exposure to a plasma
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69Inorganic materials
    • H10P14/692Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69Inorganic materials
    • H10P14/692Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69394Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing titanium, e.g. TiO2
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10PGENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/40Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
    • H10P76/405Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their composition, e.g. multilayer masks

Definitions

  • creating patterned layers comprises the application of a thin layer of radiation-sensitive material, such as photoresist, to an upper surface of a substrate.
  • This radiation-sensitive material is transformed into a relief pattern which can be used as an etch mask to transfer a pattern into an underlying layer on a substrate.
  • Patterning of the radiation-sensitive material generally involves exposure to actinic radiation through a reticle (and associated optics) onto the radiation-sensitive material using, for example, a photo-lithography system.
  • This exposure can then be followed by the removal of irradiated regions of the radiation-sensitive material (as in the case of positive photoresist), or non-irradiated regions (as in the case of negative resist) depending on a developing solvent used.
  • This mask layer can comprise multiple sub-layers.
  • SAB Self-aligned blocking
  • a multi-line layer is formed with alternating lines of different materials. These materials are different in that one or more of these materials can be selectively etched without etching remaining materials.
  • tuning a given etch process to target one of these materials means that the etch mask opening is essentially further narrowed so that combining the etch mask opening with the multi-line layer (with at least one material removed) effectively creates a combined, sub-resolution etch mask for pattern transfer into an underlying layer.
  • Such patterning can be made especially useful if used with spin-on metal hard mask (MHM) materials.
  • Techniques herein provide methods for depositing spin-on metal materials for creating metal hard mask (MHM) structures. This includes effective spin-on deposition of TiOx, ZrOx, SnOx, HFOx, TaOx, et cetera. Such materials can help to provide differentiation of etch resistivities which is referred to as providing different "colors" of a multi-line layer.
  • spin-on metal hard mask (MHM) for use with a multi-line layer, multiple color decomposition is achieved on a given pattern, which enables a slit-based or self-aligned blocking strategy.
  • Techniques herein include identifying a fill material to fill particular openings in a given relief pattern, modifying a surface energy value such that a contact angle value of an interface between the fill material in liquid form and the sidewaii surfaces enables gap free filling.
  • FIG. 1 is a cross-sectional schematic view of an example substrate segment showing a process flow according to embodiments disclosed herein.
  • FIG. 2 is a cross-sectional schematic view of an example substrate segment showing surface modification according to embodiments disclosed herein.
  • FIG. 3 is a cross-sectional schematic view of an example substrate segment showing a process flow according to embodiments disclosed herein.
  • FIG. 4 is a magnified image of a substrate segment showing voids in a fill material.
  • FIG. 5 is a magnified image of a substrate segment showing void-free filling according to techniques herein.
  • Techniques herein provide methods for depositing spin-on metal materials for creating metal hard mask (MHM) structures. This includes effective spin-on deposition of TiGx, ZrOx, SnOx, HFOx, TaQx, et cetera. Such materials can help to provide differentiation of etch resistivities which is referred to as providing different "colors" of a multi-line layer.
  • spin-on metal hard mask (MHM) for use with a multi-line layer, multiple color decomposition is achieved on a given pattern, which enables a slit-based or self-aligned blocking strategy,
  • a challenge during this spin-on metal oxide (MeOx) integration is gap fill. Filling the gaps for the sub-18 nm space in SAQP pattern, with aspect ratios reaching 5-6: 1 , is significantly challenging. Techniques herein, however, resolve some of the challenges in advanced node narrow pitch back end of line (BEOL) trench patterning.
  • BEOL back end of line
  • Techniques herein resolve the gap fill issue for the spin-on MeOx materials.
  • void-free filling of the trenches is achieved.
  • Techniques herein include several methods by which the surface energy of the side-wail and/or floor can be improved. Such methods include surface treatments such as post-etch treatment with oxygen, nitrogen, hydrogen, and fluorine containing gases. Another treatment includes post etch wet cleans with dilute hydrofluoric acid (dHF), sulphuric peroxide (SPN), et cetera.
  • dHF dilute hydrofluoric acid
  • SPN sulphuric peroxide
  • Another treatment includes pre ⁇ appiying treatment in a coater/developer system with solvents such as isopropyl alcohol, de-ionized water, tetramethylammonium hydroxide (TMAH), hexamethyldisilazane (HMDS), et cetera.
  • solvents such as isopropyl alcohol, de-ionized water, tetramethylammonium hydroxide (TMAH), hexamethyldisilazane (HMDS), et cetera.
  • TMAH tetramethylammonium hydroxide
  • HMDS hexamethyldisilazane
  • et cetera et cetera
  • conformal films such as by atomic layer deposition (ALD), chemical vapor deposition (CVD), direct current superposition, and so forth.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • direct current superposition and so forth.
  • the spin-on IVIeQx material is hydrophilic
  • the surface of the trench including the sidewa!ls and the floor
  • the hydrophilic material will not wet the trench completely and thus will result in voids during the baking process.
  • FIG. 4 illustrates an example of the gap fill problem with conventional techniques.
  • F!G. 4 is an enlarged image of a substrate segment that has openings filled by a metal oxide material 207, Note, however, that the deposition of metal oxide material 207 resulted in voids 21 1 at the bottom of openings being filled by the metal oxide.
  • Techniques herein include a method for depositing material on a substrate.
  • a substrate is received or otherwise provided that has a relief pattern.
  • the relief pattern defines openings that uncover an underlying layer.
  • the relief pattern provides sidewall surfaces that define the openings.
  • the underlying layer provides floor surfaces that define the openings.
  • the relief pattern has trenches or holes or other openings that extend to an underlying layer. These trenches or openings have side surfaces and a bottom surface.
  • the relief pattern provides the side surfaces, while a top surface of an underlying layer functions as a floor surface or bottom surface of a given hole or trench.
  • the relief pattern can define openings having critical dimensions less than 40
  • FIG. 1 illustrates an example substrate segment defining openings. Note that this substrate segment includes relief pattern 150 and underlying layer 135. Relief pattern 150 includes lines of two different materials. Letters "A” and “B” appear above these materials. The letter “C” appears above openings in the relief pattern. By way of a non-limiting example, the opening designated with the letter C can be trenches to be filled with a metal-containing material.
  • a fill material is identified or otherwise selected to fill the defined openings by being deposited on the substrate via spin-on deposition.
  • Fill materials can include metal oxide or other metal-containing materials,
  • a surface energy modification treatment is executed.
  • the surface energy modification treatment modifies at least one of the first surface energy value and the second surface energy value such that a contact angle value of an interface between the fill material in liquid form and the sidewail surfaces or the floor surfaces is less than 80 degrees.
  • Such a surface energy modification treatment can thus target either the sidewail surfaces, the floor surfaces, or both.
  • the contact angle value of the interface between the fill material in liquid form and the sidewail surfaces can be less than 60 degrees or less than 30 degrees or less than 20 degrees.
  • Executing the energy modification treatment can include modifying the second surface energy value such that a contact angle value of an interface between the fiil material in liquid form and the floor surfaces is less than 60 degrees, or less than 30 degrees, or less than 20 degrees, depending on a type of modification treatment executed.
  • Techniques herein provide several alternative treatments for modifying surface energies of surfaces to be filled.
  • One example treatment is exposing the substrate to plasma products within a plasma processing system.
  • F!G. 2 illustrates such an example treatment.
  • a plasma 172 can be formed over a working surface of a substrate such that plasma products react with substrate surfaces or otherwise bombard substrate surfaces to change surface energies. Isotropic flow of plasma products is beneficial for modifying sidewail surfaces.
  • a liquid-based modifier can be deposited on the relief pattern, which can react with or otherwise alter surfaces.
  • a liquid-based treatment can include executing a post-etch wet clean. With particular cleaning chemicals selected based on relief pattern materials and underlying layer materials, the substrate can be simultaneously cleaned and modified.
  • Alternative modification techniques include depositing a conformal film on the relief pattern such as by atomic layer deposition, chemical vapor deposition, direct current superposition, or combinations thereof.
  • one or more modification treatments can be executed.
  • a first modification treatment can be used to modify sidewall surfaces, while a second modification treatment is used to modify floor surfaces.
  • two or more treatments can be executed to modify a given surface as desired.
  • the fill material— which can be metal-containing— is deposited on the substrate via spin-on deposition. This deposition is executed such that the fill material fills the defined openings with the fill material being in contact with the sidewall surfaces and the floor surfaces. With surface energies being tuned to a given fill material, such deposition results in a void free filling.
  • FIG. 3 illustrates an example result of a substrate segment after the fill operation and after an optional planarization step to remove any overburden of fill material.
  • a low-temperature titanium oxide (TiOx) solvent system based on propanoi (an alcohol) is deposited on a substrate.
  • an oxidative post-etch treatment is executed as well as a wash with isopropyi alcohol. As shown in FIG. 5, the result is a void-free fill of metal oxide.
  • substrate or "target substrate” as used herein generically refers to an object being processed in accordance with the invention.
  • the substrate may include any material portion or structure of a device, particularly a semiconductor or other electronics device, and may, for example, be a base substrate structure, such as a semiconductor wafer, reticle, or a layer on or overlying a base substrate structure such as a thin film.
  • substrate is not limited to any particular base structure, underlying layer or overlying layer, patterned or un-patterned, but rather, is contemplated to include any such layer or base structure, and any combination of layers and/or base structures.
  • the description may reference particular types of substrates, but this is for illustrative purposes only.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Physics & Mathematics (AREA)
  • Drying Of Semiconductors (AREA)
  • Plasma & Fusion (AREA)
  • Formation Of Insulating Films (AREA)
  • General Physics & Mathematics (AREA)
PCT/US2017/015097 2016-01-28 2017-01-26 Methods of spin-on deposition of metal oxides Ceased WO2017132351A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201780013847.5A CN108701587B (zh) 2016-01-28 2017-01-26 旋涂沉积金属氧化物的方法
JP2018539823A JP6928764B2 (ja) 2016-01-28 2017-01-26 金属酸化物のスピンオン堆積の方法
KR1020187024190A KR102405203B1 (ko) 2016-01-28 2017-01-26 금속 산화물의 스핀온 퇴적 방법

Applications Claiming Priority (2)

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US201662288253P 2016-01-28 2016-01-28
US62/288,253 2016-01-28

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WO2017132351A1 true WO2017132351A1 (en) 2017-08-03

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US (1) US10141183B2 (https=)
JP (1) JP6928764B2 (https=)
KR (1) KR102405203B1 (https=)
CN (1) CN108701587B (https=)
TW (1) TWI643251B (https=)
WO (1) WO2017132351A1 (https=)

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CN108701587A (zh) 2018-10-23
JP2019510366A (ja) 2019-04-11
US20170221704A1 (en) 2017-08-03
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US10141183B2 (en) 2018-11-27
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