WO2007105674A1 - Procede de fabrication par depot d'aerosol d'un corps forme a partir d'un film - Google Patents

Procede de fabrication par depot d'aerosol d'un corps forme a partir d'un film Download PDF

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Publication number
WO2007105674A1
WO2007105674A1 PCT/JP2007/054789 JP2007054789W WO2007105674A1 WO 2007105674 A1 WO2007105674 A1 WO 2007105674A1 JP 2007054789 W JP2007054789 W JP 2007054789W WO 2007105674 A1 WO2007105674 A1 WO 2007105674A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
film
raw material
fine particles
incident angle
Prior art date
Application number
PCT/JP2007/054789
Other languages
English (en)
Japanese (ja)
Inventor
Michiyori Miura
Seiichi Yokoyama
Original Assignee
Hoya Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoya Corporation filed Critical Hoya Corporation
Publication of WO2007105674A1 publication Critical patent/WO2007105674A1/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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/214—Al2O3
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/17—Deposition methods from a solid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • C03C2218/328—Partly or completely removing a coating
    • C03C2218/33—Partly or completely removing a coating by etching

Definitions

  • the present invention relates to a method for manufacturing a film-thickness film with a film thickness using an aerosol deposition method.
  • the aerosol deposition method (hereinafter referred to as the AD method) is a ceramic having a particle size of several tens of nanometers to several ⁇ m, or a mixture of raw materials such as fine metal particle particles mixed with gas.
  • a film is formed by spraying onto a substrate through a nozzle.
  • the AD method has attracted attention as a method capable of forming a dense film having the same crystal structure as that of fine particles as a raw material at a low substrate temperature and at a high film formation rate.
  • FIG. 6 is a schematic diagram showing the basic configuration of the film forming apparatus.
  • 61 is a deposition substrate
  • 62 is an XY stage that moves the deposition substrate 61
  • 63 is a nozzle
  • 64 is a deposition channel
  • 65 is a classifier
  • 66 is an aerosol generator
  • 67 is a high-pressure gas supply.
  • the raw material fine particles that also have ceramics or metal power are mixed with a carrier gas (not shown) supplied through a mass flow controller 68 inside the aerosol generator 66 to be aerosolized.
  • a carrier gas not shown
  • the inside of the film forming chamber 64 is depressurized to about 50 Pa by a vacuum pump (not shown), and the raw material aerosolized by the gas flow generated by the differential pressure between this pressure and the pressure inside the aerosol generator 66.
  • the fine particles are introduced into the film forming chamber 64 through the classifier 65, accelerated through the nozzle 63, and sprayed onto the film forming substrate 61.
  • the raw material particles transported by the gas are accelerated to several hundred mZs by passing through a nozzle with a fine opening of 1 mm or less.
  • the average particle size of the fine particles is 50 nm or more, and the shape thereof is an aspherical amorphous shape. It is disclosed that by forming a shape with corners beyond the force point, the impact force at the time of the substrate collision is concentrated on the corners, and the crushing of the raw material fine particles is promoted, resulting in a dense film formation. Has been.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-73855
  • the first means provided by the present invention is:
  • Aerosol deposition in which the raw material fine particles are mixed with a carrier gas to form an aerosol, and together with the carrier gas, the raw material fine particles are accelerated through a nozzle and sprayed toward the surface of the substrate to be deposited to form a film in a vacuum chamber.
  • the substrate incident angle of the raw material fine particles sprayed from the nozzle to the deposition surface of the deposition substrate is approximately 0 degrees, and only the substrate incidence angle and the etching effect at which the etching effect is manifested are manifested.
  • the method for producing a film-deposited body by the aerosol deposition method is characterized in that the film is formed while being changed up to an arbitrary angle in a range between the substrate incident angle and the substrate incident angle.
  • the second means provided by the present invention includes:
  • a change in the substrate incident angle is continuous and periodic, and is a method for manufacturing a film-formed body by an aerosol deposition method.
  • the third means provided by the present invention includes:
  • the change in the incident angle of the substrate is intermittent and periodic.
  • FIG. 7 is a schematic diagram schematically showing a cross-sectional structure of a film formed under a condition where the carrier gas flow rate is constant, in which 71 is a substrate, 72 is a film formation layer, and 73 is a green compact layer. It is.
  • the structure of the film prepared under the condition that the carrier gas flow rate is constant and the substrate incident angle of the raw material fine particles substantially coincides with the normal direction of the surface of the substrate 71 is as shown in FIG.
  • the diameter of the particles constituting the film forming body layer 72 was about 1Z10 to 1Z5, which is the particle diameter of the raw material fine particles.
  • the green compact layer 73 as the distance from the substrate 71 increases (as the film thickness increases), both the number and size of voids increase and the size of the particles constituting the green compact layer increases. It became clear that the diameter also increased and finally became the same as the particle diameter of the raw material fine particles. It is also clear that the boundary between the film-forming body layer 72 and the green compact layer 73 is not clearly distinguishable, and that the film-forming body layer force and the structure change to the green compact layer occur continuously. It became power.
  • the cause of the formation of the green compact layer 73 is that the raw material fine particles are crushed as the film thickness is increased. It means both crushing itself and crushing raw material particles already attached to the substrate surface. It turns out that it is difficult to live.
  • the cause of the crushing of the raw material fine particles is an impact force accompanying the release of the kinetic energy of the raw material fine particles at the time of the substrate collision, and the kinetic energy of the raw material fine particles is determined by the substrate collision speed. Is done.
  • the substrate collision speed of the raw material fine particles is determined by the flow rate of the carrier gas, the substrate collision speed of the raw material fine particles is always constant when the film is formed under a condition where the carrier gas flow rate is constant. Sometimes the kinetic energy solved is also constant. Therefore, ideally, crushing of the raw material fine particles should occur in the same manner regardless of the formed film thickness.
  • FIG. 8 is a diagram schematically showing the relationship between the pressure generated by the substrate collision of the raw material fine particles and the strain generated in the film forming body layer and the green compact layer.
  • the pressure (stress) and strain increase linearly according to the pressure in the region where the pressure is low (in the figure, the elastic deformation region).
  • the strain does not follow the pressure increase, and eventually breaks up (breaking point in the figure).
  • the pressure required for the occurrence of crushing hereinafter referred to as the following
  • the critical pressure is also increasing.
  • uncrushed raw material fine particles adhering to the substrate surface or fine particles that are insufficiently crushed are used as a source for forming the green compact layer. Need to be removed.
  • uncrushed raw material fine particles or fine particles that are not sufficiently crushed are considered to have a low adhesive force with the substrate surface or a film formed on the substrate, and can be removed relatively easily. Conceivable.
  • the present invention provides an etching effect of raw material fine particles incident on a substrate described below. Focusing on the fruit, it is intended to form a dense film body while removing uncrushed raw material fine particles or fine particles that are not sufficiently crushed.
  • 3 to 5 show the influence of the incident direction of the raw material fine particles, in other words, the incident angle.
  • FIG. 3a is a schematic diagram showing the relationship between the incident direction and the incident angle of the raw material fine particles, in which 31 is a substrate, 32 is a film formed, 33 is a nozzle, 34 is a nozzle opening, and 35 is Raw material fine particles ejected from the nozzle opening 34.
  • Fig. 3b schematically shows the shape of the film formed for a fixed time with the substrate position fixed.
  • 36 is the shape of the film formation body
  • 37 is a uniform film thickness line
  • P is the point where the thickest point is projected onto the substrate.
  • the incident direction of the raw material fine particles means a direction parallel to a straight line connecting the point P and the center of the nozzle opening 34 and toward the point P from the nozzle opening 34.
  • the substrate incident angle here means the angle ⁇ formed by the normal direction of the substrate surface and the incident direction, as shown in FIG. 3a.
  • FIG. 4 shows the relationship between the substrate incident angle and the film thickness of the film-deposited film formed for a certain period of time.
  • the arrow in the figure corresponds to the case where the carrier gas flow rate is small, and the mouth mark corresponds to the case where the carrier gas flow rate is large.
  • the film thickness is standardized by the film thickness obtained when the film is formed with a substrate incident angle of 0 degree.
  • the substrate incident angle exceeds 20 degrees, the film thickness of the film formation starts to decrease sharply, and when the carrier gas flow rate is small, the decrease is when the flow rate is large. Smaller than that. It is estimated that this is because the etching effect of particles incident on the substrate becomes obvious as the substrate incident angle increases.
  • FIG. 5 shows the relationship between the amount of decrease in film thickness and the incident angle after the raw material fine particles are allowed to enter the substrate for a certain period of time after forming a film-forming body having a certain film thickness.
  • the mark in the figure corresponds to the case where the carrier gas flow rate is small
  • the mouth mark corresponds to the case where the carrier gas flow rate is large.
  • the film thickness reduction amount of 0 means both the case where the film thickness does not decrease and the case where the raw material fine particles incident on the substrate are deposited and the film thickness is increased. .
  • the substrate incident angle at which the etching effect becomes apparent for example, the substrate incident angle at which the film thickness starts to decrease in FIG. 4 is referred to as “substrate incident angle at which the etching effect becomes apparent”.
  • substrate incident angle at which the etching effect becomes obvious both etching and film deposition occur simultaneously.
  • the substrate incident angle at which only the etching effect appears for example, in FIG. 5, the angle at which the film thickness begins to decrease is referred to as the “substrate incident angle at which only the etching effect appears”.
  • the substrate incident angle where only the etching effect is manifested film deposition does not occur and only etching proceeds.
  • the substrate incident angle at which the etching effect is manifested, and the substrate incident angle at which only the etching effect is manifested are not constant, but vary depending on, for example, the carrier gas flow rate.
  • the etching effect of the raw material fine particles can be controlled by appropriately selecting the substrate incident angle of the raw material fine particles and the carrier gas flow rate for the AD method.
  • the object of the present invention is to form the film while changing the substrate incident angle of the raw material fine particles ejected from the nozzle, thereby reconciling the above-mentioned etching effect and deposition effect, and the source of the formation of the green compact layer. In this way, it removes uncrushed raw material particles adhering to the substrate surface, or fine particles that are not sufficiently crushed, and does not form a film with a large thickness and excellent density. is there.
  • FIG 1 and 2 are schematic diagrams showing an embodiment of the present invention.
  • FIG. 1 is a diagram schematically showing how the angle formed between the nozzle and the substrate during film formation changes.
  • 11 is a nozzle
  • 13 is raw material fine particles ejected from the first nozzle.
  • the arrows and block arrows in the figure indicate the incident direction of the raw material particles 13 to the substrate, and (1), (2), (3), and (4) are added to the block arrows to indicate the order in which the substrates rotate. It is shown. That is, at the start of film formation, as shown in FIG. La, the raw material fine particles 13 are incident from a direction substantially perpendicular to the film formation surface of the substrate 21 and film formation is performed for a certain time.
  • the substrate 21 rotates clockwise and stops when the desired angle is reached, and film formation is performed for a certain period of time in this state (corresponding to FIG. 1 lb).
  • the substrate 21 is rotated again counterclockwise, is stationary in the state shown in FIG. La, and film formation is performed for a certain time.
  • the substrate 21 rotates counterclockwise and stops when a desired angle is reached, and film formation is performed for a certain time in this state (corresponding to FIG. 1c).
  • the substrate 21 rotates again clockwise, stops in the state shown in FIG. La, and film formation is performed for a certain time.
  • FIG. 2 shows this as a relationship between the film formation time and the incident angle of the raw material fine particles 13.
  • “0” corresponds to the case of FIG. La in which the raw material fine particles are incident on the substrate from the direction orthogonal to the substrate surface
  • the positive and negative maximum corresponds to, for example, the cases of FIG. Lb and FIG. Figure 2a shows the case where the substrate incident angle changes intermittently
  • Figure 2b shows the case where the same angle changes continuously.
  • the film formation can be continued or interrupted while the substrate is rotated.
  • the substrate incident angle of the raw material fine particles 13 is changed, and the state in which film deposition is preferentially performed and the etching effect becomes apparent or the etching is realized.
  • the film is formed while removing the uncrushed raw material fine particles adhering to the surface of the film forming body or particles that are not sufficiently crushed. The film is blocked and a dense film is formed.
  • Which region should be selected as the maximum or minimum value of the substrate incident angle, in other words, whether to select the substrate incident angle at which only the etching effect appears or the substrate incident angle at which the etching effect manifests It should be selected as appropriate depending on the type of raw material fine particles and the ease with which a green compact is produced.
  • Alumina particles having an average particle size of 0.7 ⁇ m were used as the raw material fine particles, and air was used as the carrier gas.
  • the nozzle opening of the nozzle is 5 nm X O. 3 nm, and the substrate used is quartz glass.
  • the carrier gas flow rate is 4 lZmin.
  • the fine alumina particles injected from the nozzle The substrate collision velocity of the particles was 240 mZs, and the deposition rate was ⁇ 5 ⁇ mZmin when the substrate incident angle of the alumina fine particles was 0 degree.
  • film formation was performed using alumina particles having an average particle size of 0.7 ⁇ m as the raw material fine particles and air as the transport gas.
  • the nozzle opening of the nozzle is 5 nm X O. 3 nm, and the substrate used is quartz glass.
  • the carrier gas flow rate is 4 lZmin
  • the substrate collision speed of the alumina fine particles injected from the nozzle cap at this time is 240 mZs, and when the substrate incident angle of alumina fine particles is 0 degree, the deposition rate is ⁇ 5 / z mZmin.
  • the angle is 25 degrees, it is ⁇ 4 ⁇ mZ min.
  • the substrate incident angle at the start of film formation was set to 0 degree, and the substrate incident angle was changed in the manner shown in Fig. 2a. That is, the substrate incident angle is kept at 0 degree, the film is formed for 2 minutes, the substrate incident angle is set to 25 degrees, the film is formed in the same manner for 2 minutes, and then the substrate incident angle is again set to 0 degree. By repeating the cycle of film formation for 2 minutes, a 40 m-thick alumina film was formed. The time required to change the incident angle was about 10 seconds.
  • a 40 ⁇ m-thick alumina film was formed under the same conditions as in Example 1. However, the substrate incident angle was changed to a sine wave as shown in Fig. 2b. The amplitude was 30 degrees (in this case the deposition rate was ⁇ 3 ⁇ mZmin) and the period was 3 minutes.
  • the film forming method according to the present invention is useful for stably producing a film-forming body having a thickness of more than 30 ⁇ m by using the AD method, and a component using the film-forming body, It can be used in industrial fields related to materials.
  • FIG. 1 is a diagram schematically showing a change in the substrate incident angle during film formation.
  • FIG. 2 is a schematic diagram showing a relationship between a film formation time and a substrate incident angle.
  • ⁇ 3 It is a schematic diagram for explaining the substrate incident angle.
  • FIG. 4 is a diagram showing a relationship between a film thickness of a film-formed body and a substrate incident angle.
  • FIG. 5 is a diagram showing the relationship between the film thickness reduction amount and the substrate incident angle.
  • FIG. 6 It is a schematic diagram showing the basic configuration of a film forming apparatus using the AD method.
  • FIG. 7 A schematic view schematically showing a cross-sectional structure of a sample formed by the AD method.
  • FIG. 8 is a diagram schematically showing the relationship between the pressure generated by substrate collision of raw material fine particles and the strain generated in the film formation layer and the green compact layer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

La présente invention concerne un procédé permettant de fabriquer de manière stable, par dépôt d'aérosol, un corps formé à partir d'un film avec une épaisseur de film supérieure à 30 µm. L'angle incident des microparticules de matière brute pulvérisées par une buse sur un substrat de dépôt est modifié, ce qui permet de fabriquer le corps formé à partir d'un film tout en ajustant l'équilibre entre l'attaque et le dépôt du film.
PCT/JP2007/054789 2006-03-13 2007-03-12 Procede de fabrication par depot d'aerosol d'un corps forme a partir d'un film WO2007105674A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006068420A JP2009132944A (ja) 2006-03-13 2006-03-13 エアロゾルデポジション法による成膜体の形成方法
JP2006-068420 2006-03-13

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WO2007105674A1 true WO2007105674A1 (fr) 2007-09-20

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TW (1) TW200741032A (fr)
WO (1) WO2007105674A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2636771A4 (fr) 2010-11-02 2014-10-08 Ngk Insulators Ltd Procédé de production de cristal

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001003180A (ja) * 1999-04-23 2001-01-09 Agency Of Ind Science & Technol 脆性材料超微粒子成形体の低温成形法
JP2001038274A (ja) * 1999-05-21 2001-02-13 Agency Of Ind Science & Technol 超微粒子材料平坦化成膜方法
JP2005076104A (ja) * 2003-09-02 2005-03-24 Toto Ltd 複合構造物作製装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001003180A (ja) * 1999-04-23 2001-01-09 Agency Of Ind Science & Technol 脆性材料超微粒子成形体の低温成形法
JP2001038274A (ja) * 1999-05-21 2001-02-13 Agency Of Ind Science & Technol 超微粒子材料平坦化成膜方法
JP2005076104A (ja) * 2003-09-02 2005-03-24 Toto Ltd 複合構造物作製装置

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TW200741032A (en) 2007-11-01

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