WO2018178073A1 - Couche dure à gradient ayant un module d'élasticité variable - Google Patents

Couche dure à gradient ayant un module d'élasticité variable Download PDF

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Publication number
WO2018178073A1
WO2018178073A1 PCT/EP2018/057766 EP2018057766W WO2018178073A1 WO 2018178073 A1 WO2018178073 A1 WO 2018178073A1 EP 2018057766 W EP2018057766 W EP 2018057766W WO 2018178073 A1 WO2018178073 A1 WO 2018178073A1
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WIPO (PCT)
Prior art keywords
substrate
hard layer
gradient hard
modulus
layer
Prior art date
Application number
PCT/EP2018/057766
Other languages
German (de)
English (en)
Inventor
Gerd-Peter Scherg
Ulrike Schulz
Heiko Knopf
Nancy Gratzke
Original Assignee
Rodenstock Gmbh
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 Rodenstock Gmbh filed Critical Rodenstock Gmbh
Publication of WO2018178073A1 publication Critical patent/WO2018178073A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00865—Applying coatings; tinting; colouring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/027—Graded interfaces
    • 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
    • C23C14/10—Glass or silica
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • 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
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • 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

Definitions

  • the present invention relates to a method for applying a gradient hard layer on a substrate to be coated, to a gradient hard layer applied to a substrate by the method according to the invention and to the use of the gradient hard layer as a tempering layer of a substrate.
  • the photorefractive substrates of optical components such as lenses are increasingly being made of plastics today.
  • One of the reasons for the increasing rejection of mineral glasses is, inter alia, the lower density and thus the lower weight of the plastic materials, which is particularly advantageous in eyeglass lenses due to the more comfortable fit.
  • substrates made of plastics have an increased resistance to breakage. Compared to mineral glasses, plastic materials only splinter at elevated force. Thus, the risk of injury to the eye in accidents is significantly lower for wearers of plastic lenses.
  • plastics are relatively soft materials, lenses made of plastics are susceptible to scratches. At the latter, the incident light is scattered diffusely, which makes the visual impression when looking through the spectacle lens unclear and also affects the aesthetic appearance of the spectacle lens. Therefore, lenses made of plastics require, in contrast to those made of mineral glasses of a special remuneration such as a hard-layer finishing.
  • the several micrometers thick hard layer gives as a hardening cover layer of the surface of the spectacle lens increased scratch resistance, whereby its life is extended accordingly.
  • the application of the hard layer on a substrate to be coated can be carried out by a wet chemical method, for example by means of a dip coating method, wherein the applied in the dip bath hardcoat layer can then be cured by irradiation with UV light or under the action of heat.
  • hard coatings can also be vapor-deposited on a substrate to be coated or deposited using PCVD processes (PCVD, plasma enhanced chemical vapor deposition).
  • PCVD plasma enhanced chemical vapor deposition
  • the hard coatings thus obtained have a very good scratch resistance to fine scratch marks, but a significantly poorer scratch resistance to coarse scratches, which is evident, for example, in the steel wool test using steel wool with a fineness of No. 000.
  • a method for applying a gradient hard layer on a substrate to be coated comprising the following steps (a) to (e), wherein the order of steps (b) to (d) is not further limited:
  • the method according to the invention for applying a gradient hardcoat to a substrate to be coated is based on a combination of plasma-assisted decomposition of an organosilicon precursor and evaporation of a silicon dioxide source by electron bombardment. Accordingly, in the process of the invention, a co-deposition of silicon-containing organic radicals and of silicon dioxide takes place with the formation of a hard layer with a hybrid composition.
  • the organic content decreases along the layer thickness of the forming hard layer. The organic content thus correlates with the ratio of the gas flow of the organosilicon precursor and the evaporation rate of the silicon dioxide source.
  • the modulus of elasticity of the hard layer With the decrease of this ratio is accompanied by an increase in the modulus of elasticity of the hard layer, which is why the latter is also referred to as a gradient hard layer according to the invention. If only the decomposition of the organosilicon precursor and no evaporation of the silicon dioxide source takes place at the beginning of the substrate coating, the modulus of elasticity of the gradient hard layer reaches its minimum possible value and comes as close as possible to the comparatively small modulus of elasticity of the substrate to be coated. In this context, one also speaks of an adaptation of the modulus of elasticity of the gradient hard layer to the modulus of elasticity of the substrate.
  • a vacuum chamber is provided in step (a) of the method according to the invention for applying a gradient hard layer on a substrate to be coated.
  • the vacuum chamber is necessarily designed so that the plasma gas provided in step (b) can be introduced from the plasma ion source and the organosilicon precursor provided in step (c). Consequently, the vacuum chamber has corresponding terminals. Furthermore, the vacuum chamber is necessarily such that it can accommodate the electron beam evaporator provided in step (d) and the substrate to be coated.
  • the apparatus construction used in the method according to the invention is a vapor deposition system.
  • this allows the application of at least one further optically active layer on the formed gradient hard layer in the context of the same manufacturing process.
  • the at least one further optically active layer which likewise serves for substrate compensation, may be, for example, an interference / anti-reflection layer for reducing reflections.
  • a topcoat can be applied to the thus coated or also to the uncoated gradient hard layer. The latter typically has a thickness in the range of 5 to 10 nm and is virtually not optically active.
  • step (b) of the method of applying a gradient hardcoat to a substrate to be coated there is provided a plasma gas from a plasma ion source for introduction into the vacuum chamber, wherein the plasma gas is at least one selected from the group consisting of argon, xenon, nitrogen and oxygen, is.
  • the plasma ion source used is accordingly capable of producing argon, xenon, nitrogen and / or oxygen-containing plasma gas.
  • argon is provided as plasma gas in step (b).
  • oxygen is provided as the plasma gas, or any mixture of the above-mentioned gases.
  • the oxygen content of the plasma gas may be, for example, from 1 to 50% by volume. Due to the presence of oxygen in the plasma gas, in the absence of evaporation of the silicon dioxide source, a deposition of silicon dioxide by the decomposition of the Organosilizium Weghaririuss carried out with simultaneous oxidation of the resulting silicon-containing organic radicals.
  • the plasma gas provides the energy necessary for the decomposition of the organosilicon precursor.
  • Typical ion energies of the plasma gas are in the range from 60 to 120 eV, whereby, depending on the type of plasma ion source and chemical composition of the plasma gas, its ion energy can vary and, under certain circumstances, be greater than stated above.
  • the plasma power is adjusted via the bias voltage of the plasma ion source and may be constant during the duration of the substrate coating. Alternatively, in the method of the invention, the plasma power may also be increased, e.g. gradually.
  • an organosilicon precursor is provided for introduction into the vacuum chamber.
  • the organosilicon precursor is not particularly limited, as long as it decomposes in the gas phase plasma-assisted and can be deposited on the substrate to be coated in the form of silicon-containing organic radicals.
  • the organosilicon precursor need not necessarily be provided in gaseous form in step (c) of the process of the invention. As a result of the pressure conditions prevailing in the vacuum chamber, the organosilicon precursor evaporates even when it enters the vacuum chamber.
  • Organosilizium rempliadosoren which can be used in the process according to the invention, hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDSN), hexamethyldisilane (HMDS), tetramethylsilane (TMS), tetramethyldisilane (TMDS), tetraethoxysilane (TEOS), dimethyldiethoxysilane ( DMDES), tetramethyldisiloxane (TMDSO), methyltrimethoxysilane (MTMOS), octamethylcyclotetrasiloxane (OMCTS) and 1,3-divinyltetramethyldisiloxane (DVTMDSO).
  • HMDSO hexamethyldisiloxane
  • HMDSN hexamethyldisilazane
  • HMDS hexamethyldisilane
  • TMS tetramethylsilane
  • an electron beam evaporator is provided together with the substrate to be coated in the vacuum chamber.
  • the electron beam evaporator comprises a silicon dioxide source in addition to an electron beam gun.
  • the electron gun provides for evaporation of the silica from the silica source in step (e) under high vacuum conditions, as described below.
  • the substrate to be coated which is provided together with the electron beam evaporator in the vacuum chamber, according to the invention is not subject to any particular restrictions.
  • it is a transparent plastic substrate which may be treated or untreated. It is, for example, polythiourethane, poly methyl methacrylate, polycarbonate, polyacrylate or Polydiethylenglycolbisallylcarbonat (CR 39 ®) is formed, although other transparent plastic materials may be used.
  • the substrate to be coated is further subject to no geometrical restrictions.
  • it may be plane-parallel, biconcave, plano-concave, convex-concave, concave-convex, plano-convex, or biconvex. In principle, however, it can assume any geometric shape.
  • the substrate to be coated are primarily applicable to optical components such as lenses, in particular spectacle lenses, the present invention is by no means limited thereto.
  • the substrate to be coated in turn already be coated. These include, for example, thin adhesive layers or layers for optical adjustment of the refractive indices.
  • step (e) of the method according to the invention for applying a gradient hard layer on a substrate to be coated the plasma gas from the plasma ion source and the organosilicon precursor are introduced into the vacuum chamber, resulting in the coating of the substrate.
  • the gas flow of the organosilicon precursor decreases continuously or discontinuously to a final value and the evaporation rate of the silicon dioxide source increases continuously or discontinuously to a final value.
  • a continuous or discontinuous decrease or increase means that the gas flow or the evaporation rate can be constant in phases, ie. they do not necessarily decrease or decrease permanently. Accordingly, the ratio of gas flow of the organosilicon precursor and rate of evaporation of the silicon dioxide source also decreases continuously or discontinuously over the duration of the substrate coating, which also applies to the organic content. Conversely, the modulus of elasticity increases continuously or discontinuously.
  • both the gas flow of the organosilicon precursor and the evaporation rate of the silicon dioxide source can remain constant until completion of the coating process.
  • the ratio of gas flow and evaporation rate then undergoes no change. The same applies to the organic content as well as to the modulus of elasticity.
  • the gas flow of the organosilicon precursor initially present in step (e) is not subject to any restrictions in accordance with the invention. Since it decreases to a final value during the duration of the substrate coating, the person skilled in the art will initially select a comparatively high gas flow.
  • the gas flow of the organosilicon precursor may initially be in a range of 200 to 2000 sccm, eg 800 sccm, depending in detail on the size and type of vacuum chamber.
  • the presence of the plasma gas in step (e) leads to a decomposition of the organosilicon precursor and to the deposition of silicon-containing organic radicals on the substrate to be coated. If the plasma gas contains oxygen, the silicon-containing organic radicals are partially or completely oxidized, which can lead to the deposition of pure silicon dioxide.
  • the organic content along the layer thickness of the gradient hard layer likewise decreases. If the final value of the gas flow is 0 sccm, no deposition of silicon-containing organic radicals takes place. Consequently, no organic content is present in this region of the gradient hard layer.
  • the evaporation rate of the silicon dioxide source increases to a final value during the duration of the substrate coating, with neither the initial nor the final value being further restricted.
  • Typical evaporation rates are in a range of 0 to 6 nm / s, whereby again the size and the design of the vacuum chamber influence the evaporation rate.
  • step (e) the emission current of the electron beam gun is low and the aperture above the source is closed, no deposition of silicon dioxide on the substrate takes place unless the plasma gas contains oxygen. In this way, a high organic content and thus a small modulus of elasticity can be realized on the contact side to the substrate, which comes as close as possible to the modulus of elasticity of the substrate, i. adapted to the modulus of elasticity of the substrate.
  • the organic content decreases along the layer thickness of the gradient hard layer to be formed due to the decrease in the gas flow of the organosilicon precursor and the increase in the evaporation rate of the silica source.
  • the deposition of pure silicon dioxide without organic content is required, which can be achieved by a final value of the gas flow of the organosilicon precursor of 0 sccm.
  • the plasma power is increased during the duration of the substrate coating, e.g. gradually, causing a compression of the gradient hard layer and thus a further increase of the modulus of elasticity.
  • the skilled person will routinely provide a suitable end value for the plasma power.
  • the plasma power is adjusted by the bias voltage of the plasma ion source. Typical starting and ending values of the bias voltage are in a range from 80 to 120 V, the bias voltage naturally being dependent on the type of the respective plasma ion source.
  • the gradient hard layer can be further compressed even with constant plasma power.
  • the evaporation rate of the silicon dioxide source is reduced again from its final value.
  • Slower vaporization of the silicon dioxide from the silicon dioxide source leads to a compression of the gradient hard layer and thus also to an increase in the modulus of elasticity.
  • decreasing the evaporation rate for a given plasma power equals increasing the plasma power at a given evaporation rate, provided that pure silica without organic content is deposited, therefore, the gas flow of the organosilicon precursor in this embodiment is necessarily 0 sccm.
  • the total pressure during the duration of the substrate coating at no time is more than 2-10 3 mbar in the vacuum chamber.
  • low total pressure can be achieved with respect to the substrate surface homogeneous deposition and thus adjust the thickness of the gradient hard layer targeted.
  • further gases can be introduced into the vacuum chamber in order to improve, for example, the layer quality of the gradient hard layer.
  • gases are air, nitrogen, water vapor, etc.
  • gases exert no influence on the deposited organic content and thus also have no influence on the course of the modulus of elasticity.
  • the temperature prevailing in the vacuum chamber is typically from 40 to 80 ° C. during the coating in step (e) of the process according to the invention.
  • the temperature is obtained indirectly from the energy of the electron emitted by the electron gun and from the ion energy of the plasma gas, which are converted into heat as a result of impact processes.
  • the comparatively low temperature during the coating in step (e) ensures that thermally sensitive substrates do not suffer damage.
  • the present invention relates to a gradient hard coating applied to a substrate, which can be obtained by the method according to the invention described above.
  • the gradient hard layer according to the invention is characterized in that the modulus of elasticity of the gradient hard layer on the contact side to the substrate is smaller than the modulus of elasticity on the side facing away from the substrate of the gradient hard layer.
  • the modulus of elasticity of the gradient hard layer on the contact side to the substrate can be substantially matched to the modulus of elasticity of the substrate.
  • Substantially in this context means that the gradient hard layer at the interface with the substrate has a maximum organic content and, accordingly, a minimum modulus of elasticity that comes as close as possible to the comparatively small modulus of elasticity of the substrate.
  • the modulus of elasticity of the gradient hard layer increases continuously or discontinuously up to a final value in the direction of the side facing away from the substrate.
  • the modulus of elasticity of the gradient hard layer can thus increase in steps.
  • the final value of the modulus of elasticity can already be reached before reaching the side facing away from the substrate, i. the E-modulus can be constant after reaching the final value over the further layer thickness until reaching the side facing away from the substrate.
  • the inventive profile of the modulus of elasticity along the layer thickness of the gradient hard layer starting from the substrate surface ensures that the mechanical stress within the gradient hard layer does not change abruptly when a force is applied.
  • the gradient hard layer in the direction of the side facing away from the substrate reaches the final value of the modulus of elasticity, which optionally remains constant along the further layer thickness of the gradient hard layer. Due to the comparatively large modulus of elasticity on the side facing away from the substrate, scratch tests with low pressure in the region of the microscopic bearing surfaces only cause fine scratch marks. Scratching tests with high pressure in the area of the microscopic contact surfaces, which lead to a breaking of the hard layer cause by contrast, due to the adaptation of the moduli of elasticity, clearly less visible rough scratch marks than in the case of comparable hard layers without a gradient.
  • the modulus of elasticity of the gradient hard layer reaches its final value within a layer thickness of 1 ⁇ starting from the contact side to the substrate.
  • the final value of the modulus of elasticity is in a range of 30 to 80 GPa, preferably in a range of 30 to 40 GPa.
  • the layer thickness of the gradient hard layer according to the invention is not subject to any restrictions. However, not least because of manufacturing costs, it is preferable that the layer thickness of the gradient hard layer is not more than 3 ⁇ m. If, for example, the final value of the modulus of elasticity is reached after 1 ⁇ m of layer thickness, this remains constant along a further layer thickness of 2 ⁇ m.
  • the E modulus is determined using the ASMEC "Quasi Continuous Stiffness Measure- ment” (QCSM) module up to a maximum force of 50 mN.
  • QCSM Quality of Stiffness Measure- ment
  • the normal force is kept constant at certain steps for a period of about three seconds during the penetration process, during which time it is superimposed with a sinusoidal oscillation. From the amplitude and the phase shift of the oscillations, the modulus of elasticity of a homogeneous coating on an arbitrary substrate can then be determined.
  • a determination of the gradient is basically not possible, but individual layers can be characterized with the phase-wise process parameters of the gradient.
  • the substrate to be coated is subject to no restrictions.
  • the person skilled in the art routinely selects the substrate required for the particular purpose.
  • At least one further optically active layer is applied to the gradient hard layer according to the invention, which advantageously takes place in the context of the same manufacturing process.
  • the at least one further optically active layer can, for example, be act as an interference / anti-reflection layer for reflection reduction.
  • a topcoat may be applied to the thus coated or even to the uncoated gradient hard layer.
  • the present invention relates to the use of the gradient hard layer obtainable by the method according to the invention as a tempering layer of a substrate, for example a transparent plastic substrate, such as a lens, in particular a spectacle lens.
  • a transparent plastic substrate such as a lens, in particular a spectacle lens.
  • the use of the gradient hard layer obtainable by the method according to the invention as a tempering layer is not limited to a particular substrate.
  • Substrates on which the gradient hard layer according to the invention is applied have an excellent scratch resistance, which increases their life accordingly.
  • coarse scratch marks are less conspicuous, which is due to the adaptation of the modulus of elasticity of the gradient hard layer to the modulus of elasticity of the substrate.
  • the gradient hard layer according to the invention has excellent mechanical stability.
  • FIG. 1 shows a schematic structure of a vacuum chamber with electron beam evaporator and the substrate to be coated, which is suitable for the method according to the invention, on a rotating substrate holder, including the plasma ion source with argon and the organosilicon precursor as the process gas.
  • FIG. 2 shows the time profile of the evaporation rate, the gas flow, the total coating rate and the layer thickness of a gradient hard layer obtained by the method according to the invention over a layer thickness of 1 ⁇ m.
  • a gradient hard layer was applied to a substrate to be coated by the method according to the invention in a vapor deposition system, as illustrated by way of example in FIG. 1.
  • the organosilicon precursor used was hexamethyldisiloxane (HMDSO).
  • HMDSO hexamethyldisiloxane
  • the modulus of elasticity increased to a value of 37 GPa after 1 ⁇ m layer thickness.
  • plasma power bias voltage
  • gas flow HMDSO flow
  • SiO 2 rate evaporation rate
  • the evaporation rate increased discontinuously as far as the final value, while the gas flow discontinuously decreased to the final value.
  • the evaporation rate was reduced again, which leads to a further compression of the gradient hard layer and thus to an increase of the modulus of elasticity until a layer thickness of 1 ⁇ came.
  • the layer thickness grew by a further 2 ⁇ under unchanged conditions (not shown in Fig. 2).
  • the gradient hard layer thus obtained had a decreasing organic content (content of carbon, silicon and oxygen) with increasing coating time, i. with increasing layer thickness, which was accompanied by an increase in the modulus of elasticity, as shown in FIG. 3 can be removed.
  • a further increase of the modulus of elasticity in pure SiO 2 deposition could be achieved by compaction.
  • the labeling of the data points in FIG. 3 is as follows: HMDSO flux in sccm / bias voltage in V / SiO 2 rate in nm / s.

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Abstract

La présente invention concerne un procédé permettant d'appliquer une couche dure à gradient sur un substrat à revêtir, une couche dure à gradient appliquée sur un substrat par le procédé selon l'invention, et l'utilisation de la couche dure à gradient comme couche antireflet d'un substrat.
PCT/EP2018/057766 2017-03-29 2018-03-27 Couche dure à gradient ayant un module d'élasticité variable WO2018178073A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017003042.1A DE102017003042B3 (de) 2017-03-29 2017-03-29 Gradienten-Hartschicht mit sich änderndem E-Modul
DE102017003042.1 2017-03-29

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WO2018178073A1 true WO2018178073A1 (fr) 2018-10-04

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Citations (8)

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