WO2003023084A1 - Cible de pulverisation cathodique de fluorure et son procede de preparation - Google Patents

Cible de pulverisation cathodique de fluorure et son procede de preparation Download PDF

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Publication number
WO2003023084A1
WO2003023084A1 PCT/JP2002/007264 JP0207264W WO03023084A1 WO 2003023084 A1 WO2003023084 A1 WO 2003023084A1 JP 0207264 W JP0207264 W JP 0207264W WO 03023084 A1 WO03023084 A1 WO 03023084A1
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WO
WIPO (PCT)
Prior art keywords
target
film
fluoride
sputtering
hot
Prior art date
Application number
PCT/JP2002/007264
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English (en)
Japanese (ja)
Inventor
Shuichi Irumata
Ryo Suzuki
Original Assignee
Nikko Materials Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Nikko Materials Company, Limited filed Critical Nikko Materials Company, Limited
Publication of WO2003023084A1 publication Critical patent/WO2003023084A1/fr

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Classifications

    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides

Definitions

  • the present invention relates to a fluoride sputtering apparatus which can be used for forming various optical thin films such as an antireflection film for infrared, visible and ultraviolet light, a filter film, and a gate insulating film of a highly integrated semiconductor. And its manufacturing method.
  • various optical thin films such as an antireflection film for infrared, visible and ultraviolet light, a filter film, and a gate insulating film of a highly integrated semiconductor.
  • fluoride has been used for the formation of various optical thin films such as an antireflection film for infrared, visible and ultraviolet light, a filter film, and the like.
  • the membrane was widely made.
  • L a F 3 such as a gate insulating film made from fluoride having a specific dielectric constant 60 is promising.
  • the evaporation method has been widely used so far as a method of forming a fluoride film.
  • a fluoride evaporation source By heating a fluoride evaporation source to a high temperature and sublimating the fluoride, the fluoride is sputtered onto a film-forming object, All are formed as molecules or clusters of several molecules.
  • there has been a demand for an increase in the area of a film-forming portion and there has been a problem that such a vapor deposition method cannot form an efficient and uniform thin moon. Disclosure of the invention
  • the present invention provides a fluoride sputtering target that can use sputtering capable of forming a large area film as a film forming method, and further increases the density of the target. It is therefore an object of the present invention to provide a target capable of suppressing the generation of particles and obtaining a film of a desired quality, and a method of manufacturing the same.
  • the present invention provides a fluoride sputtering target that can use sputtering capable of forming a large area film as a film forming method, and further increases the density of the target. It is therefore an object of the present invention to provide a target capable of suppressing the generation of particles and obtaining a film of a desired quality, and a method of manufacturing the same.
  • a sputtering target comprising a fluoride of at least one element selected from the group consisting of A1, Ba, Ca, Gd, La, Li, Mg, Pb, and Y.
  • Fluoride powder consisting of at least one element selected from the group consisting of Al, Ba, Ca, Gd, La, Li, Mg, Pb, and Y
  • a sputtering target characterized by hot pressing at a temperature of 50 to 70% in absolute temperature with respect to the melting point of each compound in a medium, nitrogen gas atmosphere or an inert gas atmosphere such as Ar gas.
  • a sputtering method is used to deposit a fluoride made of at least one element selected from the group consisting of A 1, Ba, Ca, Gd, La, Li, Mg, Pb, and Y. It is used to provide a target therefor, and can meet the demand for a larger area of a film-forming portion and can suppress composition deviation.
  • sputtering evening Getto i.e. A 1 F 2 a deviation from stoichiometric composition has a composition ratio within 0. 5 5 -... 3 B a FL 5 __ 2 5, C aF .. 2 5 _ 2 5, GdF 2 5 -dividing 3 5, L aF 2 5 _ 3 5, L i F 0 5 _, 5, MgF L 5 -.. 2 5, P bF x 5 _ 2. 5> YF 2. 5 3. to provide at least one or Ranaru fluoride sputtering target was selected from the fifth group.
  • fluorine gas and fluorine compound gas are extremely corrosive, so that sputter deposition that does not rely on reactive sputtering is required more often than ordinary compounds.
  • the deviation from the stoichiometric ratio of the evening get composition be small. If the deviation from the stoichiometric ratio is 0.5 or less, the characteristics of the film with the desired optical properties (transmittance, refractive index, etc.) or the properties of the insulator properties (relative dielectric constant, leak current, etc.) However, the target optical characteristics or the insulating film characteristics cannot be obtained with a film formed using a target shifted by more than 0.5.
  • the fluoride evaporation source used in the evaporation method which has been widely used so far as a method for forming a fluoride film, is heated to a high temperature and sublimated to fly the fluoride onto a substrate or an object to be formed. Therefore, it was not necessary to increase the density of the evaporation source because all of them were in the state of molecules or clusters of several molecules. However, if the target is made by extension of the evaporation source manufacturing technology, it can only be a low-density evening target with a density ratio of about 60 to 80%.
  • Such fluorides having a density ratio of less than 95% have a porous structure, and have a problem that they are fragile due to insufficient density and workability is deteriorated. Furthermore, in a film sputtered using such a low-density target, a number of particulate defects called particles are detected, and the problem that the product yield is significantly reduced occurs. Therefore, it is desirable that the present invention is a sputtering target having a density ratio of 95% or more.
  • Sputtering evening ring Target Tsu bets deviation from stoichiometric composition has a composition ratio within 0.5, i.e. A 1 F 2 5 -.. .. 3 5, B aFt 5 _ 2 5, C a F ⁇ 5 -. 2 5, GdF 2 .
  • YF 2. 5 _ 3. To produce a fluoride sputter-ring target consisting of at least one selected from the group of 5, the powder in the composition of this range, in air, oxygen, nitrogen or A, It is effective to perform hot pressing in an atmosphere of an inert gas such as r at a temperature of 50 to 70% in absolute temperature with respect to the melting point of each compound. In this case, if the hot pressing is performed in a vacuum, the dissociation of the fluoride powder proceeds. Dissociation progress can be suppressed by conducting in air, oxygen, nitrogen, or an inert gas. By hot pressing at a temperature of 50% or more in absolute temperature to the melting point of each compound in the above atmosphere, a target having a density of 95% or more can be obtained.
  • an inert gas such as r
  • hot pressing at high temperatures causes embrittlement due to compositional deviations due to the dissociation of fluorine and makes machining difficult, and is not suitable for sputtering targets.
  • the hot pressing temperature must be set at an absolute temperature relative to the melting point of each compound. By setting the content to 70% or less, a fluoride target having a small composition deviation and having sufficient strength for machining can be obtained.
  • a 1 F 3 powder was hot-pressed at 1 173 ° K, 300 kgf / cm 2 for 2 hours in an Ar gas atmosphere at 1 atm.
  • the composition ratio of the sintered body A 1 F 2. 8 was 2% 98..
  • This hot-press sintered body was processed into a target having a diameter of 76.2 mm, and the target was sputtered to form a film having a thickness of 0.1 m on a substrate having a diameter of 50 mm.
  • Example 2 When the number of particles after sputtering was measured, five particles having a size of 0.5 m or more were measured on the substrate, but the number was extremely small as compared with a comparative example described later. (Example 2)
  • the Gd F 3 powder was hot-pressed at 1 173 ° K, 300 kgf / cm 2 for 2 hours in an atmosphere of Ar gas at 1 atm. As a result, the composition ratio of the sintered body was Gd F 2. 6, next, the relative density of 97.2%.
  • This hot-press sintered body was processed into a target having a diameter of 76.2 mm, and the target was sputtered to form a film having a thickness of 0.1 im on a substrate having a diameter of 50 mm.
  • the MgF 2 powder was hot-pressed at 1 173 ° K, 300 kf / cm 2 for 2 hours in an Ar gas atmosphere at 1 atm.
  • the composition ratio was MgF ⁇ 8 and the relative density was 99.2%.
  • the hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and was sputtered using the target to form a film having a thickness of 0.1 m on a substrate having a diameter of 50 mm.
  • Example 5 When the number of particles after sputtering was measured, three of the particles having a thickness of 0.5 zm or more were measured on the substrate, but the number was significantly smaller than the comparative example described later. (Example 5)
  • the YF 3 powder 1 223 ° K, 300 were kgf / cm ⁇ 2 hour hot pressing in A r gas atmosphere of 1 atm. Composition ratio YF 2. 6, the relative density was 97.9%.
  • the hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and sputtering was performed using the target to form a film having a thickness of 0.1 / zm on a substrate having a diameter of 5 Omm.
  • the number of particles after sputtering was measured. As a result, seven particles were measured on the substrate (0.5 m or more), which was significantly smaller than the comparative example described later.
  • the B aF 2 powder was hot-pressed at 1 123 ° K, 300 kg f / cm 2 for 2 hours in an Ar gas atmosphere at 1 atm.
  • the composition ratio of the sintered body B a F 2. 8 was 2% 98..
  • This hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and the target was sputtered to form a film having a thickness of 0.1 m on a substrate having a diameter of 50 mm.
  • the number of particles after sputtering was measured. As a result, five particles having a size of 0.5 zm or more were measured on the substrate, but the number was significantly smaller than a comparative example described later.
  • the C a F 2 powder was hot pressed at 1 173 ° K, 300 kg f / cm 2 for 2 hours in an atmosphere of Ar gas at 1 atm.
  • the composition ratio of the sintered body was C a F 2. 6
  • the relative density of 97.2% was processed into a target having a diameter of 76.2 mm, and sputtering was performed using this target to form a film having a thickness of 0.1 / zm on a substrate having a diameter of 50 mm.
  • Example 8 When the number of particles after sputtering was measured, six particles having a size of 0.5 m or more were measured on the substrate, but the number was extremely small as compared with a comparative example described later. (Example 8)
  • the L iF powder was hot pressed in an Ar gas atmosphere at 1 atm at 943 ° K, 30 bkgf / cm 2 for 2 hours. Composition ratio L i F 0. 9, the relative density was 99.5%.
  • the hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and the target was sputtered to form a film having a thickness of 0.1 m on a substrate having a diameter of 5 Omm.
  • PbF 2 powder was hot-pressed at 723 ° K, 300 kgf / cm 2 for 2 hours in an Ar gas atmosphere at 1 atm.
  • the composition ratio was PbF ⁇ 8 and the relative density was 99.2%.
  • This hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and the target was sputtered to form a film having a thickness of 0.1 zm on a substrate having a diameter of 50 mm.
  • a 1 F 3 powder was hot-pressed at 1323 ° K, 300 kgf / cm 2 for 2 hours in an atmosphere of Ar gas at 1 atm. Although the relative density increased to 99.4%, it was very brittle and could not be processed into the target shape. Incidentally, 'composition ratio was A 1 F 2. 3.
  • the hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and was sputtered using the target to form a film having a thickness of 0.1 m on a substrate having a diameter of 50 mm.
  • This film had low transmittance and was not suitable for optical use. In addition, it was conductive and was not suitable for insulating films. (Comparative Example 3)
  • the LaF 3 powder was hot-pressed at 873 ° K, 300 kgf / cm 2 for 2 hours in an Ar gas atmosphere at 1 atm. Composition ratio L aF 2. 9, the relative density was 91.4%.
  • This hot-pressed sintered body was processed into a target having a diameter of 76.2 mm, and was sputtered using this evening get to form a film having a thickness of 0.1 m on a substrate having a diameter of 50 mm.
  • 120 particles having a particle size of 0.5 / im or more were measured on the substrate, and a remarkable increase in the number of particles was observed.
  • the present invention is suitable for forming various types of optical thin films such as an antireflection film for infrared, visible and ultraviolet light, a film for a filter, etc., and a gate insulating film for a highly integrated semiconductor. It is possible to form a film with a large area, and by increasing the density of the evening gate, it is possible to suppress the generation of particles, and to obtain a film of high strength, high quality, and little composition deviation or defects. It has an excellent effect.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Optical Filters (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne une cible de pulvérisation cathodique caractérisée en ce qu'elle comprend un fluorure d'au moins un élément sélectionné dans le groupe constitué de Al, Ba, Ca, Gd, La, Li, Mg, Pb et Y ; et un procédé de préparation de ladite cible. La cible de pulvérisation cathodique permet l'utilisation d'un procédé de pulvérisation cathodique dans le but de former un film de fluorure, procédé qui à son tour, permet la formation d'un film ayant une aire plus importante. Par ailleurs, l'amélioration de la densité de la cible permet la suppression de l'occurrence de particules et, par voie de conséquence, la préparation d'une cible dont la qualité est celle souhaitée.
PCT/JP2002/007264 2001-09-05 2002-07-17 Cible de pulverisation cathodique de fluorure et son procede de preparation WO2003023084A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001268217A JP2003073818A (ja) 2001-09-05 2001-09-05 フッ化物スパッタリングターゲット及びその製造方法
JP2001-268217 2001-09-05

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WO2003023084A1 true WO2003023084A1 (fr) 2003-03-20

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JP5577287B2 (ja) * 2011-03-30 2014-08-20 日本碍子株式会社 フッ化マグネシウム焼結体、その製法及び半導体製造装置用部材
JP6955748B2 (ja) * 2017-05-10 2021-10-27 国立研究開発法人物質・材料研究機構 Ｍｉｓ型半導体装置およびその製造方法
CN114163242B (zh) * 2021-12-30 2022-11-18 杭州电子科技大学 一种低介电常数高品质因数的微波介质陶瓷及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH116059A (ja) * 1997-06-18 1999-01-12 Olympus Optical Co Ltd スパッタリングターゲット及び薄膜の製造方法
JPH11106910A (ja) * 1997-10-03 1999-04-20 Olympus Optical Co Ltd 薄膜の成膜方法
JP2000086344A (ja) * 1998-09-14 2000-03-28 Kyocera Corp 高密度フッ化物焼結体およびその製造方法並びにそれを用いた半導体製造装置用部材
JP2000239066A (ja) * 1999-02-22 2000-09-05 Kyocera Corp 耐食性部材およびその製造方法、並びにそれを用いたプラズマ処理装置用部材
JP2000282233A (ja) * 1999-04-02 2000-10-10 Canon Inc 光学薄膜成膜方法および光学薄膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH116059A (ja) * 1997-06-18 1999-01-12 Olympus Optical Co Ltd スパッタリングターゲット及び薄膜の製造方法
JPH11106910A (ja) * 1997-10-03 1999-04-20 Olympus Optical Co Ltd 薄膜の成膜方法
JP2000086344A (ja) * 1998-09-14 2000-03-28 Kyocera Corp 高密度フッ化物焼結体およびその製造方法並びにそれを用いた半導体製造装置用部材
JP2000239066A (ja) * 1999-02-22 2000-09-05 Kyocera Corp 耐食性部材およびその製造方法、並びにそれを用いたプラズマ処理装置用部材
JP2000282233A (ja) * 1999-04-02 2000-10-10 Canon Inc 光学薄膜成膜方法および光学薄膜

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