US3373278A - Determination of vapor coating rate by x-rays emitted from said vapor - Google Patents

Determination of vapor coating rate by x-rays emitted from said vapor Download PDF

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Publication number
US3373278A
US3373278A US423764A US42376465A US3373278A US 3373278 A US3373278 A US 3373278A US 423764 A US423764 A US 423764A US 42376465 A US42376465 A US 42376465A US 3373278 A US3373278 A US 3373278A
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United States
Prior art keywords
vapor
coating
rays
determination
density
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US423764A
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English (en)
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Frank F Cilyo
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United States Steel Corp
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United States Steel Corp
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Priority to US423764A priority Critical patent/US3373278A/en
Priority to FR43769A priority patent/FR1461909A/fr
Priority to NL6517043A priority patent/NL6517043A/xx
Priority to GB55497/65A priority patent/GB1126001A/en
Priority to BE674605A priority patent/BE674605A/xx
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Publication of US3373278A publication Critical patent/US3373278A/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • 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
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate
    • C23C14/544—Controlling the film thickness or evaporation rate using measurement in the gas phase
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/2209—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using wavelength dispersive spectroscopy [WDS]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/076—X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/079—Investigating materials by wave or particle radiation secondary emission incident electron beam and measuring excited X-rays
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/61—Specific applications or type of materials thin films, coatings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/638—Specific applications or type of materials gas

Definitions

  • Vapor density may be correlated with deposition rate, which in turn determines coating thickness at a given speed of travel of the substrate.
  • the vapor density is determined by X-ray measurement.
  • the energy source for the X-rays may be independent of the energy source for evaporation of coating material. However, if the latter energy source is adapted to generate the required X-rays, it may perform the dual function of evaporation and X-ray production.
  • This invention relates to vapor deposition of coatings, generally in vacuum, and is particularly concerned with apparatus and method for measurement of the vapor density of the coating material, prior to deposition, for use in control of coating thickness.
  • the invention is especially advantageous in a continuous process, such as the coating of strip material which continuously moves through the vapor-deposition zone.
  • the invention is particularly applicable to thickness control in the vacuum-coating of steel strip with aluminum.
  • the invention assumes its simplest form when employed in conjunction with apparatus wherein the coating vapor is evaporated from its source by a high-energy beam, such as that from an electron gun, which beam is capable of generating characteristic X-rays when it contacts evolved Vapor.
  • a high-energy beam such as that from an electron gun, which beam is capable of generating characteristic X-rays when it contacts evolved Vapor.
  • a measurement of the molecular vapor density of the material being deposited may be correlated with the deposition rate, and resulting coating thickness. Accordingly, a purpose of the invention is to provide means and procedures for the ready determination of the vapordensity measurements required, taking into account online problems in industrial coating installations, in order to provide a basis for process control of the factors affooting coating thickness.
  • the latter may include, for eX- ample strip speed and rate of evaporation of coating component.
  • the vapor-density measurement of the invention is based on the principie that characteristic X-rays are produced when atoms of matter are bombarded by energetic particles, such as an electron beam, or other forms of energy.
  • the Wave length of the characteristic X-rays depends primariiy on the atomic structure of the material being bombarded.
  • the elements with low atomic weights are characterized by long Wave lengths that can be produced with low-energy beams; however, high-energy beams are necessary to produce the short wave lengths that characterize the elements with higher atomic numbers.
  • the intensity of the characteristic X-rays depends primarily upon the number of atoms that the energy beam intercepts, the atomic number of the material, and the energy of the incident beam.
  • the intensity of the characteristic X-rays will depend only on the density of the vapor emitted from the coating-material source. Since in vapor-deposition applications, an increased rate of evaporation of material from 3,373,278 Patented Mar. 12, 1968 the coating source results in increased vapor density, a measurement of this density constitutes a measurement of the evaporation rate, and the correlative rate and thickness of coating deposition, under given conditions.
  • FIGURE 1 schematically depicts a typical vacuumcoating operation incorporating applicants invention
  • FIGURE 2 illustrates a modification of applicants invention suitable for use with the deposition arrangement of FIGURE 1, as well as in other situations where a separate source of energy beam may be advantageous.
  • an electron gun 1 generates an electron beam 2 that is bent by a magnetic field, not shown, in a semi-circular pattern to heat and melt the evaporant 3 in crucible 4. Portions of the resulting coating vapor 5 will flow toward strip 6, under thermal influence, where they deposit to form the desired coating.
  • the electron beam 2 contacts the atoms of the coating vapor, as at points,7, with resulting production of the aforementioned characteristic X-rays 8.
  • the X-ray detector 9 picks up a portion of these X-rays, which enter through aperture 9a provided with collimator slits.
  • the X-ray detector may take many forms, although it preferably should be capable of operation in high vacuum.
  • the output of the detector is fed to conventional measuring and control equipment, adapted to amplify the detector output, eliminate scattered rays, and count the characteristic rays from the coating material.
  • This equipment, including the detector may be that shown in Norelco X-ray Instrument Brouchure, RC-212B 5M1 159 published by the Philips Electronics and Pharmaceuticals Industries Corporation of Mount Vernon, NY.
  • Detector 9 for example, may be of the type incorporated in the universal X-ray spectrograph 52360, which is provided with collimator slits.
  • the coating operation is conducted in a vacuum, apparatus for production of which is conventional, and not shown.
  • the achievement of the bent electron beam, as shown and described, may be by various methods, and details of one mode thereof maybe obtained, for example, from Patent No. 3,046,936 of John C. Simons, In, dated July 31, 1962.
  • FIGURE 2 In instances where a separate electron beam may be necessary for X-ray production, for vapor-density measuring purposes, the modification shown in FIGURE 2 is applicable, wherein an electron gun I is positioned in housing 10 which has apertures 10a for passage of an electron beam therethrough to anode 1a. Housing It) also has aperture 10b, which is oriented with its axis of flow opening generally parallel to the flow path of coating vapor, to permit passage of sample portions of coating vapor 5 therethrough, on its way from the vapor source, not shown, to the base material to be coated, not shown.
  • the device is arranged to permit contact of electron beam 2 with the coating vapor, as at points 7, with resulting production of characteristic X-rays 8, a portion of which enter detector 9 through collimator 9a.
  • the detector and related measurement and control equipment may be that described in conjunction with FIGURE 1.
  • Apparatus for vapor deposition of coatings on a substrate moving at a known speed comprising (a) means for forming a coating vapor;
  • means for measurement of density of coating vapor to permit coatingthickness determination comprising a highenergy beam of electrons and the like, adapted to'contact coating vapor and produce characteristic X-rays upon such contact, and means for measuring a predetermined sampling of said X-rays, which said high-energy beam is adapted to evaporate the coating material to form coating vapor.
  • means for measurement of density of coating vapor to permit coating-thickness determination comprising a high-energy beam of electrons and the like, adapted to contact coating vapor and produce characteristic X-rays upon such contact, and means for measuring a predetermined sampling of said X-rays
  • said means further comprising a housing having an aperture adapted to permit passage of sample portions of coating vapor therethrough on its way from the vapor source to the material to be coated, said aperture being oriented with its axis of flow generally parallel to the flow path of said coating vapor, said housing being provided with means adapted to permit said high-energy beam to pass transversely of said coating-vapor aperture and means for said sample X-rays to enter said measuring means.
  • a method for vapor deposition of coatings comprising (a) providing a coating vapor;
  • the method of measurement of density of coating vapor in a vapor-coating apparatus, to permit coatingthickness determination comprising contacting said vapor with a high-energy beam of electrons and the like, adapted to produce characteristic X-rays upon such contact, and measuring a predetermined sampling of said X-rays to determine coating-vapor density, which said high-energy beam evaporates the coating material to form coating vapor.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Immunology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Length-Measuring Devices Using Wave Or Particle Radiation (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
US423764A 1965-01-06 1965-01-06 Determination of vapor coating rate by x-rays emitted from said vapor Expired - Lifetime US3373278A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US423764A US3373278A (en) 1965-01-06 1965-01-06 Determination of vapor coating rate by x-rays emitted from said vapor
FR43769A FR1461909A (fr) 1965-01-06 1965-12-27 Procédé et appareil pour déterminer par les rayons x la vitesse de dépôt d'un revêtement à partir d'une vapeur
NL6517043A NL6517043A (nl) 1965-01-06 1965-12-28
GB55497/65A GB1126001A (en) 1965-01-06 1965-12-31 Determination of vapor coating rate by x-rays
BE674605A BE674605A (nl) 1965-01-06 1965-12-31

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US423764A US3373278A (en) 1965-01-06 1965-01-06 Determination of vapor coating rate by x-rays emitted from said vapor

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BE (1) BE674605A (nl)
FR (1) FR1461909A (nl)
GB (1) GB1126001A (nl)
NL (1) NL6517043A (nl)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3590777A (en) * 1969-03-13 1971-07-06 United Aircarft Corp Ingot feed drive
US3612859A (en) * 1968-01-31 1971-10-12 Westinghouse Electric Corp Method for measuring and controlling the density of a metallic vapor
US3667421A (en) * 1970-09-17 1972-06-06 United Aircraft Corp Mechanism for controlling the thickness of a coating in a vapor deposition apparatus
US3984581A (en) * 1973-02-28 1976-10-05 Carl Zeiss-Stiftung Method for the production of anti-reflection coatings on optical elements made of transparent organic polymers
FR2339857A1 (fr) * 1976-01-30 1977-08-26 Leybold Heraeus Inficon Methode et dispositif de controle de processus d'evaporation
US4098919A (en) * 1974-06-10 1978-07-04 Futaba Denshi Kogyo K.K. Process for producing a thin fluorescent film for electroluminescence
WO1981002419A1 (en) * 1980-02-26 1981-09-03 Western Electric Co Methods of controlling the index profile of optical fiber preforms
WO1995012008A1 (de) * 1993-10-27 1995-05-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum elektronenstrahlbedampfen mit mehrkomponentigem verdampfungsmaterial
US5754297A (en) * 1994-01-28 1998-05-19 Applied Materials, Inc. Method and apparatus for monitoring the deposition rate of films during physical vapor deposition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2125541B (en) * 1982-08-13 1986-02-12 Inst Tzvetna Metalurgia Method and device for determination of dust content in dust gas flow
FR3089299B1 (fr) * 2018-11-29 2021-06-04 Commissariat Energie Atomique Methode d’analyse de fumees d’evaporation, produit programme d’ordinateur, systeme d’analyse et installation de fabrication additive associes
WO2020104744A1 (fr) * 2018-11-20 2020-05-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Methode d'analyse de fumees d'evaporation, produit programme d'ordinateur, systeme d'analyse et installation de fabrication additive associes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230110A (en) * 1962-01-22 1966-01-18 Temescal Metallurgical Corp Method of forming carbon vapor barrier
US3246146A (en) * 1963-07-11 1966-04-12 Ass Elect Ind Apparatus for the X-ray analysis of a liquid suspension of specimen material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230110A (en) * 1962-01-22 1966-01-18 Temescal Metallurgical Corp Method of forming carbon vapor barrier
US3246146A (en) * 1963-07-11 1966-04-12 Ass Elect Ind Apparatus for the X-ray analysis of a liquid suspension of specimen material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3612859A (en) * 1968-01-31 1971-10-12 Westinghouse Electric Corp Method for measuring and controlling the density of a metallic vapor
US3590777A (en) * 1969-03-13 1971-07-06 United Aircarft Corp Ingot feed drive
US3667421A (en) * 1970-09-17 1972-06-06 United Aircraft Corp Mechanism for controlling the thickness of a coating in a vapor deposition apparatus
US3984581A (en) * 1973-02-28 1976-10-05 Carl Zeiss-Stiftung Method for the production of anti-reflection coatings on optical elements made of transparent organic polymers
US4098919A (en) * 1974-06-10 1978-07-04 Futaba Denshi Kogyo K.K. Process for producing a thin fluorescent film for electroluminescence
FR2339857A1 (fr) * 1976-01-30 1977-08-26 Leybold Heraeus Inficon Methode et dispositif de controle de processus d'evaporation
WO1981002419A1 (en) * 1980-02-26 1981-09-03 Western Electric Co Methods of controlling the index profile of optical fiber preforms
US4292341A (en) * 1980-02-26 1981-09-29 Bell Telephone Laboratories, Incorporated Method of controlling the index profile of optical fiber preforms
WO1995012008A1 (de) * 1993-10-27 1995-05-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum elektronenstrahlbedampfen mit mehrkomponentigem verdampfungsmaterial
US5754297A (en) * 1994-01-28 1998-05-19 Applied Materials, Inc. Method and apparatus for monitoring the deposition rate of films during physical vapor deposition

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Publication number Publication date
BE674605A (nl) 1966-06-30
NL6517043A (nl) 1966-07-07
GB1126001A (en) 1968-09-05
FR1461909A (fr) 1966-12-09

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