US20040209194A1 - Ultraviolet-light radiating apparatus, wet etching apparatus and wet etching method using ultravioletlight, and method of manufacturing semiconductor device - Google Patents

Ultraviolet-light radiating apparatus, wet etching apparatus and wet etching method using ultravioletlight, and method of manufacturing semiconductor device Download PDF

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Publication number
US20040209194A1
US20040209194A1 US10/797,577 US79757704A US2004209194A1 US 20040209194 A1 US20040209194 A1 US 20040209194A1 US 79757704 A US79757704 A US 79757704A US 2004209194 A1 US2004209194 A1 US 2004209194A1
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United States
Prior art keywords
film
ultraviolet light
ultraviolet
light
wavelength
Prior art date
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Abandoned
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US10/797,577
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English (en)
Inventor
Satoshi Kume
Nobuyuki Hishinuma
Hiroshi Sugahara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Renesas Technology Corp
Ushio Denki KK
Original Assignee
Semiconductor Leading Edge Technologies Inc
Ushio Denki KK
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Application filed by Semiconductor Leading Edge Technologies Inc, Ushio Denki KK filed Critical Semiconductor Leading Edge Technologies Inc
Assigned to USHIO DENKI KABUSHIKI KAISHA, SEMICONDUCTOR LEADING EDGE TECHNOLOGIES, INC. reassignment USHIO DENKI KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HISHINUMA, NOBUYUKI, KUME, SATOSHI, SUGAHARA, HIROSHI
Publication of US20040209194A1 publication Critical patent/US20040209194A1/en
Assigned to RENESAS TECHNOLOGY CORP. reassignment RENESAS TECHNOLOGY CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SEMICONDUCTOR LEADING EDGE TECHNOLOGIES, INC.
Priority to US11/964,794 priority Critical patent/US7935266B2/en
Abandoned legal-status Critical Current

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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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • 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
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means

Definitions

  • the present invention relates to an apparatus of manufacturing a semiconductor device, and specifically relates to a wet-etching apparatus provided with ultraviolet-light radiation apparatus, a wet-etching method, and a method of manufacturing a semiconductor device.
  • an organic coating e.g., oil
  • the contact angle between the chemical solution and the film increases.
  • the wetting properties of the chemical solution will be lowered. If sufficient wetting properties cannot be obtained, there has been a problem that the chemical solution cannot be coated evenly, and the uniformity of the etching rate within the substrate is deteriorated.
  • the chemical solution 31 is thickly coated as FIG. 5 shows.
  • the thickly coated chemical solution 31 interferes with the transmission of the ultraviolet light, and the light energy of the ultraviolet light is attenuated in the chemical solution 31 . Therefore, there has been a problem that the effect to break the molecular bonds of the film to be processed is weakened, and the desired etching rate cannot be achieved.
  • the present invention has been conceived to solve the previously-mentioned problems and a general object of the present invention is to provide novel and useful ultraviolet-light radiating apparatus, wet etching apparatus, wet etching method, and method of manufacturing a semiconductor device.
  • a more specific object of the present invention is to provide a wet etching apparatus and a wet etching method that can achieve a high etching rate, and excel in the uniformity of the etching rate within the substrate.
  • the above object of the present invention is attained by a following ultraviolet-light radiating apparatus, a following wet etching apparatus, a following wet etching method, and a following method of manufacturing a semiconductor device.
  • the ultraviolet-light radiating apparatus for radiating ultraviolet light to a film to be processed on a substrate comprises first ultraviolet-light radiating units for radiating ultraviolet light having a wavelength of 200 nm or shorter; and second ultraviolet-light radiating units for radiating ultraviolet light having a wavelength longer than 200 nm.
  • the wet etching apparatus comprises a stage for holding a substrate having a film to be etched.
  • First ultraviolet radiating units radiate ultraviolet light having a wavelength of 200 nm or shorter to the film.
  • a chemical-solution coating unit coats a chemical solution on the film.
  • Second ultraviolet radiating units radiate ultraviolet light having a wavelength longer than 200 nm to the film through the chemical solution.
  • first ultraviolet light having a wavelength of 200 nm or shorter is first radiated to a film to be etched on a substrate.
  • a chemical solution is coated on the film after radiating the first ultraviolet light.
  • Second ultraviolet light having a wavelength longer than 200 nm is radiated to the film through the chemical solution.
  • a high-k dielectric film is first formed on a substrate.
  • a gate electrode is formed on the high-k dielectric film.
  • First ultraviolet light having a wavelength of 200 nm or shorter is radiated to the high-k dielectric film.
  • a chemical solution is coated on the high-k dielectric film after radiating the first ultraviolet light.
  • Second ultraviolet light having a wavelength longer than 200 nm is radiated to the high-k dielectric film through the chemical solution. Diffusion regions are formed in the substrate after radiating the second ultraviolet light.
  • FIGS. 1 and 2 are schematic sectional views for illustrating a wet etching apparatus according to a first embodiment of the present invention
  • FIG. 3 is a view for illustrating the case that a chemical solution is thinly coated on a film to be etched on a substrate;
  • FIGS. 4A to 4 D are sectional process views for illustrating a method of manufacturing a semiconductor device according to a second embodiment of the present invention.
  • FIG. 5 is a view for illustrating the case that a chemical solution is thickly coated on a film to be etched on a substrate.
  • FIG. 6 is a schematic sectional view for illustrating a wet etching apparatus having a sealing mechanism.
  • FIGS. 1 and 2 are schematic sectional views for illustrating a wet etching apparatus according to a first embodiment of the present invention. Specifically, FIG. 1 is a diagram showing the wet etching apparatus before applying a chemical solution; and FIG. 2 is a diagram showing the wet etching apparatus after applying the chemical solution.
  • a substrate 5 whereon a film to be etched (film to be processed) is formed is rotatably held on a rotating stage 7 .
  • a plurality of pins 6 are installed on the rotating stage 7 , and the end portion (edge portion) of the substrate 5 is held by these pins 6 .
  • the substrate 5 is, for example, a silicon substrate or a glass substrate.
  • the substrate 5 may also be held by an electrostatic chuck in place of the pins 6 .
  • the etching apparatus has a nozzle 10 for supplying a chemical solution 4 or ultra-pure water onto the substrate 5 (i.e. film to be processed).
  • a rotating shaft 8 is installed on the center of the rotating stage 7 .
  • the substrate 5 also rotates at a desired rotating speed.
  • the rotating stage 7 rotates at a rotating speed of, for example, about 300 to 500 rpm during supplying of the chemical solution 4 , and about 2,000 to 3,000 rpm during drying.
  • the film to be etched is, for example, a high-k dielectric film (hereafter referred to as “high-k film”) such as HfO 2 film and HfAlO film formed using an ALD (atomic layer deposition) method and annealing (PDA: post deposition annealing) treatment.
  • high-k film such as HfO 2 film and HfAlO film formed using an ALD (atomic layer deposition) method and annealing (PDA: post deposition annealing) treatment.
  • a lamp house 2 is disposed as the ultraviolet-light radiating apparatus.
  • the lamp house 2 in the first embodiment is the apparatus that enables both surface reforming of the film to be etched and break of the molecular bonds of the film.
  • the lamp house 2 accommodates first lamps (first ultraviolet-light radiating units) la for radiating ultraviolet light having a wavelength of 200 nm or shorter, and second lamps (second ultraviolet-light radiating units) 1 b for radiating ultraviolet light having a wavelength longer than 200 nm.
  • the first lamps la radiate ultraviolet light for removing organic coatings (e.g., oil) formed on the film to be etched due to environmental contamination, and for making the surface of the film to be etched hydrophilic.
  • organic coatings e.g., oil
  • oxygen radicals also referred to as “active oxygen”
  • ozone gas oxygen radicals
  • the first lamps 1 a for example, Xe 2 (172 nm) excimer lamps or low-pressure mercury lamps can be used.
  • the second lamps 1 b radiate ultraviolet light having energy higher than the binding energy of the constituent molecules of the film, and radiate for break the bonds of the molecules.
  • the energy of the ultraviolet light can be controlled by the radiating time of the ultraviolet light, and the radiating time is, for example, 10 to 200 seconds.
  • the second lamps 1 b radiate ultraviolet light to the film to be etched through a chemical solution 4 coated on the film to be etched.
  • KrCl (222 nm) excimer lamps can be used as the second lamps 1 b. Since the ultraviolet light radiated from the second lamps 1 b has a low absorption coefficient to oxygen, the light energy is efficiently transmitted to the film to be etched.
  • a light-transmitting window 3 formed of a quartz glass (hereafter referred to as “quartz glass window”) having a high transmissivity to ultraviolet light from the lamps 1 a and 1 b.
  • the inside of the lamp house 2 sealed with the quartz glass window 3 is filled with an inert gas such as nitrogen. Thereby, the ultraviolet light, having a high absorption coefficient to oxygen, radiated from the first lamps 1 a is prevented from attenuation in the lamp house 2 .
  • the intensity of the ultraviolet light radiated from the second lamp 1 b at the quartz glass window 3 is preferably 5 to 20 mW/cm 2 .
  • a drive unit 9 is installed for driving the lamp house 2 in the vertical direction.
  • FIG. 1 shows a substrate 5 whereon a film to be etched (e.g., HfO 2 film) is formed is held by pins 6 on the rotating stage 7 .
  • the lamp house 2 is lowered using the drive unit 9 , and the first lamps 1 a are turned on.
  • ultraviolet light having a wavelength of 200 nm or shorter is radiated from the first lamps 1 a on the film to be etched.
  • the ultra violet-light radiation causes oxygen in the vicinity of the film to be excited, there by generating oxygen radicals and ozone gas.
  • the oxygen radicals and ozone gas decompose the organic coatings formed on the film to be etched, and vaporize the coatings as carbon dioxide and water vapor. Thereby, the surface of the film to be etched is reformed to be hydrophilic. Thereafter, the first lamps la are turned off, and the lamp house 2 is elevated using the drive unit 9 .
  • the chemical solution 4 containing a phosphoric-acid-based etchant is supplied on the film to be etched from the nozzle, while rotating the substrate 5 at a rotation speed of 300 to 500 rpm by rotating the rotating stage 7 . Thereby, the chemical solution 4 is thinly and evenly coated on the hydrophilic film to be etched. At this time, the chemical solution 4 is coated without running off the substrate 5 .
  • the lamp house 2 is lowered in the vicinity of the substrates using the drive unit 9 so that the quartz glass window 3 does not interfere with the pins 6 , as FIG. 2 shows.
  • Ultraviolet light is radiated from the second lamps 1 b, that has previously been turned on, to the film to be etched (HfO 2 film) through the chemical solution 4 . Since the chemical solution 4 is thinly coated, as FIG. 3 shows, the ultraviolet light is radiated on the film to be etched on the substrate 5 .
  • the light energy of the ultraviolet light breaks the bonds of the molecules of the film to be etched (Hf—O bonds of the HfO 2 film), and etching reaction proceeds by the etchant contained in the previously coated chemical solution 4 .
  • the second lamps 1 b are turned off, the lamp house 2 is elevated using the drive unit 9 , and ultra-pure water is ejected from the water-cleaning nozzle onto the substrate 5 to wash away the chemical solution 4 remaining on the substrate 5 .
  • the substrate 5 is rotated at about 2,000 to 3,000 rpm using the rotating stage 7 to shake off the ultra-pure water on the substrate 5 , thereby drying the substrate 5 .
  • a chemical solution 4 is coated on the film, and wet etching is performed while radiating ultraviolet light having a wavelength longer than 200 nm from second lamps 1 b. to the film through the chemical solution 4 .
  • organic coatings formed on the surface of the film to be etched can be removed by the ultraviolet light from the first lamps 1 a in the air, and the surface of the film to be etched can be made hydrophilic. Therefore, the chemical solution 4 can be thinly and evenly coated on the surface of the hydrophilic film to be etched. Thus, since the high wetting properties of the chemical solution 4 can be obtained, and the chemical solution 4 can evenly act within the surface of the substrate 5 . Accordingly, the uniformity of the etching rate within the substrate can be improved.
  • ultraviolet light from the second lamps 1 b is radiated to the film to be etched without the attenuation of energy in the air and in the chemical solution 4 . Therefore, wet etching can be performed in the state wherein the molecular bonds of the film are broken most, and the etching rate can be significantly increased.
  • the present invention can provide an etching apparatus and an etching method that can achieve a high etching rate, and excel in the uniformity of the etching rate within the substrate.
  • the atmosphere since the ultraviolet light of a wavelength of 200 nm or shorter has a high absorption coefficient to oxygen, in order to prevent the attenuation of ultraviolet light, the atmosphere must be replaced with an inert gas such as nitrogen, and the oxygen content must be maintained-to be 100 ppm by volume or less.
  • nitrogen which is a replacing gas, must be wastefully consumed, and various apparatuses must be installed to block off the atmosphere wherein the substrate is held from the air (refer to FIG. 5).
  • ultraviolet light of a wavelength longer than 200 nm having an extremely low absorption coefficient to oxygen is radiated to break molecular bonds. Therefore, ultraviolet light from the second lamps 1 b can be radiated in the air without replacing the atmosphere. Thus, the wasteful consumption of the replacing gas can be avoided, no apparatuses for blocking out the atmosphere are required, and the apparatus can be simplified. Therefore, the manufacturing costs and the operating costs of the etching apparatus can be reduced. In addition, since time for replacing the atmosphere is not required, the etching time can be shortened, and the throughput can be improved.
  • the embodiment also provides the lamp house structure that enables both the surface reformation of the film to be etched and the break of molecular bonds of the film.
  • the present invention is not limited thereto, but can also be applied to a film having a low wet-etching rate, and is particularly preferable for dense thin films.
  • an excimer laser may be used in place of excimer lamps.
  • FIGS. 4A to 4 D are sectional process views for illustrating a method of manufacturing a semiconductor device according to a second embodiment of the present invention.
  • an element isolating 22 made from oxide is formed in a substrate 21 .
  • a high-k film 23 for example HfO 2 film and HfAlO film, is formed on the entire surface of the substrate 21 by an ALD method and annealing treatment.
  • a polysilicon film is formed on the high-k film 23 .
  • a resist pattern (not shown) is formed on the polysilicon film.
  • the polysilicon film is patterned using the resist pattern as a mask to form a gate electrode 24 .
  • ultraviolet light 25 having a wavelength of 200 nm or shorter is radiated on the high-k film 23 in atmosphere containing oxygen.
  • the ultraviolet-light radiation causes oxygen in the vicinity of the high-k film 23 to be excited, thereby generating oxygen radicals and ozone gas.
  • the oxygen radicals and ozone gas decompose organic coatings (not shown) formed on the high-k film 23 , and vaporize the organic coatings as carbon dioxide and water vapor. Thereby, a surface of the high-k film 23 is reformed to be hydrophilic.
  • extension regions 28 are formed by ion implantation of impurities using the gate electrode 24 and the high-k film 23 as a mask.
  • sidewalls 29 made from nitride are formed on the sides of the gate electrodes 24 and high-k film 23 .
  • source/drain regions 30 are formed by ion implantation of impurities using the gate electrode 24 , the high-k film 23 and the sidewalls 29 as a mask.
  • a chemical solution 26 is coated on the high-k film 23 , and wet etching is performed while radiating ultraviolet light 27 having a wavelength longer than 200 nm to the high-k film 23 through the chemical solution 26 .
  • organic coatings formed on the surface of the high-k film 23 can be removed by the ultraviolet light 25 in the air (atmosphere containing oxygen), and the surface of the high-k film 23 can be made hydrophilic. Therefore, the chemical solution 26 can be thinly and evenly coated on the surface of the hydrophilic high-k film 23 . Thus, since the high wetting properties of the chemical solution 26 can be obtained, and the chemical solution 26 can evenly act within the high-k film 23 . Accordingly, the uniformity of the etching rate of the high-k film 23 within the substrate can be improved.
  • ultraviolet light 27 is radiated to the high-k film 23 without the attenuation of energy in the air and in the chemical solution 26 . Therefore, wet etching can be performed in the state wherein the molecular bonds of the high-k film 26 are broken most, and the etching rate can be significantly increased.
  • a wet etching apparatus and a wet etching method that can achieve a high etching rate, and excel in the uniformity of the etching rate within the substrate, can be provided.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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US10/797,577 2003-03-25 2004-03-11 Ultraviolet-light radiating apparatus, wet etching apparatus and wet etching method using ultravioletlight, and method of manufacturing semiconductor device Abandoned US20040209194A1 (en)

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US20040211756A1 (en) * 2003-01-30 2004-10-28 Semiconductor Leading Edge Technologies, Inc. Wet etching apparatus and wet etching method using ultraviolet light
US20050205521A1 (en) * 2004-03-17 2005-09-22 Semiconductor Leading Edge Technologies, Inc. Wet etching apparatus and wet etching method
US20070212829A1 (en) * 2006-03-10 2007-09-13 Masashi Takahashi Method of manufacturing a semiconductor device
US20080092918A1 (en) * 2006-10-24 2008-04-24 Asahi Glass Company Limited Method for removing foreign matter from substrate surface
US20080113518A1 (en) * 2003-03-25 2008-05-15 Renesas Technology Corp. Wet etching method using ultraviolet light and method of manufacturing semiconductor device
US20090047790A1 (en) * 2007-08-16 2009-02-19 Micron Technology, Inc. Selective Wet Etching of Hafnium Aluminum Oxide Films
US20160129484A1 (en) * 2014-11-06 2016-05-12 Taiwan Semiconductor Manufacturing Co., Ltd. Semiconductor apparatus and method of removing photoresist layer on substrate
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US11342220B2 (en) 2018-12-10 2022-05-24 Sciocs Company Limited Structure manufacturing method and manufacturing device, and light irradiation device
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JP6204881B2 (ja) * 2014-06-26 2017-09-27 東京エレクトロン株式会社 被処理体を処理する方法
US20160379854A1 (en) * 2015-06-29 2016-12-29 Varian Semiconductor Equipment Associates, Inc. Vacuum Compatible LED Substrate Heater
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DE102015011228B4 (de) 2015-08-27 2017-06-14 Süss Microtec Photomask Equipment Gmbh & Co. Kg Vorrichtung zum Aufbringen eines mit UV-Strahlung beaufschlagten flüssigen Mediums auf ein Substrat
US11358172B2 (en) * 2015-09-24 2022-06-14 Suss Microtec Photomask Equipment Gmbh & Co. Kg Method for treating substrates with an aqueous liquid medium exposed to UV-radiation
JP6368743B2 (ja) * 2016-06-22 2018-08-01 株式会社日立国際電気 基板処理装置、半導体装置の製造方法およびプログラム
JP7011947B2 (ja) * 2018-01-29 2022-02-10 東京エレクトロン株式会社 アッシング装置、アッシング方法及びコンピュータ読み取り可能な記録媒体
JP6668545B1 (ja) * 2019-08-14 2020-03-18 株式会社サイオクス 構造体の製造方法と製造装置、および光照射装置
JP7221177B2 (ja) * 2019-09-05 2023-02-13 住友化学株式会社 構造体の製造方法および製造装置

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