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    • 专利摘要:
    The invention relates to a coated substrate (1) with a scratch-resistant anti-reflection coating. The anti-reflection coating is designed as an interference-optical coating with at least two low-refraction layers (4, 6) and at least one high-index layer (5). The high refractive index layer (5) is a transparent hard material layer and contains crystalline aluminum nitride having a hexagonal crystal structure with a (001) preferred direction. The low-index layers (4, 6) contain SiO 2. Low refractive and high refractive layers are arranged alternately. Furthermore, the invention relates to a method for producing a corresponding coating and its use.
    公开号:CH709524B1
    申请号:CH00465/15
    申请日:2015-04-01
    公开日:2019-05-15
    发明作者:Henn Christian；Damm Thorsten；Hahn Andreas；Brauneck Ulf
    申请人:Schott Ag；
    IPC主号:
    专利说明:

    X(001) = 1(001)/(1(001) + 1(100)) und y<001) = 1(001)/(1(001) + 1(101)) [0080] Der Anteil X(Ooi) beträgt in dieser hochbrechenden Schicht 0,67 und der Anteil y(Ooi) 0,77.
    [0081] Bei der Messkurve 17 handelt es sich um das XRD-Spektrum des unbeschichteten Substrates.
    [0082] Die Hartstoffschicht wurde dabei mit einer Sputterleistung im Bereich > 15 W/cm2 bei einem geringen Target-Substratabstand im Bereich von 10 bis 12 cm abgeschieden. Die Prozesstemperatur betrug 250 °C.
    [0083] Fig. 9 zeigt XRD-Spektrum von Hartstoffschichten, die zwar eine vergleichbare Zusammensetzung wie das in Fig. 8 gezeigte Ausführungsbeispiel, jedoch andere Vorzugsrichtungen der Kristallstruktur aufweisen. So ist das Spektrum 18 einem Vergleichsbeispiel mit einer (WO)-Vorzugsrichtung und das Spektrum 19 einem Vergleichsbeispiel mit einer (101)-Vorzugsrichtung zuzuordnen.
    [0084] Die Hartstoffschicht mit der (WO)-Vorzugsrichtung (Kurve 19) wurde dabei mit einem vergleichsweise hohen Target-Substratabstand (> 15 cm) und einer geringeren Sputterleistung von 13 W/cm2 (Kurve 19) abgeschieden. Die Prozesstemperatur betrug ca. 100 °C. Unter ähnlichen Prozessbedingungen, jedoch mit einer noch geringeren Sputterleistung von bzw. 9,5 W/cm2 wurde die Hartstoffschicht mit einer (101)-Vorzugsrichtung (Kurve 18) erhalten.
    [0085] Anhand der Fig. 10a bis 10c ist dabei der Einfluss der Vorzugsrichtung der Kristallstruktur auf die mechanische Beständigkeit der jeweiligen Hartstoffschichten zu erkennen. In den Fig. 10a bis 10c handelt es sich um fotografische Aufnahmen von Substraten mit hochbrechenden Hartstoffschichten mit unterschiedlichen Vorzugsrichtungen nach einem Belastungstest mit Sand. Hierbei wurde jeweils Sand auf die beschichteten Substrate gegeben und dieser unter Verwendung von Beschwerdekörpern 100-fach in einem Behältnis oszilliert. Fig. 10a zeigt dabei die Aufnahme nach dem Belastungstest einer Probe mit einer Beschichtung mit (101)-Vorzugsrichtung, Fig. 10b eine entsprechende Aufnahme einer Probe mit (WO)-Vorzugsrichtung und Fig. 10c die Aufnahme einer Probe mit einer (OOI)-Vorzugsrichtung. Wie aus den Fig. 10a bis 10c deutlich wird, weisen die Proben mit (101)- und (WO)-Vorzugsrichtung nach dem Belastungstest eine wesentlich höhere Anzahl an Kratzern auf als die Probe mit einer (OOI)-Vorzugsrichtung. Bei der in Fig. 10c gezeigten Probe handelt es sich dabei um das Ausführungsbeispiel, dessen XRD-Spektrum in Fig. 8 abgebildet wird.
    [0086] Die Fig. 11 a und 11 b zeigen Substrate mit einer hochbrechenden Hartstoffschicht nach einem mechanischen Belastungstest mit SiC. Dieser Belastungstest simuliert insbesondere die Resistenz gegenüber sehr harten Materialien und die Reinigbarkeit gegenüber jeglichen Reinigern und Hilfsmitteln. Der Testablauf ist vergleichbar zum Sandtest. Die Beschichtung der in Fig. 11a gezeigten Probe weist dabei keine Ausrichtung der Kristallite in (OOI)-Richtung auf, während
    Description: [0001] Interference optical coatings are used as anti-reflection coatings. Depending on the particular application or field of application, these coatings are exposed to different levels of mechanical stress. Thus, corresponding coatings, such as those used in watch glasses, viewing windows of civil and military vehicles, cooking surfaces or display covers such as touch cover glasses, in addition to a reduction of the reflection must have a high mechanical resistance, in particular a high scratch resistance. Two-component systems are known as hard material coatings from the prior art. These are usually oxides and nitrides of the elements chromium, silicon, titanium or zirconium. Although the coatings have a high hardness and mechanical strength, but they are not or not sufficiently transparent to be used in an interference optical system with anti-reflection effect, ie anti-reflection effect can.
    The patent application DE 10 2011 012 160 describes layer systems for reducing the reflection for watch glasses. To increase the mechanical strength of the coatings is used as a high refractive index layer Si3N4, which is additionally doped with aluminum. The mechanical strength of the coating can be read off before and after a mechanical load test on the basis of the antireflection effect of a correspondingly coated substrate. The coated substrates described in DE 10 2011 012 160 have a higher reflection after a mechanical load test than before the load test. The reflection after the stress test is reduced by 50% compared to the reflection of the uncoated substrate.
    In addition, an increase in the system hardness by increasing the individual layer thicknesses associated with a loss of the anti-reflection effect, since the anti-reflection effect decreases with a constant number of layers with an increased layer thickness.
    OBJECT OF THE INVENTION It is therefore an object of the present invention to provide a coating or a coated substrate which, in addition to a good anti-reflection effect, has a high mechanical resistance. Another object of the invention is to provide a method for producing a corresponding layer.
    The object of the invention is achieved in a surprising manner already by the subject matter of the independent claims. Advantageous embodiments and modifications of the invention are the subject of the dependent claims.
    BRIEF DESCRIPTION OF THE INVENTION The substrate coated according to the invention has an anti-reflective coating, also referred to below as an anti-reflection coating. The anti-reflection coating is constructed as an interference-optical coating with several dielectric layers. The coating layer system has alternating low-refractive and high-index layers and is formed by at least two low-index layers and at least one high-index layer. The high refractive index layer is arranged between the two low refractive index layers. The uppermost dielectric layer is a low refractive index layer. The uppermost layer is understood to mean that layer which has the greatest distance to the substrate. Accordingly, the lowermost layer of the coating is arranged directly on the substrate.
    Preferably, the low-index layers have a refractive index in the range of 1.3 to 1.6, in particular in the range of 1.45 to 1.5 at a wavelength of 550 nm. As a result, a high anti-reflection effect can be achieved.
    The low-index layers contain SiO 2. According to one embodiment, the low-refractive layers consist of SiO 2 or doped SiO 2. The doped SiCk is, in particular, a SiO 2 doped with one or more oxides, nitrides, carbides and / or carbonitrides selected from the group of the elements aluminum, boron, zirconium, titanium, chromium or carbon. Alternatively or additionally, the low-refractive-index layer may contain N2. The doped SiO 2 is preferably an aluminum-doped SiO 2 having silicon contents in the range from 1 to 99% by weight, preferably in the range from 85 to 95% by weight.
    The coating may contain several low-refractive layers of the same composition. Alternatively, the individual low-index layers of the coating may also have different compositions.
    The high-index layer or the high-index layers of the coating are formed as a transparent hard material layer. The high refractive index layer, hereinafter also referred to as the hard material layer, contains crystalline aluminum nitride having a hexagonal crystal structure with a predominant (OOI) preferential direction. According to the invention, the proportion of AIN in the hard material layer is greater than 50% by weight.
    The mechanical resistance of the coating is ensured by the high refractive index hard material layer.
    The inventors have surprisingly found that a particularly scratch-resistant and wear-resistant and polishing resistant coating can be obtained when the AIN of the hard material layer is crystalline or at least substantially crystalline and has a hexagonal crystal structure. In particular, the AlN layer has a degree of crystallinity of at least 50%.
    This is surprising in that it is usually assumed that amorphous coatings due to the absence of crystallites have a lower surface roughness than corresponding crystalline coatings. A small layer roughness is associated with a lower susceptibility to the occurrence of defects, for example caused by the friction of a foreign body on the surface of the coating. Nevertheless, the inventive coating not only has a high scratch resistance, but also an increased resistance to environmental influences and polishing and Verschleissbelastungen. Thus, the hard material layer has a high chemical resistance, for example to detergents and detergents on. In addition, the coating according to the invention, in spite of its crystalline structure, is transparent to light having wavelengths in the visible and infrared spectral range, so that the coating is optically inconspicuous and can be used, for example, in optical components as well as coating cooktops. Thus, the coating in particular has a transparency for visible light of at least 50%, preferably of at least 80%, based on the standard illuminant C and for infrared light, a transparency of at least 50%, preferably of at least 80%. The coating may also have a stiction μ against metal bodies μ <0.5, preferably μ <0.25.
    In one embodiment, the high-index layer has a refractive index in the range from 1.8 to 2.3, preferably in the range from 1.95 to 2.1, at a wavelength of 550 nm.
    In order to use the high refractive index layer together with low refractive index layers in an interference optical system, the high refractive index layer must have sufficient transparency. The high transparency of the high-index layer can be achieved in particular by the small size of the individual crystallites in the layer. For example, the small size prevents scattering effects. In one embodiment of the invention, the mean crystal size is at most 25 nm, preferably at most 15 nm and particularly preferably 5 to 15 nm. Another advantage of the small crystal size is the higher mechanical resistance of the layer containing the crystallites. Thus, larger crystallites often have an offset in their crystal structure, which adversely affects the mechanical resistance.
    The AIN crystallites in the hard material layer have a hexagonal crystal structure with a predominantly preferred direction in (OOI) direction, ie parallel to the substrate surface. In a preferential crystal structure, one of the symmetry directions of the crystal structure is preferentially occupied by the crystallites. For the purposes of the invention, an AIN crystal structure with a preferred direction in (OOI) direction is understood to mean, in particular, a crystal structure which, in the case of an X-ray diffractometric measurement in the corresponding XRD spectrum (X-ray-diffraction spectrum), ranges between 34 ° and 37 ° ° shows maximum reflection (grazing incidence measurement: GIXRD). The reflection in this region can be assigned to an AIN crystal structure with an (OOI) preferred direction.
    It has surprisingly been found that inventive hard material layers with a predominantly preferred direction in (OOI) direction both a higher modulus of elasticity and a greater hardness than hard material layers having an identical or comparable composition without (OOI) preferred direction.
    The high modulus of elasticity of the embodiment with a predominantly (OOI) preferred direction can be explained by the fact that the modulus of elasticity of a crystalline substance depends on its preferred direction. Thus, the modulus of elasticity in the high refractive index hard coating of the coating is greatest parallel to the substrate surface. In one embodiment of the invention, the hard material layers have an E modulus at a test force of 10 mN parallel to the substrate surface in the range of 80 to 250 GPa, preferably in the range of 110 to 200 GPa.
    The scratch resistance of a coating depends not only on the hardness but also on how good the adhesion between the individual layers or partial layers is with each other and how well the coating adheres to the substrate. In addition, if the individual layers of the coating and / or the substrate show different coefficients of thermal expansion, this can lead to the formation of stresses in the coating and to a flaking off of the coating. The resistance of the high refractive index hard material layer and thus also the inventive coating against abrasion is also dependent on the ratio of hardness and modulus of elasticity of the respective layer. The high-index layers therefore preferably have a ratio of hardness to modulus of elasticity of at least 0.08, preferably 0.1, more preferably greater than 0.1. This can be achieved by the (OOI) preferred direction. Compared to their composition comparable layers with different preferred direction show comparatively low values in the range of 0.06 to 0.08.
    The properties described above can be achieved, in particular, when the (OOI) preferential direction of the crystal structure is most pronounced compared to the (100) and (101) directions. In addition, in a development of the invention, moreover, the proportion of (WO) -oriented crystal structures is greater than the proportion of (101) -ori-terminated crystal structures.
    To determine the proportion of the crystal structure which has a (OOI) preferred direction, the following procedure can be used: Recording of an XRD spectrum of the corresponding layer under grazing incidence, ie thin-layer X-ray diffraction (GIXRD) Determination of the maximum intensity of the corresponding (OOI) reflection l (Ooi) in the range between 34 ° and 37 ° - Determination of the maximum intensity of the (WO) -reflex Ι (-ιΟο) in the range between 32 ° and 34 ° - Determination of the maximum intensity of (1O1) Reflections l (10i) in the range between 37 ° and 39 ° The proportions of the crystal structure with (OOI) preferred direction x (Ooi) and y (Ooi; are calculated as follows: * (001) = 1 (001) / (1 (001) + 1 (100)) and yjooi) = l (ooi / (l (ooi) + l (ioi)) [0025] A proportion x (00i) greater than 0.5 has been found to be particularly advantageous. preferably greater than 0.6 and particularly preferably greater than 0.75 and / or a proportion y (00i) greater than 0.5, preferably greater than 0.6 and more preferably greater than 0.75 herausgest In one embodiment of the invention, the proportion of oxygen in the high-index layer is at most 10 at%, preferably at most 5 at% and particularly preferably at most 2 at%.
    Due to the low oxygen content in the layer, the formation of oxynitrides is prevented, which adversely affect the crystal growth, in particular on the formation of a preferred direction of the crystal structure.
    The properties of the high refractive index hard material layer described above and thus the anti-reflection coating can be achieved in particular if the hard material layer has been applied by a sputtering method.
    The high-refractive-index hard material layer may be a pure aluminum nitride layer or the hard material layer may contain, in addition to aluminum nitride, further constituents, for example one or more further nitrides, carbides and / or carbonitrides. The nitrides, carbides or carbonitrides are preferably the corresponding compounds of the elements silicon, boron, zirconium, titanium, nickel, chromium and / or carbon.
    By doping properties of the hard material layer such as hardness, modulus of elasticity or resistance to abrasion, such as polishing resistance, can be further modified.
    To ensure that forms a crystalline aluminum nitride phase in these embodiments, an aluminum content of the hard material layer is> 50 wt .-%, preferably> 60 wt .-% and particularly preferably> 70 wt .-%, each based on the additional elements silicon, boron, zirconium, titanium, nickel, chromium and / or carbon, particularly advantageous.
    Corresponding mixed layers are referred to as doped AIN layers in the context of the invention. The compounds in addition to AIN are referred to as dopants, wherein the content of dopant can be up to 50 wt .-%. For the purposes of the invention, doped layers are also understood as meaning layers which contain up to 50% by weight of dopant.
    In mixed layers, ie doped AIN layers, AIN crystallites are embedded in a matrix of the dopant. The degree of crystallinity of the layer can thus be adjusted via the proportion of dopant in the mixed layer. In addition, the crystallite size is limited by the matrix. A crystallite size of not more than 20 nm, preferably of not more than 15 nm, has proven to be particularly advantageous. In particular, the average size of the AIN crystallites is in the range of 5 to 15 nm. This crystallite size ensures high transparency and mechanical resistance of the hard material layer.
    In one embodiment of the invention, the high refractive index hard material layer contains boron nitride in addition to aluminum nitride, ie the layer is doped with boron nitride. The contained boron nitride reduces the coefficient of friction of the layer, which in particular leads to a higher resistance of the layer compared to polishing processes. This is advantageous both in terms of the resistance of a correspondingly coated substrate when used by the end user and also with regard to possible method steps in the further processing of the coated substrate.
    In another embodiment of the invention, the high refractive index hard material layer is doped with silicon nitride, ie, it is an AIN: SiN material system, by which individual properties such as adhesion, hardness, roughness, friction coefficient and / or thermal resistance can be influenced. According to a development of this embodiment, the hard material layer in addition to silicon nitride at least one further of the above-mentioned components.
    Furthermore, the thermal expansion coefficient of the hard material layer can be influenced by the type and amount of dopant used or be adapted to the low-index layers and / or the substrate.
    As substrates, glasses, in particular sapphire glasses, borosilicate glasses, aluminosilicate glasses, soda lime glasses, synthetic quartz glasses (so-called fused silica glasses), lithium aluminosilicate glasses, optical glasses or glass ceramics can thus be used. Also, crystals for optical applications such as potassium fluoride crystals can be used as a substrate. In one development of the invention, the substrate is a hardened glass, in particular a chemically or thermally toughened glass.
    Be particularly advantageous, the use of the inventive coating has been found to scratch protection on a sapphire crystal. Correspondingly coated substrates are outstandingly suitable for use as coverslips on watches.
    Preferably, the substrates have a thermal expansion coefficient a2o-3oo in the range of 7 * 10 "® to 10 * 10-6 K_1. This is advantageous because in this embodiment substrate and coating have very similar thermal expansion coefficients.
    However, it is also possible to coat substrates with deviating coefficients of thermal expansion without leaving the field of the invention. Thus, an embodiment of the invention provides that the substrate is a glass ceramic, in particular a glass ceramic with a thermal expansion coefficient "20-300 smaller than 1 * 10-6 K" 1.
    The novel coatings are also permanently stable to temperatures of at least 300 ° C, preferably of at least 400 ° C. Thus, a substrate coated according to the invention can be used, for example, as a furnace window or cooking surface. Due to the high temperature stability, the coating can also be applied to the hot zones of the hob.
    In particular with hobs, a decor is often printed on the glass ceramic surface. An embodiment therefore provides that the substrate is at least partially provided with a decorative layer and the decorative layer is arranged between the substrate and the coating. Due to the high transparency of the coating according to the invention, the decoration is easily perceivable by the coating. In addition, the decorative layer is protected by the hard material layer from mechanical stresses, so that lower demands can be placed on the decorative layer with regard to their mechanical strength. Anti-reflective, scratch-resistant coatings for cooktops have the advantage over scratch-resistant coatings that the coated cooktops are visually less conspicuous, and thus also the polish loads are less noticeable.
    Depending on the intended use and the substrate used, the coating may be a layer system with three or more dielectric layers. For the purposes of the invention, a dielectric layer is understood in particular to mean a low- or high-index layer which contributes to an anti-reflection effect of the coating. In order to ensure an anti-reflective effect, the top, dielectric is a low refractive index layer.
    The inventive coating shows a good anti-reflection effect with a simultaneous high mechanical resistance and wear resistance. The high mechanical resistance can be recognized, for example, by the fact that the residual reflection at a wavelength of 750 nm after a mechanical load according to the so-called Bayer test changes to at most 35% based on the reflection of the uncoated substrate, preferably by at most 25%. By contrast, interference-optical coatings, as known from the prior art, show a change of about 50% relative to the uncoated substrate.
    In the case of the Bayer test, a coated substrate of a diameter of 30 mm is loaded with 90 g of sand and this is guided in 13 500 oscillations over the substrate for a period of about 1 hour.
    The residual reflection of the coated substrate at a wavelength of 750 nm after the Bayer test in an advantageous embodiment of the invention is less than 5%, preferably less than 3% and particularly preferably less than 2.5%.
    Another measure of the high mechanical resistance of a substrate coated according to the invention is the turbidity of the coating after the Bayer test, which is determined according to ASTM D1003, D1044. Preferably, after the Bayer test, the coated substrate has a haze which is at most 5% or even only at most 3% higher than the haze of the coated substrate before the Bayer test.
    According to one embodiment, the coating has three dielectric layers. Here, the coating comprises a first and a second low refractive layer and a high refractive index hard material layer. The first low refractive index layer is disposed between the substrate and the high refractive index hard material layer and the second low refractive index layer is disposed above the high refractive index hard material layer. The layer thickness of the first low-index layer is preferably in the range 5 to 50 nm, in particular in the range of 10 to 30 nm, the layer thickness of the second low-index layer in the range of 40 to 120 nm, preferably in the range of 60 to 100 nm second, ie upper low-refractive layer is greater than the layer thickness of the first low-refractive layer, since the second low-refractive layer is exposed to stronger mechanical loads than the first low-refractive layer. The layer thickness of the high refractive index hard material layer is preferably in the range of 80 to 1200 nm, in particular in the range of 100 to 1000 nm, preferably in the range of 100 to 700 nm. According to one embodiment of the invention, the hard material layer has a thickness <500 nm, preferred <400 nm and more preferred <200 nm. Hard material layers with corresponding layer thicknesses ensure a high mechanical strength of the coating with a simultaneous high anti-reflection effect.
    A development of the invention provides that the coating has at least five dielectric layers. Here, the coating comprises a first, a second and a third low-refractive layer and a first and a second high refractive index hard material layer. Low refractive and high refractive layers are alternately arranged, with the lowermost and uppermost layers being low refractive layers.
    The first low refractive index layer is thus arranged between the substrate and the first high refractive index hard material layer, the second low refractive index layer between the first and second high refractive index hard material layers and the third low refractive index hard material layer over the second high refractive index hard material layer. The first low-refractive-index layer preferably has a layer thickness in the range from 10 to 60 nm, the second low-refractive-index layer has a layer thickness in the range from 10 to 40 nm, the third low-index layer has a layer thickness in the range from 60 to 120 nm, and the first high-index hard material layer has a layer thickness in the range of 10 to 40 nm and / or the second high refractive index hard material layer has a thickness in the range of 100 to 1000 nm.
    According to an advantageous embodiment of the invention, the layer thickness of the entire coating is at most 600 nm or even less than 600 nm. The small layer thickness allows high transparency of the coating, moreover, the coatings are color neutral, ie the coating appears colorless. On the other hand, thicker coatings can have a color cast. Thus, in particular with the embodiment described above, a colorless design of the coating is possible. Another advantage of a thin coating is that even with thin substrates little or no warp, ie no or only slight faults occur. The warp is all the more pronounced the smaller the ratio of the layer thicknesses of the substrate and the coating. Thus, for example, thin substrates with a relatively thick coating have a stronger warp than corresponding substrates with a thin coating.
    The coating according to the invention or the substrate coated according to the invention has good mechanical strength and scratch resistance even with a low overall layer thickness. This is due in particular to the hard layer.
    The coated substrate according to the invention can be used in particular as an optical component, cooking surface, viewing window in the vehicle area, watch glasses, furnace window, glass or glass ceramic components in household appliances or as a display for example for tablet PCs or mobile phones, in particular as a touch display.
    Furthermore, the invention relates to a process for the preparation of the substrate coated according to the invention.
    The method comprises at least the following steps: a) providing a substrate, b) coating the substrate with a low-refraction SiO 2 -containing layer, c) providing the substrate coated in step b) in a sputtering apparatus with an aluminum-containing target, d) dispensing of sputtered particles having a power density in the range of 8 to 1000 W / cm 2, preferably 10 to 100 W / cm 2 per target surface; and e) applying a further low-refraction SiO 2 -containing layer to the coated substrate obtained in step d).
    In step a), the substrate may be, for example, a glass, in particular a sapphire glass, a borosilicate glass, an aluminosilicate glass, a soda lime glass, a synthetic quartz glass, a lithium aluminosilicate glass, an optical glass, a glass ceramic and / or a crystal for optical purposes are provided.
    The low-refractive layer can be applied by sputtering, sol-gel or CVD technology.
    The deposition of the high refractive index hard layer on the substrate obtained in step b) with a low refractive index layer takes place in step d) only from comparatively low final pressures. Thus, the final pressure in the coating system, ie the pressure from which a coating process can be started, is at most 2 * 10 -5 mbar, preferably even at pressures in the range of 0-6 to 5 * 10-6 mbar At the end pressures, the amount of foreign gas is minimized, ie the coating process is carried out in a very pure atmosphere, which ensures a high purity of the applied layers, thus preventing the formation of oxynitrides by the incorporation of oxygen due to process-related low residual gas content Crystal growth of AIN crystallites is of importance because it is disturbed by oxynitrides, and thus a highly refractive layer with an oxygen content of at most 10% by%, more preferably of at most 5 at% or even less than 2 at%, can be obtained In conventional sputtering processes, it is usually already coated from a final pressure in the range of at least 5 × 10 -5 mbar tet, accordingly, the oxygen content in the deposited coating is higher here.
    In the sputtering process, after reaching the end pressure according to the invention, in one embodiment of the hard material coating, a nitrogen-containing process gas is introduced. The proportion of nitrogen in the total flow is at least 30% by volume, preferably 40% by volume, particularly preferably 50% by volume. The proportion of nitrogen in the total flux during the sputtering process can influence the chemical resistance of the deposited layer, for example with respect to detergents or cleaners. Thus, the resistance of the layer to chemicals increases with increasing nitrogen content.
    The deposition of the high-index layer in step d) takes place with high sputtering powers. The sputtering powers in the process according to the invention in this case amount to at least 8-1000 W / cm 2, preferably at least 10-100 W / cm 2. In one embodiment of the invention, a high power impulse magnetron sputtering (HiPIMS) method is used. Alternatively or additionally, a negative voltage or an alternating voltage can be maintained between the target and the substrate.
    The deposition of the high refractive index hard layer in step d) may alternatively or additionally be carried out with the aid of ion bombardment, preferably with ion bombardment from an ion beam source and / or by applying a voltage to the substrate.
    The sputtering process can be done with a continuous deposition. Alternatively, the hard material layer may consist of interfaces which, due to the processing, arise when moving out of the coating area.
    Aftertreatment by a further process step can further improve the crystal appearance of the AIN coating. In addition, individual properties can be positively influenced by a post-treatment, such as the coefficient of friction. As aftertreatment methods are laser treatment or various thermal treatment methods, eg irradiation with light in question. Implantation by ions or electrons is also conceivable.
    According to one embodiment, the particles produced by sputtering are deposited preferably at a deposit ion temperature greater than 100 ° C., preferably greater than 200 ° C., and particularly preferably greater than 300 ° C. In combination with the low process pressures and the high sputtering powers, the growth of the AlN crystallites, in particular the crystallite size and the preferred direction of the crystal structure, can thus be influenced in a particularly advantageous manner. However, it is also possible to deposit at lower temperatures, for example at room temperature. The hard material layers produced according to this embodiment also show good mechanical properties such as a high scratch resistance.
    In one embodiment of the invention, in addition to aluminum, the target contains at least one of the elements silicon, boron, zirconium, titanium, nickel, chromium or carbon. These additional elements in addition to aluminum are referred to as Dopant in the context of the invention. Preferably, the proportion of aluminum in the target is greater than 50 wt .-%, more preferably greater than 60 wt .-% and most preferably greater than 70 wt .-%.
    In one embodiment of the invention, the process sequence with the method steps c) to d) is performed several times. For example, coatings with five or more dielectric layers can be obtained.
    According to one embodiment of the invention, the anti-reflection coating is deposited on a substrate with a roughened or etched surface.
    In a variant of the production method, a substrate is provided in step a) which already has a high-index hard layer.
    DETAILED DESCRIPTION OF THE INVENTION The invention will be explained in more detail below with reference to FIGS. 1 to 11 as well as exemplary embodiments.
    In the drawings:
    1 and FIG. 2 the schematic representation of two embodiments according to the invention coated substrates,
    Fig. 3 shows the change of reflection by a Bayer test of an embodiment and a
    Comparative Example
    4 shows the reflection curve of a first exemplary embodiment and of a comparative example before and after a load according to the Bayer test,
    5 shows the reflection curve of a second exemplary embodiment and of a comparative example before and after a load according to the Bayer test,
    6 shows an EDX spectrum of a high refractive index hard material layer,
    7a and 7b TEM images of two AlN-SiN mixed layers with different AIN contents,
    8 shows the XRD spectrum of an embodiment of a high refractive index hard material layer,
    9 shows the XRD spectra of two AlN hard-material layers with different preferred directions,
    10a to 10c are photographs of various coated substrates with high refractive index hard material layers with different preferred directions after a mechanical load test with sand and
    11a and 11b are photographs of various coated substrates with high refractive index hard material layers with different preferred directions of the crystal structure after a mechanical load test with silicon carbide.
    FIG. 1 schematically shows an exemplary embodiment of a substrate 1 coated according to the invention. The substrate 2 is in this case coated with a three-layer interference-optical coating 3a. The coating 3a in this case has the layers 4, 5 and 6. Layers 4 and 6 are low refractive layers, and layer 5 is a high refractive index layer. The first low-refractive-index layer 4 is deposited directly on the substrate 2 and exhibits a layer thickness in the range from 10 to 30 nm. Above the first low-refractive-index layer 4, the first high-indexing layer 5 is arranged whose layer thickness is 100 to 1000 nm. The first high refractive index layer 5 is arranged between the first low refractive index layer 4 and the second low refractive index layer 6. In the exemplary embodiment illustrated in FIG. 1, the second low-refractive-index layer 6 forms the uppermost layer of the coating 3a and has a layer thickness in the range from 60 to 100 nm. The layer thickness of the second low-refractive-index layer 6 is greater than the layer thickness of the first low-refractive-index layer 4, since the second low-refractive-index layer 6 is subjected to greater mechanical stresses as the uppermost layer of the coating 3a. The layer thickness of the first high-index layer 5 is not only adapted to optical requirements for producing a layer system with an anti-reflection effect, but also ensures a significant contribution to the mechanical strength of the entire coating 3a and thus of the coated substrate 1.
    Fig. 2 shows the schematic representation of a second embodiment 9. In this embodiment, the substrate 2 is provided with a five-layer coating 3b. In addition to the first and second low-refractive-index layers (4, 6) and the first high-refractive-index layer 5, the coating 3b has a second high-index layer 7 and a third low-index layer 8. In this case, the second high-index layer 7 is arranged between the second and the third low-index layer (6, 8). In the exemplary embodiment 9, the third low-refraction layer 8 forms the uppermost layer of the coating and has a layer thickness in the range from 60 to 120 nm. The layer thickness of the first low-refraction layer 4 is in the range of 10 to 60 nm and the layer thickness of the second low-refractive layer 6 in the range of 10 to 40 nm. Since the mechanical strength of the coating 3b is ensured mainly by the second high-index layer 8, FIG First high-refractive layer 5 in this embodiment has a smaller layer thickness of 10 to 40 nm, while the layer thickness of the second high-index layer is in the range of 100 to 1000 nm.
    FIG. 3 shows the average change in the reflection of a substrate 11 coated according to the invention and a comparative example 10 after a bayer test. For this purpose, in each case samples with a size of 30 mm in diameter were loaded with 90 g of sand and 13 500 oscillations were carried out. Subsequently, the reflection of the thus treated samples was determined by means of spectrometers and compared with the reflection of an untreated sample. The comparative sample 10 is a coated substrate as described in DE 10 2011 012 160. It is clear from FIG. 3 that the reflection of the comparative sample 10 changes substantially more strongly as a result of the mechanical load than is the case with the substrate 11 coated in accordance with the invention. The anti-reflection coating of sample 11 is many times more resistant to mechanical stresses such as scratches, as simulated by the Bayer test, than anti-reflective coatings known from the prior art.
    FIG. 4 shows the reflection course as a function of the wavelength of an exemplary embodiment and of a comparative example before and after a Bayer test. Comparative Example 12 is a coated substrate as described in DE 10 2011 012 160. The five-layer coating of embodiment 13 has low refractive index SiO 2 layers. The high refractive index layers are silicon nitride coated aluminum nitride (AIN: SiN) coatings. The curves 12a and 13a show the reflection curve of the comparative example and of the exemplary embodiment before the Bayer test. The reflection courses after the Bayer test, as already described above, are shown in curves 12b (comparative example) and 13b (embodiment). While the comparative sample and the exemplary embodiment show comparable reflection characteristics before the Bayer test, the comparative example after the Bayer test has a significantly higher reflection over the entire measured wavelength range than the exemplary embodiment.
    FIG. 5 shows the reflection as a function of the wavelength before and after a bayer test of a comparative example (14a, 14b) and of a further exemplary embodiment (15a, 15b). The coating of this embodiment has low-refraction layers of the composition SiAIOx. As is clear from the curves 14a and 15a, the exemplary embodiment before the Bayer test (curve 15a) has a higher residual reflection than the comparative example (curve 14a). Due to the Bayer test, however, the reflection in the comparative example (curve 14b) increases considerably more than in the exemplary embodiment (curve 15b). In addition, it can be observed in the comparative example that the reflection change increases more with increasing wavelength. Thus, the comparison sample from wavelengths of about 600 nm after the Bayer test a higher reflection than the correspondingly treated embodiment. In addition, in the exemplary embodiment, the change in the reflection is not or only slightly dependent on the wavelength, so that a largely constant reflection change can be observed over the entire measured wavelength range by the Bayer test. This is particularly advantageous, so that the color impression of the coating is largely retained.
    Fig. 6 shows the spectrum of an EDX analysis (energy dispersive X-ray spectroscopy or energy-dispersive X-ray analysis) of a hard material layer, as it is present as a high refractive index layer in the inventive coating. In this exemplary embodiment, the hard material layer is an AIN layer alloyed with silicon.
    FIG. 7 a shows a transmission electron microscopic (TEM) image of a high-index hard material layer according to the invention. The TEM image shown in Fig. 7a is a photograph of an AIN layer doped with SiN, ie, an AIN: SiN layer, wherein the content of AIN is 75% by weight and the content of SiN 25 wt .-% is. It can be seen from FIG. 7a that the AIN of the hard material layer is present in crystalline form in a SiN matrix. In contrast, an AIN: SiN layer in which AIN and SiN are equal parts is amorphous. A TEM image of a corresponding layer is shown in Fig. 7b. The high content of SiN prevents the formation of AIN crystallites.
    Fig. 8 shows the XRD spectrum (X-ray diffraction, X-ray diffraction) of an embodiment of a substrate with a high refractive index hard material layer. For this purpose, a SiO 2 substrate was coated with an AIN / SiN hard material layer and an XRD spectrum of the coated substrate was recorded. The spectrum 16 shows three reflections which can be assigned to the three orientations (100), (001) and (101) of the hexagonal crystal structure of the AlN. It becomes clear that the hard material layer predominantly has an (OOI) preferred direction. The corresponding reflex at 36 ° is much more pronounced than the reflections of the (WO) orientation (33.5 °) and the (101) orientation (38 °). The proportion of the crystal structure with (OOI) preferred direction can be determined from spectrum 16 as follows:
    X (001) = 1 (001) / (1 (001) + 1 (100)) and y <001) = 1 (001) / (1 (001) + 1 (101)) The content of X (Ooi) in this high refractive index layer is 0.67 and the proportion of y (Ooi) is 0.77.
    The measurement curve 17 is the XRD spectrum of the uncoated substrate.
    The hard material layer was deposited with a sputtering power in the range> 15 W / cm 2 at a low target-substrate distance in the range of 10 to 12 cm. The process temperature was 250 ° C.
    FIG. 9 shows the XRD spectrum of hard material layers which, although having a comparable composition to the exemplary embodiment shown in FIG. 8, have other preferred directions of the crystal structure. Thus, the spectrum 18 is assigned to a comparative example with a (WO) preferred direction and the spectrum 19 to a comparative example with a (101) preferred direction.
    The hard material layer with the (WO) preferred direction (curve 19) was deposited with a comparatively high target substrate distance (> 15 cm) and a lower sputtering power of 13 W / cm 2 (curve 19). The process temperature was about 100 ° C. Under similar process conditions, but with an even lower sputtering power of 9.5 W / cm 2, the hard material layer was obtained with a (101) preferred direction (curve 18).
    The influence of the preferred direction of the crystal structure on the mechanical resistance of the respective hard material layers can be recognized with reference to FIGS. 10a to 10c. FIGS. 10a to 10c are photographic images of substrates having high refractive index hard material layers with different preferred directions after a stress test with sand. In each case, sand was added to the coated substrates and this was oscillated 100 times in a container using body of appeal. 10a shows the image after the stress test of a sample with a coating with (101) preferred direction, FIG. 10b shows a corresponding image of a sample with (WO) preferred direction and FIG. 10c shows the image of a sample with an (OOI) preferred direction. As is clear from Figs. 10a to 10c, the specimens with (101) and (WO) preferential directions after the stress test have a much higher number of scratches than the specimen with an (OOI) preferential direction. The sample shown in FIG. 10c is the exemplary embodiment whose XRD spectrum is depicted in FIG. 8.
    11 a and 11 b show substrates with a high refractive index hard material layer after a mechanical load test with SiC. This stress test simulates in particular the resistance to very hard materials and the cleanability against all cleaners and auxiliaries. The test procedure is comparable to the sand test. The coating of the sample shown in Fig. 11a has no orientation of the crystallites in (OOI) direction, while
    权利要求:
    Claims (15)
    [1]
    A coated substrate having an anti-reflection coating, wherein the anti-reflection coating is formed as an interference-optical coating with at least two low-refractive layers and at least one high-refractive layer, wherein the high-refractive layer is a transparent hard material layer and the hard material layer with crystalline aluminum nitride a hexagonal crystal structure having a predominantly (001 J preferred direction and the low refractive index layers SiO2 and wherein the high refractive index layer is arranged between the low refractive layers.
    [2]
    2. Coated substrate according to claim 1, wherein the low-refractive layers SiO2 and / or doped SiO2, preferably containing Al as dopant and / or at least one low-refractive layer with one or more oxides, nitrides, carbides and / or carbonitrides selected from the group of Elements silicon, boron, zirconium, titanium, nickel, chromium or carbon, doped and / or contains nitrogen.
    [3]
    3. Coated substrate according to one of the preceding claims, wherein the low refractive index layers have a refractive index at a wavelength of 550 nm in the range of 1.3 to 1.6, preferably 1.45 to 1.5 and the high refractive index layers a refractive index at one wavelength of 550 nm in the range of 1.8 to 2.3, preferably 1.95 to 2.1.
    [4]
    4. Coated substrate according to one of the preceding claims, wherein the proportions of the crystal structure in the high refractive index layer with (OOI) preferred direction x (00i) and y (00i) with X (001) = 1 (001) / (1 (001) + 1 (100)) and Y (001) = 1 (001) / (1 (001) + 1 (101)) are greater than 0.5, preferably greater than 0.6 and more preferably greater than 0.75, the intensities l (Ooi), l (ioo) and l (ioi) are determined by means of an X-ray diffractometry spectrum, XRD spectrum, of the corresponding layer under grazing incidence, wherein the intensity Ι (00ΐ) of the maximum intensity of the corresponding (WO) reflection Ι (-ιΟο) in the range between 34 ° and 37 °, the intensity l (1Oo) of the maximum intensity of the corresponding (WO) reflection in the range between 32 ° and 34 ° and the intensity l (10i) of the maximum intensity of the corresponding (WO) 101) reflectance in the range of 37 ° to 39 ° in an XRD spectrum of the grazing incidence layer.
    [5]
    5. Coated substrate according to one of the preceding claims, wherein the total layer thickness of the high refractive index hard material layer is at most 600 nm, preferably less than 600 nm.
    [6]
    6. Coated substrate according to one of the preceding claims, wherein the proportion of oxygen in the high refractive index hard material layer is at most 10 at%, preferably less than 5 at% and particularly preferably less than 2 at%.
    [7]
    7. Coated substrate according to one of the preceding claims, wherein the substrate is a glass, preferably a chemically or thermally toughened glass or a sapphire glass, a borosilicate glass, an aluminosilicate glass, a soda lime glass, a synthetic quartz glass, a lithium aluminosilicate glass, an optical glass, a Crystal for optical purposes or a glass ceramic is.
    [8]
    8. The coated substrate according to claim 1, wherein the coating comprises three dielectric layers in the form of a first and a second low refractive index layer and a high refractive index hard material layer, wherein the first low refractive index layer between the substrate and the high refractive index hard material layer and the second low refractive index layer over the the layer thickness of the first low-refractive layer in the range 5 to 50 nm, preferably in the range of 10 to 30 nm, the layer thickness of the second low-refractive layer in the range of 40 to 120 nm, preferably in the range of 60 to 100 nm , and / or the layer thickness of the high refractive index hard material layer in the range of 80 to 1200 nm, preferably in the range of 100 to 1000 nm and particularly preferably in the range of 100 to 700 nm.
    [9]
    9. The coated substrate according to claim 1, wherein the coating has at least five dielectric layers, wherein the coating preferably has a first, a second and a third low refractive layer and a first and a second high refractive index hard material layer, wherein the first low refractive index Layer between the substrate and the first high refractive index hard material layer, the second low refractive index layer between the first and second high refractive index hard material layers and the third low refractive index hard material layer over the second high refractive index hard material layer, and wherein the first low refractive index layer has a thickness in the range of 10 to 60 nm, the second low-refractive-index layer has a layer thickness in the range from 10 to 40 nm, the third low-index layer has a layer thickness in the range from 60 to 120 nm, the first high-refractive-index hard material layer has a layer thickness in the range from 10 to 40 nm and / or the second hard material layer has a layer thickness in the range from 100 to 1000 nm.
    [10]
    10. A method for producing a coated substrate with an anti-reflection coating according to claim 1, wherein the anti-reflection coating is formed as an interference-optical coating with at least two low-refractive layers and at least one high-refractive layer at least with the following steps: a) providing a Substrates, b) coating of the substrate with a low-refraction, SiO 2 -containing layer, c) providing the substrate coated in step b) in a sputtering apparatus with an aluminum-containing target, d) discharging sputtered particles with a power density in the range from 8 to 1000 W. / cm2, preferably 10-100 W / cm2 per target area from a final pressure of the highest 2 * 10-5 mbar and e) applying a further, low refractive SiO2-containing layer to the coated substrate obtained in step d).
    [11]
    11. The method according to claim 10, wherein in step a) a substrate with a high refractive index hard material layer is provided and / or the sequence of process steps c) to e) is performed several times.
    [12]
    12. Use of a coated substrate according to one of claims 1 to 9 as a watch glass or as a display for example for tablet PCs or mobile phones, in particular as a touch display.
    [13]
    13. Use of a coated substrate according to one of claims 1 to 9 as an optical component.
    [14]
    14. Use of a coated substrate according to one of claims 1 to 9 as a display or viewing windows in the vehicle area.
    [15]
    15. Use of a coated substrate according to any one of claims 1 to 9 as a glass or glass ceramic component in household appliances.
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    同族专利:
    公开号 | 公开日
    CN104977632A|2015-10-14|
    JP6682188B2|2020-04-15|
    CN112130233A|2020-12-25|
    CH709524B8|2019-09-13|
    JP2015200888A|2015-11-12|
    DE102014104798B4|2021-04-22|
    DE102014104798A1|2015-10-08|
    CN104977632B|2020-11-10|
    US20150355382A1|2015-12-10|
    CH709524A2|2015-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA2000597C|1988-10-21|1995-07-11|Toshio Ishikawa|Optical recording element|
    FR2728559B1|1994-12-23|1997-01-31|Saint Gobain Vitrage|GLASS SUBSTRATES COATED WITH A STACK OF THIN LAYERS WITH INFRARED REFLECTION PROPERTIES AND / OR IN THE FIELD OF SOLAR RADIATION|
    FR2730990B1|1995-02-23|1997-04-04|Saint Gobain Vitrage|TRANSPARENT SUBSTRATE WITH ANTI-REFLECTIVE COATING|
    US20070113881A1|2005-11-22|2007-05-24|Guardian Industries Corp.|Method of making solar cell with antireflective coating using combustion chemical vapor deposition and corresponding product|
    US7994600B2|2005-12-21|2011-08-09|Texas Instruments Incorporated|Antireflective coating|
    FR2898295B1|2006-03-10|2013-08-09|Saint Gobain|TRANSPARENT ANTIREFLECTION SUBSTRATE WITH NEUTRAL COLOR IN REFLECTION|
    US20080055777A1|2006-09-06|2008-03-06|Seagate Technology Llc|Perpendicular magnetic recording media with improved scratch damage performance|
    JP2011058084A|2009-09-14|2011-03-24|Toyama Univ|Hard protective film and method for producing the same|
    JP5413978B2|2010-05-20|2014-02-12|東海光学株式会社|Plastic optical products and eyeglass plastic lenses|
    DE102011012160B4|2011-02-23|2017-04-06|Schott Ag|Antireflection coating substrate and method of making the same|
    EP2492251B1|2011-02-23|2017-01-04|Schott Ag|Substrate with antireflective coating and method for producing same|
    DE102011081234A1|2011-08-19|2013-02-21|Schott Ag|Glass ceramic, which is at least partially provided with a hard material layer|US9366784B2|2013-05-07|2016-06-14|Corning Incorporated|Low-color scratch-resistant articles with a multilayer optical film|
    US9335444B2|2014-05-12|2016-05-10|Corning Incorporated|Durable and scratch-resistant anti-reflective articles|
    US11267973B2|2014-05-12|2022-03-08|Corning Incorporated|Durable anti-reflective articles|
    US9790593B2|2014-08-01|2017-10-17|Corning Incorporated|Scratch-resistant materials and articles including the same|
    US10649588B2|2014-10-14|2020-05-12|Corning Incorporated|Piezoelectric film structures and sensors and display assemblies using same|
    US10730790B2|2015-02-25|2020-08-04|Corning Incorporated|Optical structures and articles with multilayer stacks having high hardness and methods for making the same|
    KR20180052701A|2015-09-14|2018-05-18|코닝 인코포레이티드|High light transmittance and anti-scratch anti-reflection products|
    WO2018062858A1|2016-09-27|2018-04-05|주식회사 엘지화학|Anti-reflection film|
    CN106410422A|2016-10-28|2017-02-15|东南大学|3-bit transmission type electromagnetic code metamaterial applied in terahertz band|
    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|
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    TW201937204A|2018-01-09|2019-09-16|美商康寧公司|Coated articles with light-altering features and methods for the production thereof|
    DE102018116993A1|2018-07-13|2020-01-16|Schott Ag|Optical component with scratch-resistant anti-reflection coating and process for its production|
    DE102019211256A1|2018-08-01|2020-03-19|Schott Ag|LAYERED OPTICAL COMPOSITE, WHICH HAS A REDUCED CONTENT OF STRONG LIGHT-REFLECTING LAYERS, AND ITS AUGMENTED REALITY APPLICATION|
    CN114085038A|2018-08-17|2022-02-25|康宁股份有限公司|Inorganic oxide articles with thin durable antireflective structures|
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    法律状态:
    2019-07-15| PK| Correction|Free format text: ANMELDER BERICHTIGT. |
    2019-09-13| PK| Correction|Free format text: BERICHTIGUNG: INHABER UND TITEL. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102014104798.2A|DE102014104798B4|2014-04-03|2014-04-03|Hard anti-reflective coatings as well as their manufacture and use|
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