• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention is based on the object to improve a hard anti-reflection coating with respect to the scratch resistance. For this purpose, an optical element (1) having a substrate (10) which is transparent in the visible spectral range and a multilayer antireflection coating (2) deposited on the substrate (10) is provided which alternately has layers with a first refractive index and a second, higher refractive index the higher refractive index layers include nitride or oxynitride; and the first refractive index layers comprise oxide of silicon and at least one other element, and wherein the molar ratio of silicon in the first refractive index layers is greater than molar proportions of the one or more other elements; top layer of the multilayer antireflection coating is a layer with a first refractive index, and wherein on the antireflection coating, a layer (3) of chain-like fluoroorganic molecules is arranged, wherein the molecules are bound end to the surface of the optical element.
    公开号:CH709768B1
    申请号:CH00794/15
    申请日:2015-06-03
    公开日:2019-01-31
    发明作者:Apitz Dirk；Walther Marten；Henn Christian
    申请人:Schott Ag；
    IPC主号:
    专利说明:

    Description: The invention relates generally to optical elements such as viewing windows or cover glasses for optical displays, for example of mobile telephones or watches, or for optical systems, such as, for example, lenses or optical measuring devices. In particular, the invention relates to measures to improve the surface's resistance to scratching.
    In order to protect surfaces of optical elements from scratching, it is known to provide the surface with a hard coating. A hard anti-reflective coating is known from EP 2 492 251 A1. The invention is based on the object of improving the scratch resistance of such coatings. This object is solved by the subject of the claims.
    Accordingly, the invention provides an optical element with high scratch resistance, with a transparent substrate in the visible spectral range, in particular in at least a partial range of the wavelength range from 380 nanometers to 780 nanometers. A multilayer antireflection coating is deposited on the substrate, which alternately has layers with a first refractive index and a second, higher refractive index, the layers with a higher refractive index containing nitride or oxynitride and the layers with the first refractive index containing oxide of silicon and at least one further element, wherein the molar fraction of silicon in the layers with the first refractive index outweighs the molar fraction of the further element or elements, and the top layer of the multilayer antireflection coating is a layer with the first refractive index, and the top layer is a layer of chain-shaped fluoroorganic molecules, the molecules preferably being bound at the end to the surface of the top layer of the anti-reflective coating. Due to the end-to-end bond to the surface, the chains of the fluoroorganic coating are oriented away from the surface or have a preferred orientation along the surface normal.
    An optical element is then scratch-resistant in the sense of the invention if, after an abrasive stress on the coating, scratches are at least visually less noticeable or not visible compared to the uncoated substrate.
    [0005] The layers containing nitride or oxynitride are preferably also silicon-based, like the layers with the first refractive index. In particular, the layers with a second refractive index as well as the layers with the first refractive index can be doped with at least one further element. According to this embodiment, the layers with a higher refractive index contain nitride or oxynitride of silicon and at least one further element.
    However, it is also possible to form the layers with a second, higher refractive index from nitrides or oxynitrides of other elements other than silicon. For example, layers with nitrides or oxynitrides of titanium or chromium may be mentioned as the sole constituent or main constituent.
    It is not excluded that there are also intermediate layers between the alternating layers with the first and second refractive index. For example, doped silicon oxynitride layers could also be inserted between layers with the first and second refractive index, which contain silicon oxide or nitride, preferably silicon nitride, if this results in a favorable optical design.
    In addition, gradients of layers are to be understood as intermediate layers, which at least partially change the oxygen or nitrogen content.
    It has surprisingly been found that the organofluorine molecules again considerably improve the scratch resistance of the anti-reflective coating, which is already very hard due to the nitride layers. In wear tests, this manifests itself in a significantly longer period of time until there is a significant increase in light scattering and a change in the anti-reflective properties.
    [0010] In particular, the layer of organofluorine molecules is particularly preferably very thin, namely monomolecular. This individual molecule layer is therefore not optically or hardly effective and is accordingly also visually unremarkable.
    [0011] It is believed that the organofluorine layer, although not itself hard, reduces interaction with the surface. It is particularly important here that the oxidic top layer of the anti-reflective coating has a lower hardness than the nitride layer that follows due to the alternating layer sequence. One effect is based on a reduction in the coefficient of friction of the surface by the fluoroorganic molecules.
    The fluoroorganic layer prevents the formation of chemical bonds between the surface and the abrasive medium, as occurs with an effective abrasion. For example, glass is often polished with cerium oxide, because this material forms covalent bonds with glass and thus significantly increases the removal. Abrasion and polishing is typically a physico-chemical process.
    The coating of the optical element is thus more resistant to scratching as long as the fluoroorganic molecules are bound to the surface. A detachment of the fluoroorganic molecules can occur, however, if the surface is chemically attacked through the fluoroorgan layer or in places where the fluoroorgan layer has been degraded. This is where the additional element present as oxide in the top layer comes to the tra
    CH 709 768 B1. By means of this at least one further element, the chemical resistance of the surface can namely be considerably improved and thus indirectly the durability of the fluoroorganic molecules can also be improved.
    According to a particularly preferred embodiment of the invention, the layer of organofluorine molecules is therefore deposited directly on the surface of the uppermost, oxidic layer of the antireflection coating. If necessary, a thin, optically ineffective intermediate layer can also be provided, which serves as an adhesion promoter. Such an adhesion promoter layer preferably has a layer thickness of less than 10 nm, preferably less than 8 nm, particularly preferably less than 6 nm, in order not to be optically effective. A layer containing silicon oxide, in particular a mixed oxide layer with silicon oxide as the main constituent, is suitable for such an adhesion promoter layer.
    The hard anti-reflective coating with the layer of fluoroorganic molecules is particularly suitable for likewise hard substrates with high Knoop hardness and / or a high modulus of elasticity. A high Knoop hardness is essentially maintained or even improved even after coating. Accordingly, according to one embodiment of the invention, the Knoop hardness of the optical element on the coated surface is at least 600 kilograms per square millimeter (600 kg / mm 2 ). According to a further embodiment, a substrate is selected which has an elastic modulus of at least 50 GPa. One of the preferred materials for the substrate is sapphire or Al 2 O 3 .
    The invention is explained in more detail below, also with reference to the accompanying drawings.
    [0017] The figures show:
    Fig. 1 3 shows a cross section through an optical element according to a first embodiment, Fig. 2 2 shows a cross section through a variant of the example shown in FIG. 1, Fig. 3 Diagrams of the spectral reflectivity measured on two samples before and after an abrasion test, Fig. 4 Bar graphs of the percentage increase in haze after a sandpaper test for an uncoated, chemically toughened glass substrate and for three differently coated, chemically toughened glass substrates, 5 and 6 Diagrams of the increase in haze value and reflectivity depending on various influencing factors, and 7 and 8 further embodiments of optical elements.
    Fig. 1 and Fig. 2 show examples of optical elements 1 according to the invention with high scratch resistance, with a transparent substrate 10 in the visible spectral range and a multi-layer antireflective coating 2 deposited on the substrate 10. Layers 25, 27 of the antireflective coating 2 with a first refractive index alternate with layers 24, 26 with a second refractive index that is higher than the first refractive index.
    On the top layer 27 of the antireflection coating, a layer of 3 chain-shaped fluoroorganic molecules is arranged, the molecules being bound at the end to the surface of the top layer 27 of the antireflection coating 2.
    The fluoroorganic molecules preferably contain perfluorinated carbon chains, in which in particular all hydrogen atoms can be replaced by fluorine atoms. Furthermore, the fluoroorganic molecules are preferably individually covalently bound to the surface of the optical element 1. The individual molecules can also form more than just a covalent bond with the surface.
    Suitable for the layer 3 are, without limitation to the specific embodiments, in particular perfluoroethers with a terminal silane radical, for example the “Optool ™ AES4-E” coating or the “Optool ™ DSX” coating from Daikin Industries LTD, perfluoroethers with two terminal Silane residues, for example the «Fluorolink S10» coating Solvay Solexis, perfluoroalkylsilane, preferably with a purely inorganic silicon oxide content.
    [0022] The coating is preferably carried out by liquid coating using a coating fluid. Roll coating, spin coating, dip coating or the spray process are suitable for this purpose.
    According to yet another embodiment of the invention, the layer 3 is applied by a vacuum coating process, the fluoroorganic molecules evaporating in a vacuum and being deposited on the surface of the substrate 10 coated with the anti-reflective coating 2. For example, the “Duralon UltraTec” from Cotec GmbH, Karlstein, sold in tablet form, is suitable.
    An adhesion promoter layer between the layer 3 and the anti-reflective coating 2, as is provided, for example, according to WO 2012/163 946 A1, is not necessary in order to improve the scratch resistance of the surface of an optical element 1 according to the invention.
    CH 709 768 B1 The layers 24, 26 with a higher refractive index essentially contain nitride or oxynitride and the layers with a first refractive index oxide of silicon and at least one further element. The main proportion of the nitridically or oxidically present elements is formed according to a preferred embodiment, but in any case by silicon, so that the molar proportion of silicon in the layers outweighs the molar proportion of the further element or elements. The ratio of the amounts of silicon and the additional element or elements in the individual layers of the anti-reflective coating is preferably at least 5: 1, preferably at least 8: 1. In other words, the antireflection coating 2 contains at least five times, preferably at least eight times, more silicon compared to the amount of the at least one further element.
    The at least one further element is selected from the elements aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, barium, strontium, cesium, niobium, boron.
    [0027] These elements form both oxides and nitrides and at the same time improve the chemical resistance of the coating.
    According to another embodiment, nitrides or oxynitrides of an element other than silicon are used for the layers with a second, higher refractive index as the main component or even the sole component. For example, titanium nitride, boron nitride, aluminum nitride and / or chromium nitride or oxynitrides of titanium, boron, aluminum and / or chromium are considered.
    The improvement in the chemical resistance of the coating according to the invention can be demonstrated, for example, by means of a salt water spray test, preferably in accordance with DIN EN 1096-2: 2001-05.
    Vacuum deposition processes are particularly suitable for the production of the anti-reflective coating. Accordingly, the invention generally provides, without limitation to the example shown, a method for producing an optical element 1 according to the invention, in which
    a substrate 10 which is transparent in the visible spectral range is provided and
    - A multi-layer anti-reflective coating 2 is applied to the substrate 10 by
    - Layers with a first refractive index and a second, higher refractive index are alternately deposited by means of a vacuum deposition process, the layers with a higher refractive index containing nitride or oxynitride and the layers with the first refractive index containing oxide of silicon and at least one further element, and the molar fraction of Silicon in the layers with the first refractive index outweighs the molar proportions of the further element or elements, and wherein the top layer of the multilayer antireflection coating is a layer with the first refractive index, and a coating with a layer of 3 chain-shaped fluoroorganic molecules is applied to the antireflection coating, wherein the molecules are bound at the end to the surface of the optical element, particularly preferably to the uppermost layer 27 of the anti-reflective coating 2.
    It is further preferred that the layers 24, 25, 26, 27 of the anti-reflective coating 2 are deposited by reactive magnetron sputtering. A silicon sputtering target can be used for this purpose, which is doped with at least one further element. Aluminum is particularly preferred as at least one further element, preferably with a content of at most 20 mol% in the target. The layers of the anti-reflective coating 2, which are produced by means of such a target, are therefore oxide layers with a first refractive index and nitridic layers with a second refractive index of silicon and aluminum, the quantitative ratio of silicon to aluminum being at least 5: 1. Instead of aluminum, however, the other elements mentioned or, in addition to aluminum, at least one other of the elements mentioned can also be present.
    As an alternative to the deposition by reactive magnetron sputtering, ion beam sputtering can also be used to apply the layers of the anti-reflective coating.
    According to a particularly preferred embodiment, on which the exemplary embodiments in FIGS. 1 and 2 are based, an anti-reflective coating 2, which comprises a layer stack of four successive layers 24, 25, 26, 27, is deposited on the substrate 1 , The lowermost layer 24 is a higher refractive index layer containing silicon nitride, the further higher refractive index layer 26 containing silicon nitride, which forms the uppermost high refractive index layer of the layer stack, having the greatest layer thickness within the layer stack, and the uppermost layer 27 of the layer stack having a layer forms a lower refractive index made of silicon oxide, preferably with a proportion of aluminum, and has the second largest layer thickness under the layers of the layer stack, the first layer 24 and the second layer 25, which like the top layer 27 form a layer with a lower refractive index made of silicon oxide with a The proportion of aluminum is composed of a layer thickness that is thinner than the layer thickness of the top layer.
    In particular in the example shown in FIG. 2, the layer thickness of the uppermost, high-index layer of the likewise four-layer antireflection coating is very large. The example shown in Fig. 2 is optimized for a very high scratch resistance. Surprisingly, however, the anti-reflective properties are only slightly worse than in the example shown in FIG. 1 and optimized for low reflectivity.
    In addition to the anti-reflective coating 2, the coating of the surface 13 of the substrate 10 can also comprise further layers. According to one embodiment, in general, without being limited to that shown in FIGS
    CH 709 768 B1 shown examples provided that a layer 28 containing silicon oxide is deposited on the surface 13 of the substrate 10, which layer serves as an adhesion promoter for the subsequently deposited anti-reflective coating 2. The layer 28 forms an inorganic coating 20 together with the antireflection coating 2. For example, a thin silicon oxide layer is suitable for the layer 28, in particular a layer with a composition such as that of the low-refraction layers 25, 26 of the antireflection coating 2.
    Such an adhesion promoter layer in the form of a layer 28 made of silicon oxide is particularly suitable for coupling the hard antireflection coating to hard substrates. Such a coating is particularly suitable for a substrate 10 made of sapphire or Al 2 O 3 . According to one embodiment of the invention, an optical element 1 in the form of a watch glass with a sapphire substrate 10 and a coating according to the invention is provided. The coating makes it possible to achieve the scratch resistance of uncoated sapphire, or at least to approach it, but at the same time also to improve the optical properties with regard to reflectivity. Sapphire has a high refractive index of over 1.7, so sapphire glasses are highly reflective. This disadvantage is avoided with the anti-reflective coating.
    The relative thicknesses of the layers explained above for the embodiment of FIG. 1 are also met in the example shown in FIG. 2 and preferably also apply to the embodiment explained below with a very thick top layer 26 with a high refractive index.
    In the variant of FIG. 2, the uppermost layer containing silicon nitride or the uppermost layer 26 with a second refractive index is significantly thicker than in the example shown in FIG. 1. In general, without being limited to the specific example shown, it is provided according to one embodiment of the invention that the anti-reflective coating 2 comprises a layer stack of four successive layers 24, 25, 26, 27 with two layers 24, 26 with a second, higher refractive index which the upper of the two layers 26 with a second, higher refractive index has a layer thickness which is at least 40% of the thickness of the antireflective coating 2, preferably at least 60% of the thickness of the antireflective coating 2, particularly preferably at least 70% of the thickness of the antireflective coating 2.
    In the example shown in FIG. 2, the thickness of the layer 26 is even more than 70% of the layer thickness of the anti-reflective coating 2.
    According to yet another embodiment of the invention, it is provided that the antireflection coating 2 comprises a layer stack in which the top layer 26 with a second refractive index has the greatest layer thickness of all layers of the antireflection coating and a layer thickness in the range from 100 nm to 700 nm, preferably from 300 nm to 600 nm, very particularly preferably from 400 nm to 500 nm. This embodiment of the invention preferably also applies to the examples shown in FIGS. 1 and 2, but can also be applied to other anti-reflective coatings with more or fewer layers. The thickness of the upper nitride hard material layer ensures high resistance.
    An abrasion test can be carried out to test and compare the scratch resistance of the optical elements according to the invention. The test used for the tests is a modified Bayer test according to ASTM F735-11. The optical elements to be tested are covered in a trough with a granular, abrasive medium and the trough is set into oscillation. Aluminum oxide sand with a grain size between 297 μm and 420 μm and a Mohs hardness of 9 was used as the abrasive medium. The tub was filled with a quantity of 2 kg of sand, resulting in a layer of sand about 18 mm thick. The tub oscillates at 150 cycles per minute.
    Fig. 3 shows the spectral reflectivity of two optical elements in the visible spectral range between 450 nm and 700 nm, each measured before and after an abrasion test as described above with 8000 cycles.
    Curve "A" is the reflectivity of a sapphire substrate coated with a four-layer anti-reflective coating, curve "C" is the reflectivity of this sample after the abrasion test.
    Curve "B" shows the spectral reflectivity of an optical element according to the invention with a sapphire substrate, in which the anti-reflective coating 2 was additionally coated with a layer of fluoroorganic molecules 3. Finally, curve “D” shows the reflectivity of this sample after the abrasion test. As can be seen from the curves, the spectral reflectivity changes less with the optical element according to the invention after the abrasion test (ie from curve “B” to curve “D”) than with the anti-reflective coating without an organofluorine coating (curves “A” and “C”) , The difference between curves "A" and "B" is due to fluctuations in process parameters during coating as well as the presence of the fluoroorganic coating.
    The effect of the mechanical resistance or the effectiveness with regard to the susceptibility to scratching of the optical elements coated according to the invention can also be carried out using a sandpaper test. The effect of the layer system according to the invention is explained below using chemically toughened glass elements. The effect of grains of sand on the glass elements is simulated.
    Measurements of the percentage increase in the haze value as a result of the sandpaper test on anti-reflective coatings, as also shown in FIGS. 1 and 2, were carried out. A chemically toughened aluminosilicate glass serves as the transparent substrate 10.
    CH 709 768 B1 The haze measurement is carried out in accordance with the ASTM D1003-95 standard. In the case of the light transmitted through the glass element, the proportion of scattered light is compared with the intensity of the total transmitted light.
    The scattered radiation is a measure of the proportion of the area damaged by scratches. A defect in the surface of the glass leads to a deflection of the beam incident perpendicular to the glass surface and is deflected from its incident direction. The more damage there is on the surface, the more radiation is kept away from the detector. The haze value, expressed as a percentage, is a measure of the degree of damage to the surface.
    The results of the haze measurements are shown in FIG. 4 as bar graphs. The measured values in FIG. 4 thus reflect the percentage increase in the scattered light component due to scratches and other damage to the substrate surface after the sandpaper test. The sample designated “Design 8” has a four-layer structure similar to the example in FIG. 1. In the sample designated “Design 1”, the layer structure corresponds to the four-layer structure according to FIG. 2, in which the upper layer 26 with a second refractive index has a layer thickness that makes up more than 70% of the total layer thickness of the anti-reflective coating 2.
    The change in the haze value after the sandpaper test shows that the coating of the glass substrate with the layer system according to Design 1, which is optimized for scratch resistance with a particularly large layer thickness of the upper nitride hard material layer of the anti-reflection coating 2, is a surprisingly significant improvement compared to the uncoated glass substrate and also compared to the layer system of the design 8 (according to FIG. 1), the upper layer 26 of which with the second refractive index of the anti-reflection coating 2 is less than a third as thick as that according to design 1.
    Surprisingly, it is also shown that a layer system according to the invention, in which a layer 3 of fluoroorganic molecules is additionally applied, considerably improves the avoidance of scratches. As can be seen from FIG. 4, the measured increase in the haze value is reduced again by a factor of three compared to the hard anti-reflective coating without layer 3 and is now only 0.2%. In contrast, the increase in the haze value for the uncoated, chemically toughened aluminosilicate glass reference sample is 21.8% greater by a factor of 100.
    In the following, the effect of individual influencing variables on the scratch resistance is explained with reference to FIGS. 5 and 6. 5 and 6 show graphs of the increase in haze (referred to as "haze_diff") and the increase in reflectivity (referred to as "R_diff") by an abrasion test (modified Bayer test with 8000 abrasion cycles), depending on the various influencing factors. The diagrams were created by comparing a large number of samples, each with a different material of the substrate 10, with and without an anti-reflective coating 2, with and without chemical pretension, and with and without a layer 3 of fluoroorganic molecules.
    The effect of the individual influencing variables can thus be isolated. In FIG. 5, these influencing variables are evaluated in each case on optical elements without layer 3, in FIG. 6 with an applied layer 3. The scale on the abscissa indicates the proportion to which the influencing variable is present. Four diagrams are juxtaposed, which from left to right are the influencing factors substrate material (diagram designation “material”), chemical preload (diagram designation “ehern.str”), anti-reflective coating 2 (diagram designation “AR”) and fluoroorganic layer 3 (diagram designation “FOC”) ) represent. Except for the "material" diagram, the value "0" represents the absence of the influencing variable and the value "1" indicates its existence. In the "material" diagram, the value "0" denotes a borosilicate float glass and the value "1" an aluminosilicate glass. The reflectivity is the average value in the wavelength range from 380 to 780 nm.
    With an organic fluorine coating, the reflectivity increases on average by 0.55% in the abrasion test. Without an organic fluorine coating, this increase due to abrasion is 0.61%. That is, Due to the fluoroorganic layer 3, the increase in reflectivity due to abrasion is reduced by 10%.
    With an organic fluorine coating, the haze (the light scattering) increases on average by 0.037% in the abrasion test. Without a layer 3, this increase due to abrasion is 0.051%. This means that layer 3 reduces the abrasion-related haze increase by 27%.
    If all the patterns are considered in an evaluation independently of other parameters, one does not see the comparison with the degree of influence of the other parameters, but only the influence of the organofluorine layer and comes to the following values: With organofluorine layer 3, the reflectivity of all patterns increases in the abrasion test on average by 0.527%. Without an organic fluorine coating, this increase due to abrasion is 0.565%. This means that the increase in reflectivity caused by abrasion is reduced by 7% thanks to the fluoroorganic coating. With a fluoroorganic coating, the haze (the light scattering) increases by an average of 0.025% on all samples during the harsh abrasion test. Without fluoroorganic layer 3, this increase due to abrasion is 0.041%. This means that the organic fluorine layer 3 reduces the abrasion-related haze increase by 38%.
    It can be seen from the diagrams (FIGS. 5 and 6) that the influence on abrasion resistance (change in reflectivity or haze due to abrasion) depends more on material, prestress and anti-reflective coating. The influence of the fluoroorganic layer 3 is nevertheless clearly present.
    CH 709 768 B1 It also shows, however, that the combination of the organofluorine layer 3 with the anti-reflective coating 2 produces a significantly stronger effect than both influencing factors taken by themselves. The effect of the sand paper test shown in FIG. 4 is considerably greater. The anti-reflective coating 2 alone causes a reduction in the haze increase by a factor of 30. With the layer 3, this effect is again considerably increased and causes a reduction by a factor of 100. The effect only caused by the fluoroorganic layer 3 according to FIGS. 5 and 6 (modified Bayer test with 8000 cycles) is significantly smaller, even if it has to be taken into account that the abrasion test of FIGS. 5 and 6 simulates clearly harsher conditions and the results are therefore not directly comparable.
    The fact that the layer 3 interacts with the anti-reflective coating 2 according to the invention is also evident from the table below:
    Haze increase with layer 3 Haze increase without layer 3 Improvement in haze growth without AR 0.04 0.07 43% with AR 0.06 0.3 80%
    The table shows the effect of the layer 3 for a borosilicate float glass substrate 10 with and without an anti-reflective coating 2 based on the percentage improvement in the increase in the haze value after the abrasion test. A percentage improvement means that the increase in haze compared to the sample before the abrasion test is low. Layer 3 accordingly reduces the haze increase compared to the uncoated substrate.
    However, if, in contrast, an inventive combination of antireflective coating 2 and fluoroorganic layer 3 is used, there is an even more significant improvement in the increase in light scattering (haze) compared to a sample coated with antireflective coating 2 but without layer 3. At 80%, the improvement in the increase in haze is almost twice that of the uncoated sample. When the reflectivity increases, the effect is smaller (see FIG. 3), but is still clear. It should also be noted here that the reflectivity in an antireflection coating is sensitive to a reduction in the layer thickness of the top layer 27. If the layer thickness is reduced by abrasion, this leads to a spectral shift in the interference effects. In contrast, in the case of an uncoated glass, the refractive index and thus the reflectivity per se do not change in the case of abrasion. In this respect, the improvement achieved by layer 3 in the anti-reflective coating that is more sensitive to abrasion with respect to reflectivity also represents a very clear effect.
    The disproportionately large effect in improving the scratch resistance is attributed to the interaction of the doping of the top layer 27 of the antireflection coating with the coating by means of the layer 3 of fluoroorganic molecules. On the one hand, the chemical resistance is increased by at least one further oxide in addition to silicon oxide. This oxide of a further element may also influence the covalent bond of the organofluorine molecules to the surface of the top layer 27 of the antireflection coating.
    [0063] Examples of optical elements 1 are explained below.
    A preferred substrate 10 is a chemically toughened glass, in particular in the form of a chemically toughened glass pane. 7 shows such an example. The disk-shaped substrate 10 has exchange layers 11, 12 on both side surfaces 100, 101, which are under compressive stress due to the exchange of alkali ions of the glass by larger homologues (in particular by an exchange of nations by K + ions). The two side surfaces 100, 101 form the surface which is provided with the anti-reflective coating 2. Alternatively, depending on the intended use, only one of the side surfaces 100, 101 can be provided with an anti-reflective coating 2.
    As in the examples shown in FIGS. 1 and 2, it may also be advantageous, in the case of a chemically biased substrate 10, to deposit a layer 28 containing silicon oxide as an adhesion promoter for the subsequently deposited antireflection coating 2. This layer 28 preferably has the same composition as the layers of the anti-reflective coating 2 with the first refractive index.
    The optical element 1 can be used, for example, as a terminating element or window of the optics of a camera or another optical sensor. The optical element can also be a cover glass of an optical display of a mobile electronic device, such as a smart phone, a tablet PC or a watch.
    For such displays, sapphire or Al 2 O 3 can also be used as the substrate 10 and provided with the coating according to the invention with an anti-reflective coating 2 and an organofluorine layer 3. Here, as already mentioned above, a layer 28 containing silicon oxide is preferably used as an adhesion promoter between the sapphire surface and the anti-reflective coating 2. The advantages are the same as in the embodiment of a sapphire watch glass explained above.
    According to another embodiment of the invention, a substrate 10 made of or with zirconium oxide, ZrO 2 is used. A ZrO 2 mixed crystal is preferably used for such a substrate in order to stabilize a crystal phase, such as the cubic phase. Calcium oxide, magnesium oxide or yttrium oxide are included as stabilizers.
    CH 709 768 B1 ZrO 2 has a high elastic modulus of about 200 GPa. The bending stiffness is even higher than with sapphire. In this respect, this material is also suitable for applications where high substrate strength is important. With the coating according to the invention, scratch resistances similar to sapphire are also achieved. In addition, disturbing reflections are suppressed by the very high refractive index of over 2.
    Further zirconium-containing possible substrates are hard material materials such as zirconium carbide and zirconium nitride. However, these materials are generally not or not very transparent. Another possible hard substrate material is silicon carbide, which is also used as a material in optics.
    Instead of using a cover glass for an optical system, a lens can also be produced directly as an optical element 1 with a coating according to the invention. 8 shows such an example. In the example shown, the substrate 10 in the form of a lens 8 is only provided on one side with the anti-reflective coating 2 and the fluoroorganic layer 3 applied thereon. This is useful, for example, if the lens 8 is to be cemented with another lens on the non-coated lens surface. Of course, both lens surfaces can also be coated here. Optical glasses, such as crown or flint glasses or high-index glasses, are preferably used for the substrate 10.
    Such lenses 8 can advantageously form with the layer 3 facing outward an objective or ocular lens of an objective, for example camera optics, a microscope or a telescope.
    权利要求:
    Claims (13)
    [1]
    claims
    1. Optical element (1) with a transparent substrate (10) in the visible spectral range and a multi-layer antireflective coating (2) deposited on the substrate (10), which alternately has layers with a first refractive index and a second, higher refractive index, the layers with a higher refractive index nitride or oxynitride and the layers with a first refractive index oxide of silicon and at least one further element which is selected from the elements aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, barium, strontium, niobium, boron and wherein the molar proportion of silicon in the layers with the first refractive index outweighs the molar proportions of the further element or elements, and wherein the top layer of the multilayer antireflection coating is a layer with the first refractive index, and wherein on the antireflection coating a layer (3) of chain-shaped fluoroorganic molecules is arranged, the molecules at the end of di e surface of the optical element, preferably to the uppermost layer (27) of the anti-reflective coating (2).
    [2]
    2. Optical element according to claim 1, wherein the layer of chain-shaped organofluorine molecules is a monomolecular layer.
    [3]
    3. Optical element according to one of the preceding claims, wherein the fluoroorganic molecules contain perfluorinated carbon chains.
    [4]
    4. Optical element according to one of the preceding claims, characterized by a sapphire substrate.
    [5]
    5. Optical element according to one of claims 1 to 3, characterized by a chemically toughened glass substrate.
    [6]
    6. Optical element according to one of the preceding claims, characterized in that the anti-reflective coating (2) comprises a layer stack of four successive layers (24, 25, 26, 27), in which the bottom layer (24) is a silicon nitride-containing higher refractive index layer wherein the further silicon-nitride-containing higher refractive index layer (26), which forms the uppermost high refractive index layer of the layer stack, has the greatest layer thickness within the layer stack, and wherein the top layer (27) of the layer stack has a layer with a lower refractive index made of silicon oxide, preferably with a portion of aluminum, and has the second largest layer thickness under the layers of the layer stack, the first layer (24) and the second layer (25), which like the top layer (27) is a layer with a lower refractive index made of silicon oxide with a The proportion of aluminum is composed of a layer thickness that is thinner than the layer thickness of the upper most location (27).
    [7]
    7. Optical element according to one of the preceding claims, characterized in that the antireflection coating (2) comprises a layer stack in which the top layer (26) with a second refractive index has the greatest layer thickness of the antireflection coating and a layer thickness in the range from 100 nm to 700 nm, preferably from 300 nm to 600 nm, very particularly preferably from 400 nm to 500 nm.
    [8]
    8. Optical element according to one of the preceding claims, characterized in that the ratio of the amounts of silicon and the at least one further element in the individual layers of the anti-reflective coating is at least 5: 1, preferably at least 8: 1.
    [9]
    9. Optical element according to one of the preceding claims, wherein
    - The Knoop hardness of the optical element (1) on its coated surface (13) is at least 600 kg / mm 2 , or
    - The substrate (10) has an elastic modulus of at least 50 GPa.
    CH 709 768 B1
    [10]
    10. Optical element according to one of the preceding claims, wherein the anti-reflective coating (2) comprises a layer stack of four successive layers (24, 25, 26, 27) with two layers (24, 26) with a second, higher refractive index, in which the upper of the two layers (26) with a second, higher refractive index has a layer thickness which is at least 40% of the thickness of the antireflection coating (2), preferably at least 60% of the thickness of the antireflection coating (2), particularly preferably at least 70% of the thickness of the antireflection coating (2 ).
    [11]
    11. A method for producing an optical element (1) according to one of the preceding claims, in which
    - A substrate (10) provided in the visible spectral range and
    - A multi-layer anti-reflective coating (2) is applied to the substrate (10) by
    - Using a vacuum deposition process, layers with a first refractive index and a second, higher refractive index are alternately deposited, the layers with a higher refractive index containing nitride or oxynitride and the layers with the first refractive index oxide of silicon and at least one further element, and the molar fraction of Silicon in the layers with the first refractive index outweighs the molar proportions of the further element or elements, and the top layer of the multilayer anti-reflective coating is a layer with the first refractive index, and a coating with a layer (3) of chain-like fluoroorganic molecules is applied to the anti-reflective coating , The molecules being bound at the end to the surface of the optical element, preferably to the uppermost layer (27) of the antireflection coating (2).
    [12]
    12. The method according to claim 11, characterized in that the layers (24, 25, 26, 27) of the anti-reflective coating (2) are deposited by reactive magnetron sputtering.
    [13]
    13. The method according to claim 11 or 12, characterized in that the layer (3) of fluoroorganic molecules is applied by liquid coating or by evaporation in a vacuum deposition process.
    CH 709 768 B1
    CH 709 768 B1
    CH 709 768 B1
    类似技术:
    公开号 | 公开日 | 专利标题
    CH709768B1|2019-01-31|Scratch-resistant optical element.
    DE102014104798B4|2021-04-22|Hard anti-reflective coatings as well as their manufacture and use
    DE102008054139B4|2010-11-11|Glass or glass-ceramic substrate with scratch-resistant coating, its use and process for its preparation
    DE112014000613B4|2019-05-29|Transparent base body with coating-inhibiting coating
    DE60109592T2|2006-02-09|METHOD FOR PRODUCING A RELATED LAYER ON INORGANIC IMPLANTED SUBSTRATES
    DE19530331B4|2009-05-07|Coated base and method of formation
    DE102014104799B4|2021-03-18|Substrate with a coating to increase scratch resistance, process for its production and its use
    DE60019704T2|2006-01-19|Dyed anti-fog mirror
    DE102006014796B4|2009-04-09|Highly resilient low-E coating system for transparent substrates
    DE3941859C1|1991-01-24|
    DE102015114877B4|2020-10-01|Scratch-resistant anti-reflective coating and mobile electronic device
    DE10342397B4|2008-04-03|Transparent protective layer for a body and its use
    DE102014108057A1|2015-12-17|Scratch-resistant, chemically toughened glass substrate and its use
    EP2628818A1|2013-08-21|Article with reflection reducing coating, and method for producing the same
    EP2492251A1|2012-08-29|Substrate with antireflective coating and method for producing same
    CH713317A2|2018-06-29|Substrate comprising anti-reflection coating system with hard material coating and method for its production.
    DE102018112039A1|2018-11-29|GLASS OBJECT AND DISPLAY DEVICE
    DE102014108679A1|2015-12-24|Optical element with a reflective coating
    DE102005000911B4|2010-11-04|Environmentally stable highly reflective mirror coating system and method for its production
    DE202015104722U1|2015-09-16|Scratch-resistant antireflective coating
    DE102015116644A1|2017-04-06|Scratch-resistant coatings with improved cleanability, substrates with scratch-resistant coatings with improved cleanability and process for their preparation
    DE2050556C3|1978-11-30|Process for the production of a highly refractive, optically homogeneous and absorption-free oxide layer
    WO2010048975A1|2010-05-06|Hafnium oxide coating
    DE102005056110A1|2007-05-31|Temperature stable film material for coating of the surfaces of optical materials e.g. architectural glass and lenses
    DE102020122475A1|2022-03-03|Element comprising a transparent substrate and a multi-layer anti-wear layer with adapted reflection and method for its production
    同族专利:
    公开号 | 公开日
    US11079514B2|2021-08-03|
    CN105301675A|2016-02-03|
    US20150355380A1|2015-12-10|
    DE102014108058A1|2015-12-17|
    JP2015230486A|2015-12-21|
    CH709768A2|2015-12-15|
    US20190113657A1|2019-04-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE3941796A1|1989-12-19|1991-06-20|Leybold Ag|Optical multilayer coating - with high anti-reflection, useful for glass and plastics substrates|
    FR2730990B1|1995-02-23|1997-04-04|Saint Gobain Vitrage|TRANSPARENT SUBSTRATE WITH ANTI-REFLECTIVE COATING|
    IT1282106B1|1996-01-31|1998-03-12|Sola Optical Italia S P A|TRANSPARENT PHOTOCROMATIC SUBSTRATE INCLUDING AN ANTI-REFLECTIVE SURFACE COATING|
    US5871843A|1996-03-27|1999-02-16|Asahi Glass Company Ltd.|Laminate and process for its production|
    FR2748743B1|1996-05-14|1998-06-19|Saint Gobain Vitrage|GLASS WITH ANTI-REFLECTIVE COATING|
    US20030039843A1|1997-03-14|2003-02-27|Christopher Johnson|Photoactive coating, coated article, and method of making same|
    FR2793889B1|1999-05-20|2002-06-28|Saint Gobain Vitrage|TRANSPARENT SUBSTRATE WITH ANTI-REFLECTIVE COATING|
    FR2799005B1|1999-09-23|2003-01-17|Saint Gobain Vitrage|GLAZING PROVIDED WITH A STACK OF THIN FILMS ACTING ON THE SOLAR RADIATION|
    FR2800998B1|1999-11-17|2002-04-26|Saint Gobain Vitrage|TRANSPARENT SUBSTRATE HAVING AN ANTI-REFLECTIVE COATING|
    EP1148037A1|2000-04-19|2001-10-24|Blösch Holding AG|Process for the production of an anti-reflective coating on watchcover glasses|
    FR2810118B1|2000-06-07|2005-01-21|Saint Gobain Vitrage|TRANSPARENT SUBSTRATE HAVING ANTIREFLECTION COATING|
    JP2002006103A|2000-06-23|2002-01-09|Toppan Printing Co Ltd|Antireflective film, optically functional film and display device|
    DE60309441T2|2002-03-01|2007-09-20|Cardinal Cg Co., Eden Prairie|THIN FILM COATING WITH A TRANSPARENT FOUNDRY LAYER|
    FR2836912B1|2002-03-06|2004-11-26|Saint Gobain|TRANSPARENT SUSBRATE WITH ANTI-REFLECTIVE COATING WITH ABRASION RESISTANCE PROPERTIES|
    FR2841894B1|2002-07-03|2006-03-10|Saint Gobain|TRANSPARENT SUBSTRATE HAVING ANTIREFLECTION COATING|
    US20040089535A1|2002-08-16|2004-05-13|The Regents Of The University Of California.|Process and apparatus for pulsed dc magnetron reactive sputtering of thin film coatings on large substrates using smaller sputter cathodes|
    JP2004093437A|2002-09-02|2004-03-25|Citizen Watch Co Ltd|Cover glass for watch|
    JP2004271480A|2003-03-12|2004-09-30|Citizen Watch Co Ltd|Cover glass for timepiece|
    US7750575B2|2004-04-07|2010-07-06|Zond, Inc.|High density plasma source|
    FR2858816B1|2003-08-13|2006-11-17|Saint Gobain|TRANSPARENT SUBSTRATE HAVING ANTIREFLECTION COATING|
    FR2861386B1|2003-10-23|2006-02-17|Saint Gobain|SUBSTRATE, IN PARTICULAR GLASS SUBSTRATE, CARRYING A PHOTOCATALYTIC LAYER COATED WITH A PROTECTIVE THIN LAYER.|
    FR2866643B1|2004-02-24|2006-05-26|Saint Gobain|SUBSTRATE, ESPECIALLY GLASS, WITH A HYDROPHOBIC SURFACE, WITH IMPROVED DURABILITY OF HYDROPHOBIC PROPERTIES|
    JP4619166B2|2005-03-28|2011-01-26|シチズンホールディングス株式会社|Windshield glass for watches|
    FR2889182B1|2005-07-29|2007-10-26|Saint Gobain|GLAZING PROVIDED WITH A STACK OF THIN LAYERS ACTING ON SOLAR RADIATION|
    FR2898295B1|2006-03-10|2013-08-09|Saint Gobain|TRANSPARENT ANTIREFLECTION SUBSTRATE WITH NEUTRAL COLOR IN REFLECTION|
    DE102006046312B4|2006-09-29|2010-01-28|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Solar cells with stable, transparent and conductive layer system|
    JP4851953B2|2007-02-07|2012-01-11|株式会社日立製作所|Optical member|
    DE102007033338B4|2007-07-16|2010-06-02|Schott Ag|Hard material-coated glass or glass-ceramic article and method for its production and use of the glass or glass-ceramic article|
    AU2007360138B2|2007-10-18|2013-09-19|Midwest Research Institue|High temperature solar selective coatings|
    KR101923221B1|2007-12-07|2018-11-28|에바텍 아크티엔게젤샤프트|Reactive sputtering with hipims|
    WO2009099615A1|2008-02-05|2009-08-13|Corning Incorporated|Damage resistant glass article for use as a cover plate in electronic devices|
    WO2009108393A2|2008-02-29|2009-09-03|The University Of Houston System|Anti reflection coatings and methods of preparing and using same|
    US8586144B2|2008-03-25|2013-11-19|Pentax Ricoh Imaging Company, Ltd.|Method for forming anti-reflection coating and optical element|
    JP5326407B2|2008-07-31|2013-10-30|セイコーエプソン株式会社|Watch cover glass and watch|
    US20100031365A1|2008-07-31|2010-02-04|Balachander Krishnamurthy|Method and apparatus for providing network access privacy|
    KR20100020906A|2008-08-13|2010-02-23|소니 가부시끼가이샤|Optical film and manufacturing method therefor, antiglare film, optical layer-attached polarizer, and display apparatus|
    EP2427586B1|2009-05-07|2020-11-25|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Method for the production of oxide and nitride coatings and its use|
    DE102010009584B4|2010-02-26|2015-01-08|Schott Ag|Chemically toughened glass, process for its preparation and use thereof|
    US20120080832A1|2010-10-05|2012-04-05|Skyworks Solutions, Inc.|Devices for methodologies related to wafer carriers|
    US20120163946A1|2010-12-22|2012-06-28|Kuka Systems Corporation North America|Flexible material handling, storage and retrieval apparatus and methods|
    EP2492251B1|2011-02-23|2017-01-04|Schott Ag|Substrate with antireflective coating and method for producing same|
    DE102011076754A1|2011-05-31|2012-12-06|Schott Ag|Substrate element for the coating with an easy-to-clean coating|
    JP5435168B2|2013-07-23|2014-03-05|セイコーエプソン株式会社|Translucent member and watch|
    JP5750718B2|2013-12-09|2015-07-22|セイコーエプソン株式会社|Translucent member and watch|WO2018064947A1|2016-10-06|2018-04-12|Hong Kong Baptist University|Sapphire thin film coated substrate|
    US10578785B2|2015-08-18|2020-03-03|Corning Incorporated|Blocking coating with adhesion layer for ultraviolet optics|
    US10459134B2|2015-08-18|2019-10-29|Corning Incorporated|UV-blocking coating with capping layer in optical assembly having UV light source|
    DE102015114877B4|2015-09-04|2020-10-01|Schott Ag|Scratch-resistant anti-reflective coating and mobile electronic device|
    CN106680905A|2015-11-05|2017-05-17|大金工业株式会社|Article with surface treatment layer|
    KR20170058789A|2015-11-19|2017-05-29|삼성전자주식회사|Electromagnetic wave reflector and optical device including the same|
    CN105676317B|2016-03-11|2017-09-05|浙江美迪凯现代光电有限公司|The protective glass machining process of camera in mobile phone|
    EP3458252A4|2016-05-17|2020-04-01|Shamir Optical Industry Ltd.|Back side anti-reflective coatings, coating formulations, and methods of coating ophthalmic lenses|
    WO2017218433A1|2016-06-13|2017-12-21|Viavi Solutions Inc.|Protected item including a protective coating|
    DE102016125689A1|2016-12-23|2018-06-28|Schott Ag|Substrate comprising anti-reflection coating system with hard material coating and method for its production|
    DE102017104523A1|2017-03-03|2018-09-06|Schott Ag|Anti-reflective coating with stable reflectivity and color at an angle and under abrasion|
    DE102017105372A1|2017-03-14|2018-09-20|Schott Ag|Anti-reflection coating|
    CH714459A9|2017-12-19|2020-01-15|Guenat Sa Montres Valgine|Watch glass.|
    IT201800000730A1|2018-01-11|2019-07-11|Coerent Srl|COATING LAYER FOR LENSES|
    JPWO2020184727A1|2019-03-13|2020-09-17|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE102014108058.0A|DE102014108058A1|2014-06-06|2014-06-06|Optical element with high scratch resistance|
    [返回顶部]