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WO1998037254A2 - Films minces - Google Patents

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Publication number
WO1998037254A2
WO1998037254A2 PCT/GB1998/000556 GB9800556W WO9837254A2 WO 1998037254 A2 WO1998037254 A2 WO 1998037254A2 GB 9800556 W GB9800556 W GB 9800556W WO 9837254 A2 WO9837254 A2 WO 9837254A2
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
aluminium
film
oxygen
nitrogen
Prior art date
Application number
PCT/GB1998/000556
Other languages
English (en)
Other versions
WO1998037254A3 (fr
Inventor
Frank Placido
Original Assignee
The Court Of The University Of Paisley
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 The Court Of The University Of Paisley filed Critical The Court Of The University Of Paisley
Priority to AU63011/98A priority Critical patent/AU6301198A/en
Priority to EP98907020A priority patent/EP1000182A2/fr
Publication of WO1998037254A2 publication Critical patent/WO1998037254A2/fr
Publication of WO1998037254A3 publication Critical patent/WO1998037254A3/fr

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • C23C14/0676—Oxynitrides
    • 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
    • C23C14/548—Controlling the composition
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

Definitions

  • This invention relates to thin films .
  • Thin film materials have attractive properties for applications in security printing of banknotes, credit cards, telephone cards, smart cards, etc.
  • thin films can have highly individual and characteristic reflection properties which are easily recognised by eye, which makes automated recognition a possibility.
  • Thin film pigments can be produced where the colour changes with the viewing angle, making it impossible to duplicate these pigments with normal colour copiers or printers.
  • a film which highly reflects light in one given wavelength range while not reflecting light in a different wavelength range.
  • the reflecting wavelength range is varied by controlling the growth and composition of the film, allowing different, distinguishable films to be produced.
  • Thin film coatings have been used to protect vulnerable surfaces and to extend the lifetime of sharpedged tools such as drill bits and knifes.
  • a variety of durable materials have been used for this purpose previously, these materials include titanium nitride and tungsten carbide.
  • a limitation of some other materials with desirable properties such as aluminium oxide and aluminium nitride is the tendency to fail as coatings because of inherent stresses in the thin films which lead to cracking or buckling of the coatings.
  • the ideal material would be one whose refractive index could be varied continuously over a large range although the so-called "digital" technique in which a high-low pair is used to approximate a continuous index range has been used with success.
  • a thin film comprising successive layers of aluminium oxide, aluminium oxynitride and aluminium nitride.
  • the thin film is stress matched to a substance to which it is applied.
  • the thin film is stress free.
  • the layers are such that the composition of the film varies generally sinusoidally with depth.
  • the thin film preferably .has a refractive index which varies, preferably sinusoidally between 1.6 and 2.2.
  • the refractive index varies between 1.6 and 2.0.
  • the thin film is transparent at thicknesses of up to 9 microns .
  • the invention further provides a method for producing a thin film on a substrate depositing aluminium in an atmosphere of oxygen and/or nitrogen, and varying the oxygen to nitrogen ratio to allow a film of aluminium oxide and/or aluminium nitride and/or aluminium oxynitride to be obtained as necessary.
  • oxygen to nitrogen ratio is also present in said atmosphere.
  • the deposition is performed at room temperature.
  • the deposition may be by sputtering which may be reactive d.c, reactive low frequency or reactive radio frequency sputtering.
  • the low frequency sputtering has a power supply operating in the kilohertz region.
  • the aluminium atoms may be removed from the aluminium target by a noble gas plasma.
  • Optionally reactive sputtering of the aluminium atoms may be achieved solely in the presence of nitrogen and/or oxygen.
  • the flow rates of the noble gas may be in the range of 0 - 100 seem.
  • the noble gas may be argon.
  • the aluminium atoms may react with oxygen and/or nitrogen to form a film or coating on a suitable surface.
  • the variation of the oxygen/nitrogen ratio is effected by varying the relative flow rates of the oxygen and nitrogen while maintaining the field strength of the reactive radio frequency.
  • the flow rates of the oxygen and nitrogen may be typically in the range of 0 - 10 seem (standard cubic centimetres per minute) .
  • the thin film produced by the method of the invention consists solely of aluminium nitride.
  • oxygen and nitrogen flow rates are varied generally sinusoidally in anti-phase.
  • the deposition rate is in the range of 100-800 nm per hour.
  • the deposition rate is in the range of 100-400 nm per hour.
  • a pigment comprising a thin film as previously defined.
  • the thin film may be ground to a suitable particle size to achieve the desired spectral properties.
  • the thin film can be incorporated into a suitable carrier material to form a paint.
  • the carrier material is transparent such that the resulting paint retains the same characteristic features of the original films.
  • the invention provides a stress matched thin film for coating a diamond surface.
  • the diamond surface can be of a natural or man-made diamond.
  • the stress matched thin film can be varied in composition to provide a surface with stress characteristics which match those stress characteristics of another material to which the diamond surface can be attached.
  • the thin film can be used to allow diamond surfaces to be attached to tools.
  • the diamond surface can be coated with a thin film which confers thermal protection to the diamond.
  • the invention provides a filter comprising a thin film as previously defined wherein the filter has high transmission except for a narrow region centred on wavelength ⁇ 0 .
  • the filter may be used as or in laser goggles , laser rejection filters, laser mirrors, head-up displays or any other suitable application.
  • the invention provides the use of a thin film as previously defined to coat and protect vulnerable surfaces from chemical attack and/or to extend the lifetime of tools, for example, tools with sharp working edges .
  • the surfaces may include metals, dielectrics, semiconductors and plastics.
  • the thin film can be used to allow an additional coating of diamond to be applied to the surface.
  • Fig 1 is a graph that illustrates how transmission var i es as ⁇ 0 var j_ es with the number of deposition cycles.
  • Fig 2 is a graph that illustrates both the calculated and the measured transmission of the films.
  • Figs 3 (a), (b) and (c) are spectra which illustrate depth profiling of a thin film using X-ray Photon Spectroscopy (XPS) of 0 Is, N Is and Al 2p binding energies.
  • XPS X-ray Photon Spectroscopy
  • Figure 1 shows how the transmission varies as ⁇ 0 varies with the number of cycles deposited for the following parameters , which are in a range appropriate to the aluminium oxynitride films .
  • Figure 2 shows the experimental realisation (full line) of such a filter on glass. After measurement of the transmission the films are broken and the thickness measured on a Hitachi S4100 field emission scanning electron microscope (SEM) .
  • SEM field emission scanning electron microscope
  • the dotted line in Fig. 2 is calculated spectrum, using the measured cycle thickness and the measured ⁇ to calculate n from Equn.2 (see Example 3) and adjusting nrange for a g ⁇ ood fit to the sp*-ectral width.
  • the calculation takes into account the glass absorption, but assumes the oxynitride films to be dispersion free.
  • the fit to the side lobes is very sensitive to the assumed starting phase of the sine wave, but is also sensitive to the end layer at the film-air boundary (the end phase of the sine wave in a sense) .
  • the spectrum in Fig.2 has 35.4 cycles and ⁇ has been adjusted for a good fit to the sidelobes.
  • Figure 3 shows that these films are varying continuously in composition and hence in refractive index since alternating layers of aluminium oxide and aluminium nitride with thicknesses close to quarter waves can show similar optical performance.
  • X-ray Photon Spectroscopy shows that the oxygen Is and nitrogen Is peaks vary sinusoidally and in antiphase with depth from the surface.
  • the aluminium 2p peak in contrast, is of constant height but varies in energy with depth. This is consistent with the composition of the film varying continuously from aluminium oxide to aluminium nitride.
  • the observed Al 2p shift varies by around 2.9 eV.
  • the aluminium peak is a single peak which varies in position rather than two peaks with varying heights which supports the conclusion that aluminium oxynitrides are continuously variable compounds rather than a mixture of phases of aluminium oxide and aluminium nitride.
  • This invention relates to the growth of aluminium oxynitride films where the composition is varied continuously from Al 0 to AlN through intermediate compositions A10xNy .
  • This material has a number of highly desirable properties being hard, wear-resistant, adhering strongly to a variety of substrates, transparent to around 9 microns with low absorption, resistant to chemical attack and offers a potential refractive index range of 1.6 to over 2.2. Additionally, this invention provides for high quality rugate filters, pigments and durable, chemical resistant coatings in which the refractive index varies sinusoidally with thickness.
  • a target of aluminium typically a disk of diameter 200 mm.
  • stress-free coatings of hard, wear- resistant, adherent coatings can be deposited on a wide variety of surfaces including metals, dielectrics, semiconductors and plastics by co-depositing aluminium oxide and aluminium nitride whereby inherent stresses are cancelled. This can be done as sequential layers of aluminium oxide and aluminium nitride or as layer of layers of aluminium oxynitride.
  • a removable shutter can be positioned between the substrates and the target and/or a means for moving the substrates into and out of the sputtering position is also commonly used.
  • the chamber is evacuated by suitable vacuum pumps, preferably to a residual vacuum of the order of 10 " torr.
  • the chamber is then filled with a noble gas, typically argon, to a pressure which is typically in the range of 1 - 10 millitorr.
  • a plasma discharge is created by means of a radio- frequency power supply, typically 1 kilowatt in power, for a 200 mm diameter aluminium target. After some time, typically 30 minutes with the shutter obscuring the substrates or having moved the substrates out of the sputtering position, the surface of the target will be conditioned by the plasma and suitable amounts of the reactive gases, oxygen and nitrogen can be added to the noble gas to commence reactive sputtering.
  • a radio- frequency power supply typically 1 kilowatt in power
  • the desired amounts of noble gas, oxygen and nitrogen can be controlled by commonly available mass-flow controllers with mass flows of noble gas, of oxygen and of nitrogen in the range of 0 - 10 seem (standard cubic centimetres per minute) .
  • the shutter can be opened or the substrates then moved into the sputtering position for the time necessary to produce the required thickness of deposit.
  • a typical system as described can produce film deposition rates in the region of 150 - 800 nm/hr (dependent of film composition and target to substrate distance) . Higher deposition rates can be achieved using reactive d.c. sputtering or preferably "low-frequency" sputtering whereby a power supply operating at a frequency in the kilohertz region is used to reduce the charging effects encountered with d.c. power supplies.
  • Pigments can be produced from thin films by depositing onto and subsequently removing the film from, a suitable surface or substrate. The film can then be ground down to produce a pigment which is long lasting, chemically resistant and can be incorporated into a suitable host to form paints which retain the same characteristic features of the original films which can then be applied to surfaces in a variety of ways.
  • the colour of pigments manufactured from such films varies with the viewing angle and cannot be reproduced by a photocopier or colour printer.
  • the films may be easily removed and recovered if they are deposited onto substrates or surfaces which are flexible or which can be dissolved in a suitable solvent.
  • a coating of a suitable material may be layed down onto the steel or iron, for instance, before laying down the diamond.
  • a thin film of material may be layed down onto a diamond surface first.
  • a thin film of aluminium oxynitride and/or oxide and/or nitride can be deposited by the technique described using the technique described herein.
  • the stress properties of the film can be modified to match those of the diamond surface so that the film forms a coherent layer on the diamond surface.
  • the composition of the film can then be altered so that the stress properties of the film match those of another material which is to be stuck to the diamond surface via the thin film of aluminium oxynitride and/or oxide and/or nitride.
  • This technique can be used for example in the manufacture of tools with diamond components where there are significant difficulties in depositing or attaching diamond films onto certain materials. For instance: in the manufacture of diamond tipped drill- bits, grinding and polishing tools.
  • the tool can be treated initially with a thin film of aluminium oxynitride and/or oxide and/or nitride. After this stage is completed the treated tool can be coated with an additional layer of diamond, grown by standard techniques .
  • Further applications include providing a thermally stable coating for diamond windows for use in optical, IR or UV sensors .
  • Rugate filters have a spectral response similar to that of a rejection filter: having high transmission everywhere except a narrow region centred on wavelength, ⁇ o .
  • the refractive index variation is generally given by
  • n ( z ) n-. ⁇ ar ⁇ + n rang9 s in ( 4 m mean Z + ⁇ ) 2 ⁇ 0
  • n-. aa- is the average refractive index
  • n ra ⁇ lg ⁇ is the refractive index range and the geometrical thickness of one sinusoidal cycle, t 0 .
  • Equn. (2) t 0 ⁇
  • phase factor ⁇ in Equn.(l) is the optical density at ⁇ Q is . important in determining the magnitudes and positions of the sidebands which are observed with this type of filter"
  • Equn. 2 shows that the centre wavelength is varied by changing the physical thickness of one cycle and Equn 3 shows that the bandwidth can be varied by changing the refractive index range of the sinusoid.
  • the optical density at ⁇ is dependent on the number of cycles deposited.
  • Such filters have application in laser goggles for protection of humans and laser rejection filters for instruments, as general purpose laser mirrors, and in head-up displays . They may also be used instead of the holographic filters in the new generations of compact Raman spectrometers.

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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)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Optical Filters (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne un film mince comprenant des couches successives d'oxyde d'aluminium, d'oxynitrure d'aluminium et de nitrure d'aluminium, variables de manière sinusoïdale sur toute l'épaisseur du film. On peut utiliser le film pour revêtir et protéger des outils aux bords de coupe tranchants, pour former un revêtement de protection thermique sans contraintes pour des diamants naturels ou artificiels, comme filtre de lumière et/ou comme pigment. Le film mince est produit par pulvérisation d'aluminium au moyen d'un gaz rare approprié, dans une atmosphère variable d'oxygène et d'azote, à température ambiante. Le film est transparent et présente un indice de réfraction qui varie entre 1,6 et 2,2, de manière sinusoïdale par rapport à l'épaisseur.
PCT/GB1998/000556 1997-02-21 1998-02-23 Films minces WO1998037254A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU63011/98A AU6301198A (en) 1997-02-21 1998-02-23 Thin films
EP98907020A EP1000182A2 (fr) 1997-02-21 1998-02-23 Films minces

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9703616.4A GB9703616D0 (en) 1997-02-21 1997-02-21 Thin films
GB9703616.4 1997-02-21

Publications (2)

Publication Number Publication Date
WO1998037254A2 true WO1998037254A2 (fr) 1998-08-27
WO1998037254A3 WO1998037254A3 (fr) 1998-11-19

Family

ID=10808066

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/000556 WO1998037254A2 (fr) 1997-02-21 1998-02-23 Films minces

Country Status (5)

Country Link
EP (1) EP1000182A2 (fr)
AU (1) AU6301198A (fr)
GB (1) GB9703616D0 (fr)
WO (1) WO1998037254A2 (fr)
ZA (1) ZA981447B (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1970465A2 (fr) 2007-03-13 2008-09-17 JDS Uniphase Corporation Procédé et système de dépôt par pulvérisation pour le dépôt d'une couche composée d'un mélange de matériaux et disposant d'un index de réfraction prédéterminé
US8072561B2 (en) 2007-04-10 2011-12-06 Jds Uniphase Corporation Twisted nematic xLCD contrast compensation with tilted-plate retarders
US8454805B2 (en) 2008-03-25 2013-06-04 Spts Technologies Limited Method of depositing amorphus aluminium oxynitride layer by reactive sputtering of an aluminium target in a nitrogen/oxygen atmosphere
CN104416206A (zh) * 2013-08-30 2015-03-18 钴碳化钨硬质合金公司 用于切削刀具的耐热涂层
US9079802B2 (en) 2013-05-07 2015-07-14 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US9366784B2 (en) 2013-05-07 2016-06-14 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US9684097B2 (en) 2013-05-07 2017-06-20 Corning Incorporated Scratch-resistant articles with retained optical properties
US9703011B2 (en) 2013-05-07 2017-07-11 Corning Incorporated Scratch-resistant articles with a gradient layer
US9726786B2 (en) 2014-05-12 2017-08-08 Corning Incorporated Durable and scratch-resistant anti-reflective articles
US9790593B2 (en) 2014-08-01 2017-10-17 Corning Incorporated Scratch-resistant materials and articles including the same
US10160688B2 (en) 2013-09-13 2018-12-25 Corning Incorporated Fracture-resistant layered-substrates and articles including the same
US10416352B2 (en) 2015-09-14 2019-09-17 Corning Incorporated High light transmission and scratch-resistant anti-reflective articles
US10948629B2 (en) 2018-08-17 2021-03-16 Corning Incorporated Inorganic oxide articles with thin, durable anti-reflective structures
US11267973B2 (en) 2014-05-12 2022-03-08 Corning Incorporated Durable anti-reflective articles
US11667565B2 (en) 2013-05-07 2023-06-06 Corning Incorporated Scratch-resistant laminates with retained optical properties
US12352924B2 (en) 2020-07-09 2025-07-08 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5437931A (en) * 1993-10-20 1995-08-01 Industrial Technology Research Institute Optically variable multilayer film and optically variable pigment obtained therefrom

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1970465A2 (fr) 2007-03-13 2008-09-17 JDS Uniphase Corporation Procédé et système de dépôt par pulvérisation pour le dépôt d'une couche composée d'un mélange de matériaux et disposant d'un index de réfraction prédéterminé
US8864958B2 (en) 2007-03-13 2014-10-21 Jds Uniphase Corporation Method and sputter-deposition system for depositing a layer composed of a mixture of materials and having a predetermined refractive index
US8072561B2 (en) 2007-04-10 2011-12-06 Jds Uniphase Corporation Twisted nematic xLCD contrast compensation with tilted-plate retarders
US8454805B2 (en) 2008-03-25 2013-06-04 Spts Technologies Limited Method of depositing amorphus aluminium oxynitride layer by reactive sputtering of an aluminium target in a nitrogen/oxygen atmosphere
US12195384B2 (en) 2013-05-07 2025-01-14 Corning Incorporated Scratch-resistant laminates with retained optical properties
US9703011B2 (en) 2013-05-07 2017-07-11 Corning Incorporated Scratch-resistant articles with a gradient layer
US9079802B2 (en) 2013-05-07 2015-07-14 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US9359261B2 (en) 2013-05-07 2016-06-07 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US9366784B2 (en) 2013-05-07 2016-06-14 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US10444408B2 (en) 2013-05-07 2019-10-15 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US9684097B2 (en) 2013-05-07 2017-06-20 Corning Incorporated Scratch-resistant articles with retained optical properties
US11667565B2 (en) 2013-05-07 2023-06-06 Corning Incorporated Scratch-resistant laminates with retained optical properties
US11231526B2 (en) 2013-05-07 2022-01-25 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US11714213B2 (en) 2013-05-07 2023-08-01 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
GB2520798A (en) * 2013-08-30 2015-06-03 Kennametal Inc Refractory coatings for cutting tools
CN104416206A (zh) * 2013-08-30 2015-03-18 钴碳化钨硬质合金公司 用于切削刀具的耐热涂层
US9427808B2 (en) 2013-08-30 2016-08-30 Kennametal Inc. Refractory coatings for cutting tools
DE102014109652B4 (de) 2013-08-30 2022-05-05 Kennametal Inc. Beschichtetes Schneidwerkzeug sowie Verfahren zum Herstellen eines beschichteten Schneidwerkzeugs
US10160688B2 (en) 2013-09-13 2018-12-25 Corning Incorporated Fracture-resistant layered-substrates and articles including the same
US10436945B2 (en) 2014-05-12 2019-10-08 Corning Incorporated Durable and scratch-resistant anti-reflective articles
US11267973B2 (en) 2014-05-12 2022-03-08 Corning Incorporated Durable anti-reflective articles
US12421398B2 (en) 2014-05-12 2025-09-23 Corning Incorporated Durable anti-reflective articles
US9726786B2 (en) 2014-05-12 2017-08-08 Corning Incorporated Durable and scratch-resistant anti-reflective articles
US9790593B2 (en) 2014-08-01 2017-10-17 Corning Incorporated Scratch-resistant materials and articles including the same
US10837103B2 (en) 2014-08-01 2020-11-17 Corning Incorporated Scratch-resistant materials and articles including the same
US10995404B2 (en) 2014-08-01 2021-05-04 Corning Incorporated Scratch-resistant materials and articles including the same
US10451773B2 (en) 2015-09-14 2019-10-22 Corning Incorporated High light transmission and scratch-resistant anti-reflective articles
US10416352B2 (en) 2015-09-14 2019-09-17 Corning Incorporated High light transmission and scratch-resistant anti-reflective articles
US11698475B2 (en) 2015-09-14 2023-07-11 Corning Incorporated Scratch-resistant anti-reflective articles
US11002885B2 (en) 2015-09-14 2021-05-11 Corning Incorporated Scratch-resistant anti-reflective articles
US11567237B2 (en) 2018-08-17 2023-01-31 Corning Incorporated Inorganic oxide articles with thin, durable anti-reflective structures
US10948629B2 (en) 2018-08-17 2021-03-16 Corning Incorporated Inorganic oxide articles with thin, durable anti-reflective structures
US11906699B2 (en) 2018-08-17 2024-02-20 Corning Incorporated Inorganic oxide articles with thin, durable anti reflective structures
US12352924B2 (en) 2020-07-09 2025-07-08 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same

Also Published As

Publication number Publication date
WO1998037254A3 (fr) 1998-11-19
GB9703616D0 (en) 1997-04-09
EP1000182A2 (fr) 2000-05-17
AU6301198A (en) 1998-09-09
ZA981447B (en) 1998-08-27

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