WO2024133817A1 - Revêtement multicouche de couleur ajustable - Google Patents

Revêtement multicouche de couleur ajustable Download PDF

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Publication number
WO2024133817A1
WO2024133817A1 PCT/EP2023/087486 EP2023087486W WO2024133817A1 WO 2024133817 A1 WO2024133817 A1 WO 2024133817A1 EP 2023087486 W EP2023087486 W EP 2023087486W WO 2024133817 A1 WO2024133817 A1 WO 2024133817A1
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layer
silicon
high refractive
multilayer coating
hydrogen
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PCT/EP2023/087486
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English (en)
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Arnaud KRUMPMANN
Thomas GODFROID
Damien Robert
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Materia Nova Asbl
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Publication of WO2024133817A1 publication Critical patent/WO2024133817A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • 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
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/302—Thickness of a layer with high refractive material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/303—Thickness of a layer with low refractive material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/304—Thickness of intermediate layers adjacent to the core, e.g. metallic layers, protective layers, rutilisation enhancing layers or reflective layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/307—Thickness of an outermost protective layer

Definitions

  • the present invention relates to a multilayer coating comprising a stack of a high refractive layer alternating with a low refractive layer.
  • the present invention also relates to a process for applying a multilayer coating to a substrate.
  • the present invention also relates to a use of a multilayer coating.
  • DBR Distributed Bragg Reflectors
  • US6500251B1 describes a multilayer interference pigment consisting of platelet like titanium dioxide as carrier material, coated with alternating layers of metal oxides of low and high refractive index, the difference in the refractive indices being at least 0.1, which is obtainable by solidification and hydrolysis of an aqueous solution of a thermally hydrolyzable titanium compound on a continuous belt, detachment of the resulting coat, coating of the resulting titanium dioxide platelets, with or without drying in between, by a wet method with, alternately, a metal oxide hydrate of high refractive index and a metal oxide hydrate of low refractive index by hydrolysis of the corresponding, water-soluble metal compounds, separation, drying and, if desired, calcining of the material obtained.
  • W02006088761A2 describes a multilayer effect pigment including a transparent substrate, a layer of high refractive index material on the substrate, and alternating layers of low refractive index and high refractive index materials on the first layer, the total number of layers being an odd number of at least three, all adjacent layers differing in refractive index by at least about 0.2 and at least one of the layers having an optical thickness which is different from all of the other layers.
  • the resulting multilayer effect pigment is not a quarter-wave stack.
  • the present multilayer effect pigment may be used in cosmetics or personal care products.
  • CN108349792A relates to the surface treatment of supports by coating thereof, and in particular, to thin-film technologies.
  • the object of the present invention is to create a simple and reliable optical coating with superior usability and a technology for producing thereof, which is suitable for mass production at a low cost.
  • the composite optical coating comprising a multi-layered antireflection coating consisting of alternating layers with high and low refractive indices, and a protective coating
  • the outlined problem is solved by means of a modified adhesive layer made of an amorphous substance having a thickness of 5 to 200 nm formed between the antireflection coating and the protective coating.
  • Two variants of the method for producing the composite optical coating are also provided.
  • the present invention relates to a multilayer coating comprising a stack of a high refractive layer alternating with a low refractive layer according to claim 1.
  • a specific preferred embodiment relates to an invention according to claim 7, 8 and 9. These claims relates to a top layer.
  • An anti-reflective layer topcoat will significantly reduce secondary reflections.
  • This comprises a transparent layer of determined thickness of a material whose refractive index is intermediate between the high refractive index and the air.
  • Several candidates were considered, for example MoOs, AI2O3, SisN 4 , SiOxNy.
  • AI2O3 was for example chosen because of the best refractive index matching. Silicon oxynitrides are even more promising as it uses a Si target and allows for refractive index fine tuning.
  • a further specific preferred embodiment relates to an invention according to claim 11 and 12. These claims relates to a bottom layer. This improvement is desired to get rid of the substrate influence and be able to obtain the same result whatever the substrate.
  • a highly absorbing black bottom layer is used for this purpose. There are numerous candidates for this absorbing layer, for example TiAIN. Selective absorption layers can also be used as bottom layer, e.g. intrinsic colour layer, to enhance certain colours.
  • the present invention relates to a process according to claim 13. More particularly, the present invention comprises a process for applying a multilayer coating to a substrate.
  • the present invention relates to a use according to claim 15.
  • the use of the multilayer coating herein provides an advantageous effect of obtaining coloured coatings, preferably red coatings.
  • Figure 1 shows a preferred embodiment according to the present invention.
  • Figure 2 shows the layers of the coating in a preferred order.
  • a substrate is provided, this can include any type of substrate.
  • the substrate is a black TiAIN layer.
  • the stack is the stack provided.
  • the stack contains an a- Si:H/SiO2 layer system.
  • an anti-reflective top layer made of AI2O3 provided on top of the stack.
  • Figure 3 shows a multilayer stack for providing a red coloured coating according to an embodiment of the present invention.
  • the present invention concerns a multilayer coating comprising a stack of a high refractive layer alternating with a low refractive layer.
  • This invention relates generally to the coating of substrates using physical or chemical vapor deposition, and more particularly to a multilayer coating of tuneable colour obtained by a distributed Bragg reflector strategy.
  • all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
  • a compartment refers to one or more than one compartment.
  • the terms "one or more” or “at least one”, such as one or more or at least one member(s) of a group of members, is clear per se, by means of further exemplification, the term encompasses inter alia a reference to any one of said members, or to any two or more of said members, such as, e.g., any >3, >4, >5, >6 or >7 etc. of said members, and up to all said members.
  • the term “thickness”, refers to a portion of a layer located substantially perpendicular to its outer surface.
  • the thickness may aim a distance from said surface, as a distance from a point below said surface.
  • % by atom refers to the proportion of any nuclide in a mixture expressed as a numerical percentage of all the atoms of that element present irrespective of their nuclidic masses.
  • the term "refractive index” is a dimensionless number and is a measure of how light propagates through a material. The higher the refractive index the slower the light travels, which causes a correspondingly increased change in the direction of the light within the material.
  • the present invention relates to a multilayer coating comprising a stack of a high refractive layer alternating with a low refractive layer.
  • the low refractive layer is silica based, more preferably the low refractive layer comprises from 30 to 50 at% silicon, from 40 to 70 at% oxygen, from 0 to 30 at% nitrogen, and from 0 to 20 at% hydrogen, more preferably from 30 to 50 at% silicon, from 50 to 70 at% oxygen, from 0 to 20 at% nitrogen, and from 0 to 10 at% hydrogen, more preferably from 30 to 50 at% silicon and 50 to 70 at% oxygen.
  • Silica is preferred for its excellent physical, optical and electrical properties. It is stable over a wide range of conditions, not toxic and widely available.
  • the low refractive layer comprises silica or has a chemical makeup as described above, and said low refractive layer is porous.
  • the low refractive layer has porosity of at least 0.5%, more preferably at least 1%, more preferably at least 3%, more preferably at least 5%, more preferably at least 10%, more preferably at least 15%, more preferably at least 20%, more preferably at least 25%; as measured by volume of the pores to the total volume of the low refractive index layer.
  • the porosity allows one to modify and finetune the desired refractive index. With an increase in the porosity, the percentage of voids in the material also increases. Since air has a refractive index of roughly 1.0, this lowers the effective refractive index of SiO?. Modifying the porosity of the layers allows the finetuning of the refractive indices between 1.10 and 1.50.
  • the low refractive layer has a thickness of less than 200 nm, more preferably less than 190 nm, more preferably less than 180 nm, more preferably less than 170 nm, more preferably less than 160 nm, more preferably less than 150 nm, more preferably less than 140 nm, more preferably less than 130 nm, more preferably less than 120 nm.
  • the low refractive layer has a thickness greater than 30 nm, more preferably greater than 40 nm, more preferably greater than 50 nm, more preferably greater than 60 nm, more preferably greater than 70 nm, more preferably greater than 80 nm, more preferably greater than 90 nm, more preferably greater than 100 nm, more preferably greater than 110 nm.
  • the low refractive layer has a thickness between 30 nm and 200 nm, more preferably between 40 and 190 nm, more preferably between 50 and 180 nm, more preferably between 60 and 170 nm, more preferably between 70 and 160 nm, more preferably between 80 and 150 nm, more preferably between 90 and 140 nm, more preferably between 100 and 130 nm, more preferably between 110 and 120 nm.
  • the importance of these thicknesses is to cover the full range of visible light.
  • the low refractive layer has a thickness between 100 nm and 200 nm, more preferably between 110 and 190 nm, more preferably between 120 and 180 nm, more preferably between 130 and 170 nm, and even more preferably between 140 and 160 nm. This particular range is well-suited for achieving the desired optical properties related to red light within the visible spectrum.
  • the high refractive layer comprises from 60 to 100 at% silicon, from 0 to 20 at% oxygen, from 0 to 30 at% nitrogen, and from 0 to 40 at% hydrogen, more preferably from 70 to 100 at% silicon, from 0 to 10 at% oxygen, from 0 to 10 at% nitrogen, and from 0 to 30 at% hydrogen, more preferably from 70 to 100 at% silicon, and from 0 to 30 at% hydrogen.
  • a a-Si:H layer with high hydrogen dilution can be used as a good-quality thin silicon layer.
  • the concentration of hydrogen atoms is relatively high compared to the concentration of silicon atoms.
  • Si-H bonds there are more Si-H bonds present in the material. These bonds contribute to the stability and electrical properties of the material.
  • Increasing the silicon content in a-Si:H layers can lead to a number of changes in the material's properties.
  • One of the main effects of increasing the silicon content is an increase in the number of Si-H bonds, which can improve the stability and electrical properties of the material.
  • increasing the silicon content can also lead to an improvement in the mechanical properties of the material, such as its strength and hardness. This is because the presence of silicon atoms can help to strengthen the material.
  • Increasing the silicon content can also affect the electrical conductivity of the material.
  • Increasing the concentration of Si-H bonds in a-Si:H layers generally has the effect of increasing the optical absorption of the film.
  • amorphous silicon absorbs visible parts of the solar spectrum 40 times more efficiently than does single-crystal silicon, so a film only about 1 pm-thick can absorb 90% of the usable light energy shining on it.
  • This allows for thin yet effective coloured PVD coatings, while reducing material and processing requirements. Further advantages are that it can be produced at lower temperatures and can be deposited on a wide range of substrates. A a-Si:H can thus be deposited by plasma- enhanced chemical-vapor deposition on almost any substrate at temperatures below 230 °C.
  • Refractive index is a measure of how light propagates through a material. The higher the refractive index the slower the light travels, which causes a correspondingly increased change in the direction of the light within the material. What this means for layers is that a higher refractive index material can bend the light more and allow the thickness of the layer to be thinner.
  • a-Si:H can be deposited at very low temperatures.
  • the high refractive index layer has a thickness of less than 95 nm, more preferably less than 90 nm, more preferably less than 85 nm, more preferably less than 80 nm, more preferably less than 75 nm, more preferably less than 70 nm, more preferably less than 65 nm, more preferably less than 60 nm, more preferably less than 55 nm.
  • the high refractive layer has a thickness greater than 10 nm, more preferably greater than 15 nm, more preferably greater than 20 nm, more preferably greater than 25 nm, more preferably greater than 30 nm, more preferably greater than 35 nm, more preferably greater than 40 nm, more preferably greater than 45 nm, more preferably greater than 50 nm.
  • the high refractive layer has a thickness between 10 nm and 95 nm, more preferably between 15 and 90 nm, more preferably between 20 and 85 nm, more preferably between 25 and 80 nm, more preferably between 30 and 75 nm, more preferably between 35 and 70 nm, more preferably between 40 and 65 nm, more preferably between 45 and 60 nm, more preferably between 50 and 55 nm.
  • the importance of these thicknesses is to cover the full range of visible light. Even more preferably, the high refractive layer has a thickness between 50 nm and 65 nm, these thicknesses are the optimum for obtaining a red coating.
  • the high refractive layer has a thickness between 45 and 120 nm, more preferably between 45 and 100 nm, more preferably between 45 and 80 and even more preferably between 45 and 60 nm.
  • the specified thickness range for the anti-reflective top layer ranging from 45 nm to 120 nm across the entire visible range, serves a specific purpose in minimizing reflections and optimizing optical performance. This range, tailored to the entire visible spectrum, ensures the reduction of light reflection across diverse wavelengths. Specifically, the narrower range of 45 to 60 nm for the red colour accounts for the wavelength characteristics of light. This precision aims to enhance efficiency in applications where colour accuracy is paramount.
  • the invention comprises also a top layer on top of the stack, preferably the top layer comprises an anti -reflective layer, more preferably the top layer comprises any transparent material that has a refractive index between 1.7 and 1.9, more preferably MoOs, AI2O3, SisN 4 , Ta2Os, HfC>2, SnCh or SiO x N y .
  • An anti- reflective layer topcoat will significantly reduce secondary reflections. This comprises a transparent layer of determined thickness of a material whose refractive index is intermediate between the high refractive index and the air.
  • AI2O3 was chosen because of the best refractive index matching and because aluminium oxide is inert to acids and alkalis, is very hard, and naturally provides a passivation layer on coated substrates that prevents weathering and environmental corrosion.
  • AI2O3 coatings can be electrically insulating, chemically inert, very wear-resistant, and stable at elevated temperatures, depending on the crystalline phase and the deposition temperature. Since not all substrates tolerate a high process temperature, both a low and a high temperature version of AI2O3 have been developed.
  • Alumina coatings are also known to have non-stick properties towards various liquids and melted metals due to hydrophobic surface properties. Even more preferably, silicon oxynitrides are chosen as a top layer.
  • Silicon oxynitrides are even more promising as it uses a Si target and allows for refractive index fine tuning.
  • One of the benefits of using silicon oxynitrides as coatings is their high temperature stability. They can withstand temperatures up to 1200 °C or higher, making them useful in high- temperature environments.
  • silicon oxynitrides have good chemical resistance, meaning they are resistant to attack by many acids and bases. This makes them useful as protective coatings in a variety of applications. Silicon oxynitride coatings also have good electrical insulation properties and can be used to insulate electrical components or to protect against electrical discharge. They can also have a low coefficient of friction, making them useful in applications where low friction is desirable.
  • Silicon oxynitrides can be synthesized through various methods, such as chemical vapor deposition (CVD) or plasma-assisted CVD. They can be used in the form of thin films or as bulk materials, and their properties can be adjusted by controlling the stoichiometry and microstructure of the material. Some potential applications of silicon oxynitrides include use as protective coatings, in structural materials for high-temperature applications, and as insulating layers in electronics.
  • CVD chemical vapor deposition
  • plasma-assisted CVD Some potential applications include use as protective coatings, in structural materials for high-temperature applications, and as insulating layers in electronics.
  • the top layer has a thickness of less than 135 nm, more preferably less than 125 nm, more preferably less than 115 nm, more preferably less than 105 nm, more preferably less than 95 nm, more preferably less than 85 nm, more preferably less than 75 nm, more preferably less than 65 nm, more preferably less than 55 nm.
  • the high refractive layer has a thickness greater than 10 nm, more preferably greater than 15 nm, more preferably greater than 20 nm, more preferably greater than 25 nm, more preferably greater than 30 nm, more preferably greater than 35 nm, more preferably greater than 40 nm, more preferably greater than 45 nm, more preferably greater than 50 nm.
  • the high refractive layer has a thickness between 10 nm and 135 nm, more preferably between 15 and 125 nm, more preferably between 20 and 115 nm, more preferably between 25 and 105 nm, more preferably between 30 and 95 nm, more preferably between 35 and 85 nm, more preferably between 40 and 75 nm, more preferably between 45 and 65 nm, more preferably between 50 and 55 nm.
  • the importance of these thicknesses is to cover the full range of visible light.
  • the invention comprises a bottom layer between said stack and a substrate, preferably said bottom layer comprises an absorbing layer.
  • the bottom layer can comprise a rather standard absorbing layer, such as Ge2Sb2Tes, TiAIN, Si3N 4 , TiAISiN, M-AIN, TiAION. This improvement is desirable to get rid of the substrate influence and be able to obtain the same result whatever the substrate.
  • a highly absorbing black bottom layer is used for this purpose.
  • a TiAIN layer has the remarkable advantage that it is a highly absorbing layer and comprises further advantages of extreme hardness, excellent abrasive wear resistance, higher reliability in dry operations, lubricants can be reduced, heat resistance, hard machining, increased hardness, high wear resistant and oxidation resistant.
  • any coloured layer can act as a bottom layer.
  • a coloured bottom layer can be customized to absorb a specific range of wavelengths, allowing them to be tailored to the specific needs of the application. Any coloured bottom layer can easily be applied using standard coating equipment, making them a convenient choice for many types of applications.
  • the invention comprises a bottom layer, wherein the bottom layer comprises a silicon compound comprising between 70 to 100 at% silicon, between 0 to 10 at% oxygen, between 0 to 10 at% nitrogen, and between 0 to 30 % hydrogen.
  • the bottom layer comprises between 70 to 100 at% silicon and between 0 to 30 at% hydrogen. This composition serves as an optimal absorbing layer.
  • the multilayer having the above characteristics is remarkable. As a result of constructive interference caused by the incident and reflected light waves, a bright colour is observed onto the prepared DBR samples in accordance with the increased number of layers in the stack.
  • the top layers comprises from 30 to 50 at% silicon, from 0 to 50 at% oxygen, from 0 to 60 at% nitrogen, and from 0 to 20 at% hydrogen, more preferably has a thickness between 45 nm and 120 nm;
  • the high refractive layer is silane based, more preferably comprises from 70 to 100 at% silicon, from 0 to 10 at% oxygen, from 0 to 10 at% nitrogen, and from 0 to 30 at% hydrogen, more preferably has a thickness between 25 nm and 65 nm;
  • the low refractive layer is silica based, more preferably comprises from 30 to 50 at% silicon, from 50 to 70 at% oxygen, from 0 to 20 at% nitrogen, and from 0 to 10 at% hydrogen, more preferably has a thickness between 55 nm and 140 nm;
  • the bottom layer comprises an absorbing layer, wherein said bottom layer comprises from 70 to 100 at% silicon, from 0 to 10 at% oxygen, from 0 to 10 at% nitrogen, and from 0 to 30 at% of hydrogen.
  • This preferred stack of layers is ideal for tuning the colour of a coating, choosing a colour from the whole visible range.
  • the top layers comprises from 30 to 50 at% silicon, from 0 to 50 at% oxygen, from 0 to 60 at% nitrogen, and more preferably has a thickness between 45 nm and 120 nm;
  • the high refractive layer is silane based, more preferably comprises from 70 to 100 at% silicon, from 0 to 10 at% oxygen, from 0 to 10 at% nitrogen, and from 0 to 30 at% hydrogen, more preferably has a thickness between 25 nm and 65 nm;
  • the low refractive layer is silica based, more preferably comprises from 30 to 50 at% silicon, from 50 to 70 at% oxygen, from 0 to 20 at% nitrogen, and from 0 to 10 at% hydrogen, more preferably has a thickness between 55 nm and 140 nm;
  • the bottom layer comprises an absorbing layer, wherein said bottom layer comprises from 70 to 100 at% silicon, from 0 to 10 at% oxygen, from 0 to 10 at% nitrogen, and from 0 to 30 at% of hydrogen.
  • This preferred stack of layers is even more ideal for tuning the colour of a coating, choosing a colour from the whole visible range.
  • the top layers comprises from 30 to 50 at% silicon, from 0 to 40 at% oxygen, from 25 to 60 % nitrogen, more preferably from 0 to 10 at% hydrogen, more preferably has a thickness between 45 nm and 60 nm;
  • the high refractive layer is silane based, more preferably comprises from 70 to 100 at% silicon and from 0 to 30 at% hydrogen, more preferably has a thickness between, 50 nm and 65 nm;
  • the low refractive layer is silica based, more preferably comprises most preferably 30 to 50 at% silicon and 50 to 70 at% oxygen, more preferably has a thickness between 110 and 140 nm;
  • the bottom layer comprises an absorbing layer, wherein said bottom layer comprises from 70 to 100 at% silicon and from 0 to 30 at% hydrogen.
  • This preferred stack of layers is ideal for the optimization of the red color purity of the coating.
  • the top layers comprises from 30 to 50 at% silicon, from 0 to 40 at% oxygen, from 25 to 60 % nitrogen, more preferably has a thickness between 45 nm and 60 nm;
  • the high refractive layer is silane based, more preferably comprises from 70 to 100 at% silicon and from 0 to 30 at% hydrogen, more preferably has a thickness between, 50 nm and 65 nm;
  • the low refractive layer is silica based, more preferably comprises most preferably 30 to 50 at% silicon and 50 to 70 at% oxygen, more preferably has a thickness between 110 and 140 nm;
  • the bottom layer comprises an absorbing layer, wherein said bottom layer comprises from 70 to 100 at% silicon and from 0 to 30 at% hydrogen.
  • This preferred stack of layers is ideal for the optimization of the red colour purity of the coating.
  • the high refractive layer has a refractive index of from 2.5 to 4, the low refractive layer has the refractive index from 1.3 to 1.8, and the top layer has the refractive index of from 1.7 to 2.1.
  • the high refractive layer has a refractive index of from 2.8 to 3.6, the low refractive layer has the refractive index from 1.4 to 1.7, and the top layer has the refractive index of from 1.7 to 1.9.
  • Different layers can be defined using indices of refraction. By selecting layers based on their refractive index, the colour of the coating can be adjusted as desired.
  • the high refractive layer comprises an amorphous silicon (a-Si) and/or a hydrogenated amorphous silicon (a- Si:H), preferably wherein the high refractive layer comprises hydrogen with a content between 5 to 30 at%, more preferably between 10 to 25 at%, more preferably between 15 to 24 at%, more preferably between 16 to 23 at%, more preferably between 17 to 22 at%, more preferably between 18 to 21 at% and in particular about 20at%.
  • a-Si amorphous silicon
  • a- Si:H hydrogenated amorphous silicon
  • the high refractive layer comprises an amorphous silicon (a-Si).
  • a-Si amorphous silicon
  • Amorphous silicon is known for its non-crystalline structure, which can provide unique optical characteristics such as high refractive index and transparency. These properties make it suitable for applications where precise control over light refraction is essential, such as in certain optical devices or coatings.
  • the high refractive layer comprises a hydrogenated amorphous silicon (a- Si:H), preferably wherein the high refractive layer comprises hydrogen with a content between 5 to 30 at%, more preferably between 10 to 25 at%, more preferably between 15 to 24 at%, more preferably between 16 to 23 at%, more preferably between 17 to 22 at%, more preferably between 18 to 21 at% and in particular about 20at%.
  • Hydrogenation introduces hydrogen atoms, altering the amorphous silicon's optical and electronic properties. This modification allows for precise tuning of transparency and refractive index, making it ideal for applications requiring controlled light refraction.
  • a-Si:H enhances stability, mitigating degradation concerns over time. Its compatibility with thin-film technology and diverse fabrication processes further supports its choice, sselling its suitability for practical implementation in the invention's design.
  • the stack of the high refractive layer alternating with the low refractive layer comprises two or more high refractive layers and two or more low refractive layers
  • each high refractive layer consisting essentially of :
  • a-Si wherein the high refractive layer consisting essentially of a-Si has a thickness between 20 and 90 nm, preferably between 50 and 60 nm; or II. a-Si:H, wherein the high refractive layer consisting essentially of a-Si:H comprises hydrogen with a content between 5 to 30 at%, more preferably between 10 to 25 at%, more preferably between 15 to 24 at%, more preferably between 16 to 23 at%, more preferably between 17 to 22 at%, more preferably between 18 to 21 at% and in particular about 20at%, and wherein said high refractive layer consisting essentially of a-Si:H has a thickness between 50 and 75 nm, more preferably between 52.5 and 75 nm, more preferably between 55 and 75 nm, more preferably between 57.5 and 75 nm, more preferably between 60 and 75 nm, more preferably between 62.5 and 75 nm, preferably between 65 nm and 75 nm, even more
  • each low refractive layer comprising SiO2 has a thickness between 100 nm and 200 nm, preferably between 140 and 160 nm.
  • the high refractive layer comprises a mix of a non-hydrogenated amorphous silicon and a hydrogenated amorphous silicon.
  • amorphous silicon possesses a greater capacity for light absorption, making it conducive to achieving darker colours. Furthermore, it also reduces the angle dependence of the colour.
  • the inventors found that incorporating both hydrogenated amorphous silicon (a-Si:H) and non-hydrogenated amorphous silicon (a-Si) proves valuable for precisely adjusting the nuances in creating a red colour.
  • controlling the hydrogenation of silica offers the ability to subtly influence both the absorption properties and the refractive index. This, in turn, provides the opportunity to introduce nuanced variations in colours.
  • Si:H and a-Si in the high refractive layer allows for precise adjustment of colour nuances, particularly in creating a red colour.
  • the optimal thickness ranges are hereby chosen to align with the wavelength characteristics of red light, enhancing efficiency and colour accuracy in applications where these factors are crucial.
  • the specific thickness range plays a role in controlling interference effects and optimizing the reflective properties of the multilayer structure.
  • the stack of the high refractive layer alternating with the low refractive layer comprises two or more high refractive layers and two or more low refractive layers, - the two or more high refractive layers, each high refractive layer consisting essentially of :
  • a-Si wherein the high refractive layer consisting essentially of a-Si has a thickness between 20 and 90 nm, preferably between 50 and 60 nm; or
  • a-Si:H wherein the high refractive layer consisting essentially of a-Si:H comprises hydrogen with a content between 5 to 30 at%, more preferably between 10 to 25 at%, more preferably between 15 to 24 at%, more preferably between 16 to 23 at%, more preferably between 17 to 22 at%, more preferably between 18 to 21 at% and in particular about 20at%, and wherein said high refractive layer consisting essentially of a-Si:H has a thickness between 50 and 75 nm, more preferably between 52.5 and 75 nm, more preferably between 55 and 75 nm, more preferably between 57.5 and 75 nm, more preferably between 60 and 75 nm, more preferably between 62.5 and 75 nm, preferably between 65 nm and 75 nm, even more preferably between 65 and 70 nm;
  • each low refractive layer consists essentially of SiO2 has a thickness between 100 nm and 200 nm, preferably between 140 and 160 nm.
  • said stack of high refractive index layer alternating with a low refractive index layer comprises three or more high refractive layers and three or more low refractive layers, more preferably four or more high refractive layers and four or more low refractive layers, and even more preferably five or more high refractive layers and five or more low refractive layers.
  • the multilayer coating further comprises an anti-reflective top layer on top of said stack of the high refractive layer alternating with the low refractive layer, the anti-reflective top layer comprising any transparent material that has a refractive index from 1.7 to 2.1, wherein the anti- reflective top layer has a thickness between 45 and 120 nm, preferably between 45 and 60 nm.
  • the anti-reflective top layer comprises from 30 to 50 at% silicon, from 0 to 50 at% oxygen, from 0 to 60 at% nitrogen, and from 0 to 20 at% hydrogen; and more preferably from 30 to 50 at% silicon, from 0 to 40 at% oxygen, from 25 to 60 % nitrogen, and from 0 to 10 at% hydrogen.
  • the top layer comprises from 30 to 50 at% silicon, from 0 to 50 at% oxygen and from 0 to 60 at% nitrogen; and more preferably from 30 to 50 at% silicon, from 0 to 40 at% oxygen and from 25 to 60 % nitrogen.
  • the optimized top layer offers flexibility, ranging for example from fully oxidized SiO2 to fully nitride Si3N4, depending on the desired nuance. Any oxynitride variation within the spectrum of SixOyNz can be employed to finely tune the refractive index.
  • the top player comprises a silicon content from 31 to 45 at%, more preferably from 32 to 44 at% and even more preferably from 33 and 43 at%, the remainder being a combination of nitrogen and oxygen.
  • the preference for this silicon oxynitride solution over other oxides lies in its unique advantage of enabling streamlined processing with only a silicon sputtering target.
  • the invention in a second aspect, relates to a process for applying a multilayer coating to a substrate, said process comprising the sequential steps of: a. providing the substrate; b. applying an optional bottom layer on top of the substrate; c. applying, layer by layer, on top of the bottom layer or the substrate a stack of a high refractive layer alternating with a low refractive layer by vapour deposition; d.
  • said low refractive layer comprises from 30 to 50 at% silicon, from 40 to 70 at% oxygen, from 0 to 30 at% nitrogen, and from 0 to 20 at% hydrogen and wherein said low refractive layer has a thickness of less than 140 nm, and that said high refractive layer comprises from 60 to 100 at% silicon, from 0 to 20 at% oxygen, from 0 to 30 at% nitrogen, and from 0 to 40 at% hydrogen, and wherein said high refractive layer has a thickness less than 75 nm.
  • the vapour deposition comprises physical or chemical vapour deposition, preferably plasma enhanced chemical vapour deposition.
  • Vapor deposition techniques offer numerous advantages compared to wet coatings such as a higher adhesion, no chemical waste, easier scaling up to industrial level. So there is an interest in creating red coatings by vapour deposition techniques, and being able to tune the shade according to the needs.
  • Vapour deposition processes are used to deposit thin layers of material onto a base material, said substrate. These processes are highly sensitive and must be carried out in a chamber that is isolated from external atmospheric conditions and contaminants at very low pressure inside a vacuum. There are two types of vapour deposition, physical vapour deposition (PVD) and chemical vapour deposition (CVD).
  • the thin layer is deposited on a base material, said substrate such as glass or silicon wafers, in theory any material can have a thin layer deposited onto its surface.
  • the substrate is essentially a foundation on which the thin layer will be deposited. Designing and executing a vapour deposition process requires careful consideration of materials and equipment to ensure compatibility of the system.
  • the substrate is then exposed to one or more vapourised sources, the presence of the vapours along with other stimuli will cause the thin layer to deposit on the surface of the substrate.
  • the type of thin layer that will deposit is dictated by the chemistry of the vapours.
  • Thin layers deposited through processes such as vapour deposition have their own unique properties. These layers are used to enhance or improve the original substrate material.
  • the layer can also be used as a component part of a composite structure. This makes it possible to create materials for a specific application. The properties desired in the final application will dictate the type of layer to deposit which requires careful consideration of the materials and operating conditions for the deposition process.
  • the source is a solid material in solid form inside the chamber with the substrate.
  • the solid material forms vapours which will coat the surface of the substrate.
  • CVP processes are different from PVD processes. Instead of forming vapours from a solid material within the chamber, gasses are pumped into the chamber from an external source which react and cause the thin layer to deposit.
  • the primary difference between PVD and CVD is the means through which the vapours are generated. In PVD the vapours need to be generated from a solid or liquid source, whereas in CVD no new generation is required because the source is already in a vapour phase. There are notable differences both in deposition and material properties between layers deposited with PVD and CVD.
  • CVD the substrate is placed in a reactor under vacuum, source gasses are pumped into the reactor which react with the surface of the substrate. This causes a thin layer to deposit on the surface. External stimuli such as heat or plasma can be used to initiate or propagate the reaction which causes the film to deposit. Gaseous by-product will form as result of the reaction and must be pumped out.
  • CVD processes are categorized and classified by conditions used. For example pressure inside the reactor, some processes are more sensitive and require a higher vacuum while others are not as critical. For this reason, there are different levels of CVD based on pressure.
  • CVD chemical vapor deposition
  • plasma-enhanced CVD which involves converting the precursors to plasma.
  • CVD makes it possible to make coatings that make materials last longer such as making metals resistant to rust and corrosion.
  • Plasma enhanced CVD is an example of a preferred deposition technique in said invention due to their numerous advantages such as good coating homogeneity, high control on the film thickness, high versatility on the materials, high adhesion on most substrates and, moreover these techniques do not use solvents.
  • the invention relates to a use of the multi-layered coating as a coloured coating, preferably as a red coating.
  • Comparative examples 1-2 A stack with only transparent layers.
  • a distributed Bragg reflector strategy was used to selectively reflect red light and obtain red-appearing materials on a substrate. To achieve this effect, several transparent materials with different refractive indices are required.
  • the stack comprises the layers as given in table 1.
  • Table 1 a 3 layer and 5 layer stack. refraction layer thickness (nm) composition index n
  • Example 1 1 2.8 50-65 TiO? 3 layer stack
  • Comparative example 3 and example 4 A stack with an a-Si:H/SiO2 system.
  • a distributed Bragg reflector strategy was used to selectively reflect red light and obtain red-appearing materials on a substrate. To achieve this effect, several transparent materials with different refractive indices are required.
  • a stack comprises alternating a-Si:H and SiO 2 layers as described in table 2.
  • Table 2 a 1 layer and 5 layer stack.
  • a-Si:H With its low bandgap ( ⁇ 2,0 eV), a-Si:H can be used to absorb high energy photons, together with the distributed Bragg reflector strategy. Except that it tends to reflect most of the blue before having the opportunity to absorb it.
  • Example 5 - 7 A multilayer stack for providing a red coloured coating.
  • a distributed Bragg reflector strategy was used to selectively reflect red light and obtain red-appearing materials on a substrate. To achieve this effect, several transparent materials with different refractive indices are required.
  • a stack comprising the layers as described in table 3. All three examples have a Si substrate as base.
  • Table 3 multilayer stack. refraction thickness layer composition index n (nm)
  • the top layer is an anti-reflective layer topcoat to significantly reduce secondary reflections, notably in the blue region.
  • This comprises a transparent layer of determined thickness of a material whose refractive index is intermediate between the high refractive index and the air. A ⁇ Os was chosen because of the best refractive index matching.
  • red colour purity ideally needs an anti-reflective top layer, a stack of a-Si:H and SiO? layers, and a bottom layer.

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Abstract

La présente invention concerne un revêtement multicouche comprenant un empilement d'une couche à réfraction élevée alternant avec une couche à faible réfraction, ladite couche à faible réfraction comprenant 30 à 50 % en atome de silicium, 40 à 70 % en atome d'oxygène, 0 à 30 % en atome d'azote et 0 à 20 % en atome d'hydrogène et ladite couche à faible réfraction présentant une épaisseur inférieure à 140 nm, ladite couche à réfraction élevée comprenant 60 à 100 % en atome de silicium, 0 à 20 % en atome d'oxygène, 0 à 30 % en atome d'azote et 0 à 40 % en atome d'hydrogène et ladite couche à réfraction élevée présentant une épaisseur inférieure à 65 nm. L'invention concerne également un procédé d'application d'un revêtement multicouche sur un substrat.
PCT/EP2023/087486 2022-12-22 2023-12-21 Revêtement multicouche de couleur ajustable WO2024133817A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6500251B1 (en) 1996-05-09 2002-12-31 Merck Patent Gesellschaft Mit Beschrankter Haftung Multi-coated interference pigments
WO2003106569A1 (fr) * 2002-06-01 2003-12-24 Ciba Specialty Chemicals Holding Inc. Structures planes-paralleles de silicium/oxyde de silicium
WO2006088761A2 (fr) 2005-02-12 2006-08-24 Engelhard Corporation Pigment a effet multicouche
US20100062244A1 (en) * 2005-11-17 2010-03-11 Ciba Corporation Process for Preparing Flake-Form Particles
US20110105676A1 (en) * 2007-08-20 2011-05-05 Ciba Corporation Process for preparing platelet-like pigments comprising a nitrogen doped carbon coating
KR101587643B1 (ko) * 2014-10-14 2016-01-25 광운대학교 산학협력단 비훈색성 투과형 컬러필터 및 그 제조방법
WO2017070769A1 (fr) * 2015-10-29 2017-05-04 ШИРИПОВ, Владимир Яковлевич Revêtemement optique combiné et procédé de sa fabrication (et variantes)
CN110777366A (zh) * 2019-10-15 2020-02-11 宁波大学 一种纳米晶氧化硅薄膜及其制备的类光刻胶氧化硅材料

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6500251B1 (en) 1996-05-09 2002-12-31 Merck Patent Gesellschaft Mit Beschrankter Haftung Multi-coated interference pigments
WO2003106569A1 (fr) * 2002-06-01 2003-12-24 Ciba Specialty Chemicals Holding Inc. Structures planes-paralleles de silicium/oxyde de silicium
WO2006088761A2 (fr) 2005-02-12 2006-08-24 Engelhard Corporation Pigment a effet multicouche
US20100062244A1 (en) * 2005-11-17 2010-03-11 Ciba Corporation Process for Preparing Flake-Form Particles
US20110105676A1 (en) * 2007-08-20 2011-05-05 Ciba Corporation Process for preparing platelet-like pigments comprising a nitrogen doped carbon coating
KR101587643B1 (ko) * 2014-10-14 2016-01-25 광운대학교 산학협력단 비훈색성 투과형 컬러필터 및 그 제조방법
WO2017070769A1 (fr) * 2015-10-29 2017-05-04 ШИРИПОВ, Владимир Яковлевич Revêtemement optique combiné et procédé de sa fabrication (et variantes)
CN108349792A (zh) 2015-10-29 2018-07-31 伊扎维克技术有限责任公司 复合光学涂层及其制造方法（变型）
CN110777366A (zh) * 2019-10-15 2020-02-11 宁波大学 一种纳米晶氧化硅薄膜及其制备的类光刻胶氧化硅材料

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