Article having substrate and multilayer coating on substrate, and solar panel comprising article

Abstract

Described herein is an article comprising: a substrate comprising a first major surface and a second major surface; and a multi-layer coating disposed on the first major surface of the substrate, the multi-layer coating comprising at least one period of a layer of a low refractive index material and a layer of a high refractive index material. The article exhibits a major surface average reflectance of less than or equal to 0.550% throughout the wavelength range from 600 nm to 750 nm. Also described herein is a solar panel comprising the article disposed over an array of photovoltaic cells as a cover glass.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 534,146, filed August 23, 2023, pursuant to 35 USC § 119, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to an article having a substrate and a multilayer coating on the substrate, wherein the article has enhanced durability and reduced reflectivity to achieve high transmittance of electromagnetic radiation in the wavelength range of 600 nm to 750 nm, and more specifically to a solar panel comprising the article as a cover glass over a photovoltaic cell. Background Technology

[0004] As the global population increases, the demand for electricity is also on the rise. Traditionally, carbon-based fuels are used to generate electricity. However, the Earth's carbon-based fuel reserves are finite. Alternative power generation methods have been developed or are under development, such as using solar, wind, ocean waves, and tidal changes to generate electricity.

[0005] As a specific example, solar panels use the sun to generate electricity. Nuclear fusion and other processes in the sun produce photons, which are energy packets with a wide range of wavelengths. These photons propagate towards Earth. Photons with specific wavelength ranges can penetrate Earth's atmosphere and reach the Earth's surface. The wavelengths of photons from the sun that reach the Earth's surface correspond to the visible, near-infrared, infrared, radio wave, and ultraviolet spectra, among others. Of the photons from the sun that reach the Earth's surface, those corresponding to the visible, near-infrared, and radio wave spectra are the most abundant (see example...). Figure 1 However, compared to photons corresponding to the visible and near-infrared spectra, photons corresponding to the radio wave spectrum have much lower energy per photon (because the energy of each photon is inversely proportional to the wavelength).

[0006] Furthermore, solar panels comprise semiconductor materials that provide the photovoltaic effect, converting photons into electrical energy. The semiconductor material absorbs photons from the sun. If the photons absorbed by the semiconductor material have sufficient energy, they excite electrons to move from the relatively lower energy valence band to the relatively higher energy conduction band. Electrons moving to the conduction band leave "holes" in the valence band, thus causing a charge imbalance. When the semiconductor material is connected to a circuit, this charge imbalance generates a current through appropriate doping and the structure of the semiconductor material, such as the various combinations of n-doped and p-doped silicon regions arranged in a junction structure known in the photovoltaic field.

[0007] Whether a photon absorbed by a semiconductor material has enough energy to excite an electron from the valence band to the conduction band depends on the band gap of the semiconductor material. For example, silicon has a band gap energy of about 1.1 electron volts (eV), which corresponds to photons with a wavelength of about 1100 nm, which falls within the near-infrared spectrum. Photons with wavelengths of about 1100 nm or shorter (and therefore higher energy per photon) will excite electrons from the valence band to the conduction band after being absorbed by a silicon semiconductor. Other semiconductor materials have different band gap energies. Photons absorbed by a semiconductor material that do not excite electrons to enter the conduction band can generate heat. The heat generated can lead to suboptimal power generation from solar panels.

[0008] In addition to the semiconductor material that converts photons into electrical energy, solar panels typically include a cover plate over which the semiconductor material sits. The cover plate separates the semiconductor material from the external environment, such as rain, hail, debris, and other things that could damage the semiconductor material or the wiring and electrical connections required for efficient energy harvesting from the photovoltaic cells within the solar panel.

[0009] Cover plates sometimes include a substrate having a glass composition. However, a typical glass-air interface reflects approximately 4% of incident visible electromagnetic radiation. These reflected photons cannot be used to generate electricity. To counteract the natural reflection at the glass-air interface, cover plates sometimes include an anti-reflective (AR) coating applied to the surface of the glass substrate. The AR coating is typically a porous SiO2 layer.

[0010] However, there are several problems: typical porous SiO2 AR coatings (i) lack durability and (ii) exhibit suboptimal antireflectivity. Regarding durability, typical porous SiO2 AR coatings are easily removed by weather events, abrasion caused by dust or sand, and cleaning. It is estimated that typical porous SiO2 AR coatings are completely removed from the substrate after only five years of use, and in some cases, as little as six months. This lack of durability is problematic because after the AR coating is removed, the glass substrate reverts to its natural reflectivity, and photons that could otherwise be converted into electrical energy are reflected back into the external environment. Furthermore, SiO2 AR coatings are prone to scratches, breakage, and partial delamination, leading to light scattering or polyelasticity events, resulting in reflectivity that is even higher (or transmittance lower) than if the substrate had no SiO2 coating at all. These degradation mechanisms cause the electrical energy generated by the solar panel to decrease over time, which in turn leads to an increase in the effective cost of electricity, quantified as a higher levelized cost of energy (LCOE) over the solar panel's lifespan. Regarding suboptimal anti-reflection properties, glass substrates with typical porous SiO2 AR coatings still reflect a considerable number of photons corresponding to the visible and near-infrared spectra. Furthermore, cover plates with typical porous SiO2 AR coatings can transmit photons associated with infrared wavelengths, the energy of which is lower than the bandgap energy of the semiconductor material in the solar panel. Although the semiconductor material does not absorb these photons and convert them into electrical energy, the low absorption levels in the various layers of the solar panel (such as polymer encapsulants, metal contacts, etc.) increase the temperature of the semiconductor and reduce the energy conversion efficiency. Summary of the Invention

[0011] This disclosure addresses the aforementioned and other problems by providing an article comprising a substrate and a multilayer coating disposed on the substrate. The multilayer coating comprises alternating layers of low-refractive-index material and layers of high-refractive-index material, each layer having a unique thickness engineered to provide destructive interference at wavelengths in and around the 600 nm to 750 nm range, thereby increasing its transmittance through the article. Increased transmittance of photons associated with this wavelength range improves the output of the photovoltaic cell. Additionally, the multilayer coating reduces the transmittance of photons associated with wavelengths in the 300 nm to 350 nm range and the 1100 nm to 1800 nm range. Photons in the former (UV range) degrade components of the solar panel, leading to a decrease in power generation over time, while photons in the latter range cannot be used by the photovoltaic cell for power generation because their energy is below the bandgap of silicon and cause the solar panel to heat up, thereby reducing the instantaneous power conversion efficiency of the solar panel. Furthermore, the multilayer coating imparts durability to the article, and the durability of the multilayer coating is far superior to that of existing porous coatings. This means that solar panels coated with the multilayer AR coating of this disclosure provide more power generation over time than solar panels coated with porous AR coatings.

[0012] According to aspect 1 of this disclosure, an article of manufacture comprises: (i) a substrate having a first main surface and a second main surface; and (ii) a multilayer coating disposed on the first main surface of the substrate, the multilayer coating comprising at least one period of a low-refractive-index material layer and a high-refractive-index material layer, wherein the article of manufacture exhibits a main surface average reflectance of less than or equal to 0.550% over the entire wavelength range of 600 nm to 750 nm.

[0013] According to aspect 2 of this disclosure, an article of aspect 1 is presented, wherein the substrate further comprises a glass composition or a glass-ceramic composition.

[0014] According to aspect 3 of this disclosure, an article of aspect 2 is presented, wherein the glass composition is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition.

[0015] According to aspect 4 of this disclosure, an article of any one of aspects 1 to 3 is presented, wherein (i) the refractive index of the low refractive index material is in the range of 1.40 to 1.60, and (ii) the refractive index of the high refractive index material is in the range of 1.70 to 2.50.

[0016] According to aspect 5 of this disclosure, an article of any one of aspects 1 to 4 is presented, wherein (i) the low refractive index material is or comprises SiO2, doped SiO2, Al2O3, GeO2, SiO, AlO x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, and (ii) the high refractive index material is or contains AlN, SiN x AlO x N y SiO x N y Or TiO2.

[0017] According to aspect 6 of this disclosure, an article of manufacture of any one of aspects 1 to 5 is presented, wherein the multilayer coating comprises a first low-refractive-index material layer in direct contact with the first main surface, the thickness of the first low-refractive-index material layer being in the range of 50 nm to 250 nm.

[0018] According to aspect 7 of this disclosure, an article of any one of aspects 1 to 6 is presented, wherein the multilayer coating further comprises a total thickness in the range of 350 nm to 1400 nm.

[0019] According to aspect 8 of this disclosure, an article of any one of aspects 1 to 6 is presented, wherein the multilayer coating further comprises a total thickness in the range of 350 nm to 800 nm.

[0020] According to aspect 9 of this disclosure, an article of any one of aspects 1 to 6 is presented, wherein the multilayer coating further comprises a total thickness in the range of 350 nm to 650 nm.

[0021] According to aspect 10 of this disclosure, an article of any one of aspects 7 to 9 is presented, wherein the combined thickness of the low refractive index material layer accounts for more than 55% of the total thickness of the multilayer coating.

[0022] According to aspect 11 of this disclosure, an article of aspect 10 is presented, wherein the combined thickness of the low refractive index material layer is in the range of 65% to 75% of the total thickness of the multilayer coating.

[0023] According to aspect 12 of this disclosure, an article of any one of aspects 1 to 11 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 2.0% over the entire wavelength range of 400 nm to 450 nm.

[0024] According to aspect 13 of this disclosure, an article of any one of aspects 1 to 12 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 450 nm to 600 nm.

[0025] According to aspect 14 of this disclosure, an article of any one of aspects 1 to 13 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 0.730% over the entire wavelength range of 750 nm to 800 nm.

[0026] According to aspect 15 of this disclosure, an article of any one of aspects 1 to 14 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm.

[0027] According to aspect 16 of this disclosure, an article of any one of aspects 1 to 15 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 1.05% over the entire wavelength range of 850 nm to 900 nm.

[0028] According to aspect 17 of this disclosure, an article of any one of aspects 1 to 16 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 2.20% over the entire wavelength range of 900 nm to 950 nm.

[0029] According to aspect 18 of this disclosure, articles of any one of aspects 1 to 17 are presented, wherein the articles of said articles exhibit a principal surface average reflectance of less than or equal to 3.00% over the entire wavelength range of 950 nm to 1000 nm.

[0030] According to aspect 19 of this disclosure, articles of any one of aspects 1 to 18 are presented, wherein the articles of said articles exhibit a principal surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 1000 nm to 1050 nm.

[0031] According to aspect 20 of this disclosure, articles of any one of aspects 1 to 19 are presented, wherein the articles of the present disclosure exhibit a principal surface average reflectance of greater than or equal to 5.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, or 1700 nm to 1800 nm.

[0032] According to aspect 21 of this disclosure, articles of any one of aspects 1 to 20 are presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa as measured by the Berkovich Indenter Hardness Test in an indentation depth range of 0 to 125 nm.

[0033] According to aspect 22 of this disclosure, articles of any one of aspects 1 to 20 are presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa as measured by a Glass indenter hardness test in the range of indentation depth from 0 to 125 nm.

[0034] According to aspect 23 of this disclosure, the article of any one of aspects 1 to 22 further comprises: an antifouling coating located on the multilayer coating, wherein (i) the antifouling coating comprises a silane or siloxane material, and (ii) the antifouling coating exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

[0035] According to aspect 24 of this disclosure, the article of any one of aspects 1 to 22 further comprises: an antifouling coating on the multilayer coating, wherein (a) the antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and (b) the antifouling layer exhibits hydrophobic, hydrophilic, or fully hydrophobic properties.

[0036] According to aspect 25 of this disclosure, an article of manufacture comprises: (a) a substrate having a first main surface and a second main surface; and (b) a multilayer coating disposed on the first main surface of the substrate, the multilayer coating comprising (i) at least four layers, (ii) a repeating period of a low-refractive-index material layer and a high-refractive-index material layer, (iii) a total thickness in the range of 350 nm to 1400 nm, and (iv) a first low-refractive-index material layer disposed directly on the first main surface of the substrate, the thickness of the first low-refractive-index material layer being in the range of 50 nm to 250 nm; wherein the combined thickness of the low-refractive-index material layer accounts for more than 55% of the total thickness of the multilayer coating.

[0037] According to aspect 26 of this disclosure, an article of aspect 25 is presented, wherein the substrate further comprises a glass composition or a glass-ceramic composition.

[0038] According to aspect 27 of this disclosure, an article of aspect 26 is presented, wherein the glass composition of the substrate is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition.

[0039] According to aspect 28 of this disclosure, an article of manufacture of any one of aspects 25 to 27 is presented, wherein the substrate includes a compressive stress region at or near the first main surface.

[0040] According to aspect 29 of this disclosure, an article of any one of aspects 25 to 28 is presented, wherein the thickness of the substrate is in the range of 0.1 mm to 5.0 mm.

[0041] According to aspect 30 of this disclosure, articles of any one of aspects 25 to 29 are presented, wherein (i) the refractive index of the low refractive index material is in the range of 1.40 to 1.60, and (ii) the refractive index of the high refractive index material is in the range of 1.70 to 2.50.

[0042] According to aspect 31 of this disclosure, an article of any one of aspects 25 to 30 is presented, wherein (i) the low refractive index material is or comprises SiO2, doped SiO2, Al2O3, GeO2, SiO, AlO x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, and (ii) the high refractive index material is or contains AlN, SiN x AlO x N y SiO x N y Or TiO2.

[0043] According to aspect 32 of this disclosure, an article of any one of aspects 25 to 31 is presented, wherein the low refractive index material layer accounts for 65% to 75% of the total thickness of the multilayer coating.

[0044] According to aspect 33 of this disclosure, an article of any one of aspects 25 to 32 is presented, wherein the multilayer coating comprises (i) a first low-refractive-index material layer directly disposed on the first main surface of the substrate, the thickness of the first layer being in the range of 175 nm to 225 nm, (ii) a second high-refractive-index material layer directly disposed on the first layer, the thickness of the second layer being in the range of 15 nm to 25 nm, (iii) a third low-refractive-index material layer directly disposed on the second layer, the thickness of the third layer being in the range of 30 nm to 40 nm, (iv) a fourth high-refractive-index material layer directly disposed on the third layer, the thickness of the fourth layer being in the range of 130 nm to 150 nm, and (v) a fifth low-refractive-index material layer directly disposed on the fourth layer, the thickness of the fifth layer being in the range of 90 nm to 110 nm.

[0045] According to aspect 34 of this disclosure, an article of any one of aspects 25 to 32 is presented, wherein the multilayer coating comprises (i) a first low-refractive-index material layer directly disposed on the first main surface of the substrate, the thickness of the first layer being in the range of 175 nm to 225 nm; (ii) a second high-refractive-index material layer directly disposed on the first layer, the thickness of the second layer being in the range of 5 nm to 15 nm; (iii) a third low-refractive-index material layer directly disposed on the second layer, the thickness of the third layer being in the range of 35 nm to 60 nm; (iv) a fourth high-refractive-index material layer directly disposed on the third layer, the thickness of the fourth layer being in the range of 20 nm to 30 nm; (v) a fifth low-refractive-index material layer directly disposed on the fourth layer, the thickness of the fifth layer being in the range of 10 nm to 25 nm; (vi) a sixth high-refractive-index material layer directly disposed on the fifth layer, the thickness of the sixth layer being in the range of 75 nm to 110 nm; and (vii) a seventh low-refractive-index material layer directly disposed on the sixth layer, the thickness of the seventh layer being in the range of 5 nm to 20 nm. (viii) an eighth high-refractive-index material layer directly disposed on the seventh layer, the thickness of the eighth layer being in the range of 15 nm to 30 nm, and (ix) a ninth low-refractive-index material layer directly disposed on the eighth layer, the thickness of the ninth layer being in the range of 90 nm to 115 nm.

[0046] According to aspect 35 of this disclosure, an article of any one of aspects 25 to 32 is presented, wherein the multilayer coating comprises (i) a first low-refractive-index material layer directly disposed on the first main surface of the substrate, the thickness of the first layer being in the range of 175 nm to 225 nm; (ii) a second high-refractive-index material layer directly disposed on the first layer, the thickness of the second layer being in the range of 15 nm to 25 nm; (iii) a third low-refractive-index material layer directly disposed on the second layer, the thickness of the third layer being in the range of 30 nm to 40 nm; (iv) a fourth high-refractive-index material layer directly disposed on the third layer, the thickness of the fourth layer being in the range of 130 nm to 160 nm; (v) a fifth low-refractive-index material layer directly disposed on the fourth layer, the thickness of the fifth layer being in the range of 25 nm to 40 nm; (vi) a sixth high-refractive-index material layer directly disposed on the fifth layer, the thickness of the sixth layer being in the range of 10 nm to 20 nm; and (vii) a seventh low-refractive-index material layer directly disposed on the sixth layer, the thickness of the seventh layer being in the range of 140 nm to 175 nm. Within the range of nm, (viii) an eighth high-refractive-index material layer directly disposed on the seventh layer, the thickness of the eighth layer being in the range of 10 nm to 20 nm; (ix) a ninth low-refractive-index material layer directly disposed on the eighth layer, the thickness of the ninth layer being in the range of 25 nm to 40 nm; (x) a tenth high-refractive-index material layer directly disposed on the ninth layer, the thickness of the tenth layer being in the range of 130 nm to 160 nm; (xi) an eleventh low-refractive-index material layer directly disposed on the tenth layer, the thickness of the eleventh layer being in the range of 30 nm to 40 nm; (xii) a twelfth high-refractive-index material layer directly disposed on the eleventh layer, the thickness of the twelfth layer being in the range of 10 nm to 20 nm; (xiii) a thirteenth low-refractive-index material layer directly disposed on the twelfth layer, the thickness of the thirteenth layer being in the range of 105 nm to 135 nm; (xiv) a fourteenth high-refractive-index material layer directly disposed on the thirteenth layer, the thickness of the fourteenth layer being in the range of 10 nm to 20 nm. In the range of nm, (xv) is a fifteenth low-refractive-index material layer directly disposed on the fourteenth layer, the thickness of the fifteenth layer being in the range of 35 nm to 50 nm; (xvi) is a sixteenth high-refractive-index material layer directly disposed on the fifteenth layer, the thickness of the sixteenth layer being in the range of 120 nm to 155 nm; and (xvii) is a seventeenth low-refractive-index material layer directly disposed on the sixteenth layer, the thickness of the seventeenth layer being in the range of 90 nm to 110 nm.

[0047] According to aspect 36 of this disclosure, an article of any one of aspects 25 to 35 is presented, wherein the article of said article exhibits a principal surface average reflectance of less than or equal to 0.550% over the entire wavelength range of 600 nm to 750 nm.

[0048] According to aspect 37 of this disclosure, articles of any one of aspects 25 to 36 are presented, wherein said articles exhibit: (i) a principal surface average reflectance of less than or equal to 2.0% over the entire wavelength range of 400 nm to 450 nm, (ii) a principal surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 450 nm to 600 nm, (iii) a principal surface average reflectance of less than or equal to 0.730% over the entire wavelength range of 750 nm to 800 nm, (iv) a principal surface average reflectance of less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm, (v) a principal surface average reflectance of less than or equal to 1.05% over the entire wavelength range of 850 nm to 900 nm, (vi) a principal surface average reflectance of less than or equal to 2.20% over the entire wavelength range of 900 nm to 950 nm, and (vii) a principal surface average reflectance of less than or equal to 2.20% over the entire wavelength range of 900 nm to 1000 nm. (viii) The main surface average reflectance is less than or equal to 3.00% over the entire wavelength range of 1000 nm to 1050 nm, and (viii) the main surface average reflectance is less than or equal to 1.40% over the entire wavelength range of 1000 nm to 1050 nm.

[0049] According to aspect 38 of this disclosure, articles of any one of aspects 25 to 37 are presented, wherein said articles of articles exhibit a principal surface average reflectance greater than or equal to 5.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

[0050] According to aspect 39 of this disclosure, an article of any one of aspects 25 to 38 is presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa as measured by a Glass indenter hardness test in the range of indentation depth from 0 to 125 nm.

[0051] According to aspect 40 of this disclosure, articles of any one of aspects 25 to 38 are presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa as measured by a Glass indenter hardness test in the range of indentation depth from 0 to 125 nm.

[0052] According to aspect 41 of this disclosure, the article of any one of aspects 25 to 40 further comprises: an antifouling coating located on the multilayer coating, wherein (i) the antifouling coating comprises a silane or siloxane material, and (ii) the antifouling coating exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

[0053] According to aspect 42 of this disclosure, the article of any one of aspects 25 to 40 further comprises: an antifouling coating located on the multilayer coating, wherein (a) the antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and (b) the antifouling layer exhibits hydrophobic, hydrophilic, or fully hydrophobic properties.

[0054] According to aspect 43 of this disclosure, a solar panel comprises: (1) an article of manufacture comprising: (a) a substrate having a first main surface and a second main surface; and (b) a multilayer coating disposed on the first main surface of the substrate, the multilayer coating comprising a repeating period of a low-refractive-index material layer and a high-refractive-index material layer; wherein the article of manufacture exhibits a main surface average reflectance of less than or equal to 0.550% over the entire wavelength range of 600 nm to 750 nm; and (2) a photovoltaic (PV) cell array disposed below the second main surface of the substrate.

[0055] According to aspect 44 of this disclosure, the solar panel of aspect 43 further includes a backsheet, wherein the PV cell array is disposed between the backsheet and the article of manufacture.

[0056] According to aspect 45 of this disclosure, the solar panel of aspect 44 further includes (a) an encapsulation comprising the article of manufacture, the PV cell array, and the backsheet; and (b) a frame comprising (i) a sidewall extending around the periphery of the encapsulation, (ii) a C-shaped channel adjacent to the sidewall, the periphery of the encapsulation being secured within the C-shaped channel, and (iii) a protrusion extending inward relative to the sidewall and forming a plane substantially parallel to the outer main surface of the backsheet opposite to the PV cell array.

[0057] According to aspect 46 of this disclosure, a solar panel of any one of aspects 43 to 46 is presented, wherein the substrate further comprises a glass composition or a glass-ceramic composition.

[0058] According to aspect 47 of this disclosure, a solar panel of aspect 46 is presented, wherein the glass composition of the substrate is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition.

[0059] According to aspect 48 of this disclosure, a solar panel of any one of aspects 43 to 47 is presented, wherein (i) the refractive index of the low refractive index material is in the range of 1.40 to 1.60, and (ii) the refractive index of the high refractive index material is in the range of 1.70 to 2.50.

[0060] According to aspect 49 of this disclosure, a solar panel of any one of aspects 43 to 48 is presented, wherein (i) the low refractive index material is or comprises SiO2, doped SiO2, Al2O3, GeO2, SiO, AlO x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, and (ii) the high refractive index material is or contains AlN, SiN x AlO x N y SiO x N y Or TiO2.

[0061] According to aspect 50 of this disclosure, a solar panel of any one of aspects 43 to 49 is presented, wherein the multilayer coating comprises a first low-refractive-index material layer in direct contact with the first main surface, the first low-refractive-index material layer having a physical thickness in the range of 50 nm to 250 nm.

[0062] According to aspect 51 of this disclosure, a solar panel of any one of aspects 43 to 50 is presented, wherein the multilayer coating further comprises a total thickness in the range of 350 nm to 1400 nm.

[0063] According to aspect 52 of this disclosure, a solar panel of aspect 51 is presented, wherein the combined thickness of the low refractive index material layer accounts for more than 55% of the total thickness of the multilayer coating.

[0064] According to aspect 53 of this disclosure, a solar panel of aspect 51 is presented, wherein the combined thickness of the low refractive index material layer accounts for 65% to 75% of the total thickness of the multilayer coating.

[0065] According to aspect 54 of this disclosure, a solar panel of any one of aspects 43 to 53 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 2.0% over the entire wavelength range of 400 nm to 450 nm.

[0066] According to aspect 55 of this disclosure, a solar panel of any one of aspects 43 to 54 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 450 nm to 600 nm.

[0067] According to aspect 56 of this disclosure, a solar panel of any one of aspects 43 to 55 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 0.730% over the entire wavelength range of 750 nm to 800 nm.

[0068] According to aspect 57 of this disclosure, a solar panel of any one of aspects 43 to 56 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm.

[0069] According to aspect 58 of this disclosure, a solar panel of any one of aspects 43 to 57 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 1.05% over the entire wavelength range of 850 nm to 900 nm.

[0070] According to aspect 59 of this disclosure, a solar panel of any one of aspects 43 to 58 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 2.20% over the entire wavelength range of 900 nm to 950 nm.

[0071] According to aspect 60 of this disclosure, a solar panel of any one of aspects 43 to 59 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 3.00% over the entire wavelength range of 950 nm to 1000 nm.

[0072] According to aspect 61 of this disclosure, a solar panel of any one of aspects 43 to 60 is presented, wherein the article exhibits a principal surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 1000 nm to 1050 nm.

[0073] According to aspect 62 of this disclosure, a solar panel of any one of aspects 43 to 61 is presented, wherein the article exhibits a principal surface average reflectance greater than or equal to 5.0% in one or more wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

[0074] According to aspect 63 of this disclosure, a solar panel of any one of aspects 43 to 62 is presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa as measured by a Glass indenter hardness test in the range of indentation depth from 0 to 125 nm.

[0075] According to aspect 64 of this disclosure, a solar panel of any one of aspects 43 to 63 is presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa as measured by a Glass indenter hardness test in the range of indentation depth from 0 to 125 nm.

[0076] According to aspect 65 of this disclosure, a solar panel of any one of aspects 43 to 64 is presented, wherein (i) the article further comprises an antifouling layer on the multilayer coating, (ii) the antifouling coating comprises a silane or siloxane material, and (iii) the antifouling coating exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

[0077] According to aspect 66 of this disclosure, a solar panel of any one of aspects 43 to 64 is presented, wherein the article further comprises an antifouling coating on the multilayer coating, the antifouling coating comprising (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and the antifouling layer exhibits hydrophobic, hydrophilic, or fully hydrophobic properties.

[0078] According to aspect 67 of this disclosure, an article of manufacture comprises: (a) a substrate having a first main surface and a second main surface; and (b) a multilayer coating disposed on the first main surface of the substrate, the multilayer coating comprising a repeating cycle of a low-refractive-index material layer and a high-refractive-index material layer, wherein (i) the multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa measured according to a Glass indenter hardness test in an indentation depth range of 0 to 125 nm, and (ii) the article of manufacture exhibits a main surface average reflectance of less than or equal to 0.900% over the entire wavelength range of 650 nm to 750 nm.

[0079] According to aspect 68 of this disclosure, an article of aspect 67 is presented, wherein the article of article exhibits: (i) a principal surface average reflectance of less than or equal to 2.50% over the entire wavelength range of 400 nm to 450 nm, (ii) a principal surface average reflectance of less than or equal to 0.650% over the entire wavelength range of 600 nm to 650 nm, (iii) a principal surface average reflectance of less than or equal to 1.00% over the entire wavelength range of 750 nm to 800 nm, (iv) a principal surface average reflectance of less than or equal to 1.00% over the entire wavelength range of 800 nm to 850 nm, and (v) a principal surface average reflectance of less than or equal to 1.30% over the entire wavelength range of 850 nm to 900 nm.

[0080] According to aspect 69 of this disclosure, articles of any one of aspects 67 to 68 are presented, wherein the articles of the present disclosure exhibit: (i) a principal surface average reflectance of less than or equal to 2.50% over the entire wavelength range of 950 nm to 1000 nm, and (ii) a principal surface average reflectance of less than or equal to 4.00% over the entire wavelength range of 1000 nm to 1050 nm.

[0081] According to aspect 70 of this disclosure, an article of any one of aspects 67 to 69 is presented, wherein the article of the present disclosure exhibits a principal surface average reflectance of greater than or equal to 17.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

[0082] According to aspect 71 of this disclosure, articles of any one of aspects 67 to 70 are presented, wherein the multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa as measured by a Glass indenter hardness test in the range of indentation depth from 0 to 125 nm.

[0083] According to aspect 72 of this disclosure, the article of any one of aspects 67 to 71 further comprises: an antifouling coating located on the multilayer coating, wherein (i) the antifouling coating comprises a silane or siloxane material, and (ii) the antifouling coating exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

[0084] According to aspect 73 of this disclosure, the article of any one of aspects 67 to 71 further comprises: an antifouling coating on the multilayer coating, wherein (a) the antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and (b) the antifouling layer exhibits hydrophobic, hydrophilic, or fully hydrophobic properties. Attached Figure Description

[0085] In the attached diagram:

[0086] Figure 1 It is a graph showing the number of photons (per unit time per unit area) reaching the Earth's surface in the solar spectrum under standard conditions known as AM1.5G (atmospheric mass 1.5 global) as a function of wavelength;

[0087] Figure 2 This is a top perspective view of the article of manufacture disclosed herein, showing a multilayer coating disposed on a first main surface of a substrate.

[0088] Figure 3 yes Figure 2 The top perspective exploded view of the article further shows that the substrate may include a compressive stress zone that sandwiches a tensile stress zone in the middle.

[0089] Figure 4 yes Figure 2 A top view of the article, which shows that the article also includes the main surface provided by the terminal layer of multi-layer coating;

[0090] Figure 5 yes Figure 2 The products passed Figure 4 An elevation view of a cross-section taken by the VV line, which shows a multilayer coating comprising (i) a period of low refractive index material layers and high refractive index material layers disposed on the low refractive index material layers, and (ii) low refractive index material terminal layers disposed on other layers of the multilayer coating, and an optional hydrophobic or hydrophilic coating located on the multilayer coating and facing the external environment.

[0091] Figure 6 This is a perspective view of the solar panel disclosed herein, showing that it includes... Figure 2 Solar panels made of [material name];

[0092] Figure 7 yes Figure 6 A top-down plan view of a solar panel, showing the structure mounted on the photovoltaic cell array and the frame surrounding the structure.

[0093] Figure 8 yes Figure 6 solar panels Figure 7An elevation view of a cross-section taken along line VIII-VIII, showing the frame holding the packaged article, PV cell array, and backing.

[0094] Figure 9 yes Figure 8 A magnified view of region IX, which shows the first and second polymer layers encapsulating the PV cell array;

[0095] Related to Example 1 Figure 10 The graph shows the variation of the reflectivity of the main surface with the wavelength of the incident electromagnetic radiation, which demonstrates that the article having the multilayer coating of this disclosure reflects less incident electromagnetic radiation in the key wavelength range (e.g., from 600 nm to about 875 nm) for solar panel applications than various comparative examples, while reflecting more incident electromagnetic radiation in the wavelength range of 300 nm to 350 nm than the comparative examples.

[0096] Related to Example 2 Figure 11 The graph shows the variation of the reflectivity of the main surface with the wavelength of the incident electromagnetic radiation, which demonstrates that the article having another multilayer coating of the present disclosure reflects less incident electromagnetic radiation in the wavelength range of 450 nm to about 875 nm than various comparative examples, while reflecting more incident electromagnetic radiation in the wavelength ranges of 300 nm to 350 nm and 1100 nm to 1200 nm.

[0097] Related to Examples 3 and 4 Figure 12 This is a graph showing the variation of the reflectivity of the main surface with the wavelength of incident electromagnetic radiation. It demonstrates that articles with other multilayer coatings of this disclosure reflect less incident electromagnetic radiation in the wavelength range of approximately 400 nm to approximately 975 nm than various comparative examples, while reflecting more incident electromagnetic radiation in the wavelength range of approximately 400 nm to approximately 975 nm, and more incident electromagnetic radiation in the wavelength ranges of 300 nm to 350 nm and 1100 nm to 1200 nm; and

[0098] Related to Examples 1 to 4 Figure 13 This is for calculating the expected short-circuit current density J of a standard PV module using the articles of Examples 1 to 4 having the multilayer coating of this disclosure. sc A schematic diagram of the modeled components. Detailed Implementation

[0099] In the following detailed description, exemplary embodiments with specific details disclosed are set forth for purposes of explanation and not limitation to provide a thorough understanding of the various principles of this disclosure. However, it will be apparent to those skilled in the art who will benefit from this disclosure that this disclosure may be practiced in other embodiments that depart from the specific details disclosed herein. Furthermore, descriptions of well-known apparatuses, methods, and materials may be omitted to avoid obscuring the description of the various principles of this disclosure. Finally, wherever applicable, the same reference numerals refer to the same elements.

[0100] In this document, a range may be expressed as from “about” one specific value and / or to “about” another specific value. As used herein, the term “about” means that a quantity, size, formulation, parameter, and other quantity and characteristic is not and need not be precise, but may be approximate and / or larger or smaller as required, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. When the term “about” is used to describe the value or endpoint of a range, this disclosure should be understood to include the specific value or endpoint mentioned. Regardless of whether the numerical value or range endpoint in the specification is referred to as “about,” the numerical value or range endpoint is intended to include two embodiments: one modified by “about” and one not modified by “about.” It should be further understood that the endpoint of each range is significant relative to and independent of the other endpoint.

[0101] As used herein, the terms “significant,” “substantially,” and their variations are intended to indicate that the described feature is equal to or approximately equal to a certain value or description. For example, a “substantially flat” surface is intended to mean a flat or substantially flat surface. Furthermore, “substantially” is intended to mean that two values ​​are equal or approximately equal. In some embodiments, “substantially” may mean values ​​within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

[0102] As used herein, the term "placement" includes coating, depositing, and / or forming material onto a surface. The placed material may constitute a layer as defined herein. The phrase "placed on" includes cases where material is formed onto a surface such that the material is in direct contact with the surface, and also includes cases where material is formed on a surface, wherein one or more intermediate materials are located between the placed material and the surface. Intermediate materials may constitute a layer as defined herein.

[0103] The directional terms used in this article, such as up, down, right, left, front, back, top, and bottom, are for reference only with reference to the accompanying drawings and are not intended to imply absolute orientation.

[0104] Unless otherwise expressly stated, no method described herein is intended to be construed as requiring its steps to be performed in a particular order. Therefore, if a method claim does not actually describe the order in which its steps should be followed, or if the claims or description do not otherwise specifically state that the steps should be limited to a particular order, then in no way is it implied that the order should be inferred. This applies to any possible non-expressive basis of interpretation, including: logical matters relative to the arrangement of steps or operational procedures; literal meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0105] As used herein, unless the context explicitly indicates otherwise, the singular forms “a / an” and “the” include plural indicators. Thus, for example, unless the context explicitly indicates otherwise, references to “component” include embodiments having two or more such components.

[0106] Now for reference Figures 2 to 5 The article 10 includes a substrate 12 and a multilayer coating 14 disposed on the substrate 12. The substrate 12 has a first main surface 16 and a second main surface 18. The first main surface 16 and the second main surface 18 are the surfaces of the substrate 12 having the largest surface area. In the illustrated embodiment, the substrate 12 is a sheet. In such embodiments, the first main surface 16 and the second main surface 18 face substantially opposite directions 20, 22 and are both substantially flat. The substrate 12 also includes one or more edges 24 at which the substrate 12 transitions between the first main surface 16 and the second main surface 18.

[0107] In the embodiments, the substrate 12 has a glass composition or a glass-ceramic composition. The difference between the substrate 12 having a glass-ceramic composition and the substrate 12 having a glass composition is that the former has both an amorphous phase and a crystalline phase, while the latter includes an amorphous phase but no substantial crystalline phase.

[0108] The substrate 12 having the glass composition can be formed by any suitable process. In embodiments where the substrate 12 is in sheet form, the substrate 12 can be formed by a float process or an overflow downdraw fusion process, but other processes are also contemplated. In the float process, a glass ribbon is formed on the surface of a molten metal bath (e.g., a molten tin bath), and after being removed from the bath, the glass ribbon is conveyed through an annealing furnace and then cut into individual sheets. In the case of the fusion process, the glass ribbon is formed by allowing molten glass to flow around the outside of a forming structure (referred to in this art as an "isopipe") to produce two glass layers that are fused together at the bottom of the forming structure (the root of the isopipe) to form the glass ribbon. The glass ribbon is pulled away from the isopipe by rollers and cooled by a temperature-controlled housing as it moves vertically downward. For example, at the bottom of the housing (the drawing bottom), individual glass sheets are cut from the glass ribbon.

[0109] Glass-ceramic compositions can be formed from glass compositions by a suitable heat treatment process, or they can be formed directly, wherein crystallization occurs during casting and no separate heat treatment process is required.

[0110] In the embodiments, the glass composition is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition. However, other glass compositions are contemplated, and the list is not intended to be exhaustive.

[0111] The alkali aluminosilicate glass composition comprises alumina, at least one alkali metal, and SiO2, such as greater than 50 mol% SiO2. The alkali aluminosilicate glass composition may include at least 58 mol% SiO2, and in other embodiments, may include at least 60 mol% SiO2, wherein the ratio ((Al2O3 + B2O3) / Σ) 改性剂 The ratio is greater than 1, where the components are expressed in mol% and the modifier is an alkali metal oxide. More specific examples include: 58 mol% to 72 mol% SiO2; 9 mol% to 17 mol% Al2O3; 2 mol% to 12 mol% B2O3; 8 mol% to 16 mol% Na2O; and 0 to 4 mol% K2O, where the ratio ((Al2O3 + B2O3) / Σ) 改性剂 )> 1.

[0112] Sodium-calcium glass compositions include SiO2, Na2O, and CaO. Example sodium-calcium compositions include 72 mol% SiO2, 1 mol% Al2O3, 14 mol% Na2O, 4 mol% MgO, and 7 mol% CaO.

[0113] Alkaline earth borosilicate glass compositions comprise alkaline earth metals, B₂O₃, alumina, and silicon dioxide. Example alkaline earth borosilicate glass compositions comprise, by oxides: 65 wt% to 75 wt% SiO₂; 7 wt% to 13 wt% Al₂O₃; 5 wt% to 15 wt% B₂O₃; 5 wt% to 15 wt% CaO; 0 to 5 wt% BaO; 0 to 3 wt% MgO; and 0 to 5 wt% SrO. These glass compositions are exemplary only and are not intended to be limiting.

[0114] In one embodiment, substrate 12 includes a compressive stress region 26 at or near a first main surface 16. Similarly, substrate 12 may include another compressive stress region 28 at or near a second main surface 18. In such cases, a tensile stress (e.g., central tensile force) region 30 is balanced with and positioned between the compressive stress regions 26, 28. The compressive stress regions 26, 28 reinforce substrate 12. Photoelastic methods (e.g., transmission photoelasticity) can be used to determine whether substrate 12 has a compressive stress region 26 or compressive stress regions 26, 28.

[0115] Compressive stress regions 26 or 26, 28 can be imparted to substrate 12 by a variety of methods. Examples include chemical tempering (e.g., ion exchange), thermal tempering, and lamination.

[0116] In the case of ion exchange, basic cations in such a cation source (e.g., a molten salt or "ion exchange" bath) exchange with smaller basic cations in the substrate 12. For example, during ion exchange, potassium ions from the cation source exchange with sodium and / or lithium ions in the substrate 12 by immersing the substrate 12 in a molten salt bath containing potassium salts (such as, but not limited to, potassium nitrate (KNO3)). Other potassium salts that can be used in the ion exchange process include, but are not limited to, potassium chloride (KCl), potassium sulfate (K2SO4), combinations thereof, etc. The ion exchange bath described herein may contain basic ions other than potassium and their corresponding salts. For example, the ion exchange bath may also include sodium salts such as sodium nitrate, sodium sulfate, sodium chloride, etc. The exchange of cations creates a compressive stress region 26 or compressive stress regions 26, 28. The compressive stress region 26 extends from the first main surface 16 to a certain depth of compression (DOC) (not described separately) within the substrate 12. Similarly, the compressive stress region 28 extends from the second main surface 18 to the DOC.

[0117] In the case of heat tempering, substrate 12 is heated to a temperature close to its softening point. Substrate 12 is then removed from the heating medium, and its first main surface 16 and second main surface 18 are rapidly cooled to below the strain point of the glass substrate 12, i.e., the temperature at which molten glass is considered to have hardened. Therefore, the main surface region of substrate 12 rapidly contracts and hardens, while the interior remains relatively more fluid and expandable. When substrate 12 is cooled to a constant ambient temperature, the interior attempts to contract more than the main surface region due to the slower cooling rate, but this is limited by the hardened main surface region. Therefore, when the temperature of substrate 12 reaches equilibrium, the stress at the first main surface 16 and second main surface 18 becomes highly compressible and is balanced by the tensile stress within the interior of substrate 12.

[0118] In the case of lamination, a surface layer or outer layer with relatively low thermal expansion is fused with a core layer with relatively high thermal expansion, such that compressive stress can be generated in the main surface area when the substrate 12 (with the laminated layer) is cooled after fusion. Lamination is similar to thermal tempering because when the substrate 12 cools, the interior (with relatively high thermal expansion) attempts to shrink, but is limited by the main surface area (with relatively low thermal expansion), which shrinks less during cooling.

[0119] The substrate 12 has a thickness 32. The thickness 32 is the linear distance between the first main surface 16 and the second main surface 18, measured orthogonally to the first main surface 16. In an embodiment, the thickness 32 of the substrate 12 is in the range of 0.1 mm to 5.0 mm. In the embodiments, the thickness 32 of the substrate 12 is 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.25 mm, 1.5 mm, 1.75 mm, 2.0 mm, 2.25 mm, 2.5 mm, 2.75 mm, 3.0 mm, 3.25 mm, 3.5 mm, 3.75 mm, 4.0 mm, 4.25 mm, 4.5 mm, 4.75 mm, or 5.0 mm, or within any range defined by any two of these values ​​(e.g., 1.75 mm to 4.0 mm, 0.4 mm to 2.75 mm, etc.). Thicknesses 32 less than 0.1 mm and greater than 5.0 mm are considered. For applications where reducing the weight of the article 10 is beneficial, such as when the article 10 covers a photovoltaic cell integrated into a vehicle or mobile device, a thickness 32 at the lower limit of the range may be useful. The thickness 32 of the substrate 12 of the product 10 can be determined using scanning electron microscopy and other methods.

[0120] As described above, the article 10 also includes a multilayer coating 14 disposed on the substrate 12. Specifically, the multilayer coating 14 is disposed on a first main surface 16 of the substrate 12. The multilayer coating 14 includes at least one period 34 of a low refractive index material layer 36 and a high refractive index material layer 38.

[0121] In an embodiment, the multilayer coating 14 includes a repeating cycle 34 of a low-refractive-index material layer 36 and a high-refractive-index material layer 38. 1、2、3、. . . n In this configuration, the cycles 34 are stacked one on top of the other. In such embodiments, the multilayer coating 14 comprises at least four layers 36, 38. For example, when the multilayer coating 14 comprises two cycles 34 (341 and 342), the multilayer coating 14 comprises a first low-refractive-index material layer 361 disposed on a first main surface 16 of the substrate 12, a second high-refractive-index material layer 382 disposed on the first low-refractive-index material layer 361 (thus ending cycle 341), a third low-refractive-index material layer 363 disposed on the second high-refractive-index material layer 382, ​​and a fourth high-refractive-index material layer 384 disposed on the third low-refractive-index material layer 363 (thus ending cycle 342). Theoretically, there is no limitation on the number of cycles 34 and therefore the number of layers 36, 38. The names of the layers 36, 38 of the multilayer coating 14, such as "first," "second," "third," etc., indicate their relative positioning and proximity to the first main surface 16 of the substrate 12.

[0122] The multilayer coating 14 terminates at a low-refractive-index material termination layer 40, which faces the external environment 42 and is away from the first main surface 16 of the substrate 12. Continuing with the example in the previous paragraph, the multilayer coating 14 includes a fifth low-refractive-index material termination layer 40 disposed on a fourth high-refractive-index material layer 384.

[0123] The "low" in "low-refractive-index material" and the "high" in "high-refractive-index material" are relative to each other. In other words, the refractive index of a low-refractive-index material is lower than that of a high-refractive-index material. Similarly, the refractive index of a high-refractive-index material is higher than that of a low-refractive-index material.

[0124] In this embodiment, the refractive index of the low-refractive-index material is in the range of 1.40 to 1.60. The refractive index of the low-refractive-index material can be 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, or 1.60, or within any range defined by any two of these values ​​(e.g., 1.49 to 1.52, 1.45 to 1.54, etc.). These values ​​are not exclusive, and the refractive index of the low-refractive-index material can be less than 1.40 or greater than 1.60, provided that the refractive index of the low-refractive-index material is lower than that of the high-refractive-index material.

[0125] In this embodiment, the refractive index of the high-refractive-index material is in the range of 1.70 to 2.50. The refractive index of the high-refractive-index material can be 1.70, 1.75, 1.80, 1.85, 1.90, 1.95, 2.00, 2.05, 2.10, 2.15, 2.20, 2.25, 2.30, 2.35, 2.40, 2.45, or 2.50, or within any range defined by any two of these values ​​(e.g., 1.85 to 2.35, 1.95 to 2.45, etc.). These values ​​are not exclusive, and the refractive indices of the high-refractive-index material can be less than 1.70 or greater than 2.50, provided that the refractive index of the high-refractive-index material is higher than that of the low-refractive-index material.

[0126] The refractive index values ​​for low-refractive-index materials and high-refractive-index materials are given at 550 nm. These values ​​can be measured using spectral ellipsometrics.

[0127] Examples of low refractive index materials include one or more of the following: SiO2, doped SiO2, Al2O3, GeO2, SiO, AlO x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3. Doped SiO2 refers to SiO2 doped with a small amount of one or more other oxides (such as 1 mol% to 10 mol% Al2O3 or ZrO2). Doped SiO2 may also include nitrogen doping, which can also be represented as SiO2. x N y Doping with SiO2 can improve durability. Examples of high refractive index materials include one or more of the following: AlN, SiNx AlO x N y SiO x N y Nb₂O₅, ZrO₂, Ta₂O₅, and TiO₂. Use chemical formulas with letter subscripts (e.g., AlO₂). x N y () is an atomic fractional expression. In an atomic fractional expression, each subscript value can be in the range of 0 to 1, the sum of all subscript values ​​is 1, and the remaining part is the first element in the material. Therefore, in AlO x N y In the example, x + y = 1, and the remainder is Al. If the atomic fraction of oxygen (represented by x) is 0.1, then the atomic fraction of nitrogen (represented by y) is 0.9. As another example, Si u Al x O y N z The subscript "u" in the text can have a value of zero, and in such cases, the material can be described as AlO. x N y Because after excluding Si when u is 0, the remaining element is the first remaining element, which in this case is Al. The subscripts of any particular atomic fraction cannot all be 0, otherwise it would result in pure elemental forms (e.g., pure silicon, pure aluminum metal, oxygen, etc.). Atomic fractions are described in many general textbooks and are commonly used to describe alloys. AlO x N y and SiO x N y It can be a low-refractive-index material or a high-refractive-index material, depending on the concentrations of Al, Si, O, and N. The concentrations of any one or more of Si, Al, O, and N can be varied to increase or decrease the refractive index. The examples of low-refractive-index and high-refractive-index materials provided in this article are not exclusive.

[0128] In an embodiment, the first low-refractive-index material layer 361 of the multilayer coating 14 is or contains SiO2 or doped SiO2 (as a low-refractive-index material) and is directly disposed on the first main surface 16 of the substrate 12. This first low-refractive-index material layer 361 can improve the adhesion of the multilayer coating 14 to the substrate 12. Similarly, in an embodiment, the low-refractive-index material termination layer 40 is or contains SiO2 or doped SiO2.

[0129] The multilayer coating 14 can be formed using various deposition methods, such as vacuum deposition techniques, including chemical vapor deposition (e.g., plasma-enhanced chemical vapor deposition (PECVD), low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or non-reactive sputtering or laser ablation, including metal-mode reactive sputtering), thermal or electron beam evaporation, and / or atomic layer deposition. Liquid-based methods, such as spraying, dipping, spin coating, or slot coating (e.g., using sol-gel materials), can also be used. In cases utilizing vacuum deposition, in-line processes can be used to form the multilayer coating 14 in a single deposition run. In some cases, vacuum deposition can be performed using a linear PECVD source. Typically, vapor deposition techniques can include a variety of vacuum deposition methods that can be used to produce thin films. For example, physical vapor deposition uses physical processes (such as heating or sputtering) to generate material vapor, which is then deposited onto the object to be coated.

[0130] Specifically, TiO2 can be deposited in the form of amorphous, semi-crystalline, or polycrystalline materials, wherein the crystalline phase may contain anatase or rutile. TiO2 can be semi-crystalline or polycrystalline, having at least 50 vol% or at least 80 vol% rutile. Among the TiO2 phases, the rutile phase exhibits the highest hardness. Example thin film deposition techniques for depositing rutile are described in, for example, the following references: Pradhan, Swati S., et al., “Low temperature stabilized rutile phase TiO2 films grown by sputtering”, *Thin Solid Films*, 520.6 (2012):1809-1813; and Guillén, C., J. Montero, and J. Herrero., “Anatase and rutile TiO2 thin films prepared by reactive DC sputtering at high deposition rates on glass and flexible polyimide substrate 12s”, *Journal of Materials Science*, 49 (2014):5035-5042. Both references are incorporated herein by reference in their entirety.

[0131] Furthermore, SiNx and SiO x N y Amorphous materials with high hardness and high refractive index can be deposited by reactive sputtering or metal mode reactive sputtering.

[0132] The anti-reflective properties exhibited by the multilayer coating 14 on substrate 12 are due to the thickness 44 of the low-refractive-index material layer 36, the high-refractive-index material layer 38, and the low-refractive-index material terminal layer 40. 1、2、3、. . . n The function of. Without being bound by theory, the multilayer coating 14 reduces reflection by utilizing the principles of electromagnetic radiation interference and wave behavior. Individual layers 36 to 40 have a thickness of 44. 1、2、3、. . . n It is engineered to achieve destructive interference within a specific wavelength range, thereby reducing reflections within that range.

[0133] Although embodiments of multilayer coating 14 include a repeating cycle 34 of low-refractive-index material layer 36 and high-refractive-index material layer 38. 1、2、3、. . . n However, the thickness 44 of the low-refractive-index material layer 36 in one period 34 does not necessarily have to be the same as the thickness 44 of the low-refractive-index material layer 36 in another period 34. The same applies to the different high-refractive-index material layers 38 in different periods 34. In fact, in many embodiments, the thickness 44 of layers 36, 38, and 40 of the multilayer coating 14 is different. The thickness 44 of any particular layer 36, 38, or 40 of the multilayer coating 14 can be measured using scanning electron microscopy.

[0134] In an embodiment, the thickness 441 of the first low-refractive-index material layer 361 of the multilayer coating 14 is in the range of 50 nm to 250 nm. The thickness 441 of the first low-refractive-index material layer 361 can be 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, or 250 nm, or within any range (e.g., 70 nm to 120 nm, 100 nm to 200 nm, etc.) defined by any two of these values. The thickness 441 of the first low-refractive-index material layer 361, ranging from 50 nm to 250 nm, is associated with low reflectivity at wavelengths in the near-infrared region (e.g., from 700 nm to about 975 nm), especially when the refractive index of the first low-refractive-index material layer 361 is less than that of the substrate 12 (e.g., less than 1.51 or 1.50). An example of such a low-refractive-index material is SiO2.

[0135] The multilayer coating 14 has a total thickness 46. The total thickness 46 can be in the range of 350 nm to 1400 nm, 350 nm to 1000 nm, 350 nm to 800 nm, or 350 nm to 650 nm. However, a total thickness 46 less than 350 nm and greater than 1400 nm (e.g., 1500 nm) is envisioned. The total thickness 46 can be 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 1050 nm, 1100 nm, 1150 nm, 1200 nm, 1250 nm, 1300 nm, 1350 nm, or 1400 nm, or within any range defined by any two of these values ​​(e.g., 750 nm to 1350 nm, 650 nm to 850 nm, etc.). In preferred embodiments, the total thickness 46 can be less than 1400 nm, less than 1000 nm, less than 800 nm, less than 650 nm, or even less than 600 nm. Reducing the total thickness 46 can lower costs, while increasing the total thickness 46 can improve hardness or durability, and these two criteria can be balanced when the total thickness is within the aforementioned ranges.

[0136] In this embodiment, the combined thickness 44 of the low-refractive-index material layer 36 is greater than 55% of the total thickness 46 of the multilayer coating 14. For example, the combined thickness 44 of the low-refractive-index material layer 36 is in the range of 55% to 75% of the total thickness 46 of the multilayer coating 14. The combined thickness 44 of the low-refractive-index material layer 36 can be 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, or 75% of the total thickness 46 of the multilayer coating 14, or within any range defined by any two of these values ​​(e.g., 65% to 75%, 56% to 66%, etc.). These percentages are merely exemplary, and the combined thickness 44 of the low-refractive-index material layer 36 can be less than or equal to 55% of the total thickness 46 of the multilayer coating 14 or greater than or equal to 75% of the total thickness.

[0137] In a more specific embodiment, the multilayer coating 14 has two cycles 34 1、2In this case, five layers 36, 38, and 40 are included, thus providing four layers 36 and 38 and a fifth terminal layer 40 thereon. A first low-refractive-index material layer 361 is disposed directly on the first main surface 16 of the substrate 12 and has a thickness 441 in the range of 175 nm to 225 nm. The thickness 441 of the first low-refractive-index material layer 361 can be 175 nm, 180 nm, 185 nm, 190 nm, 195 nm, 200 nm, 205 nm, 210 nm, 215 nm, 220 nm, or 225 nm, or within any range defined by any two of these values ​​(e.g., 200 nm to 210 nm, 180 nm to 195 nm, etc.). A second high-refractive-index material layer 382 is disposed directly on the first low-refractive-index material layer 361 and has a thickness 442 in the range of 15 nm to 25 nm. The thickness 442 of the second high-refractive-index material layer 382 can be 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, or 25 nm, or within any range defined by any two of these values ​​(e.g., 16 nm to 22 nm, 18 nm to 21 nm, etc.). The third low-refractive-index material layer 363 is disposed directly on the second high-refractive-index material layer 382 and has a thickness 443 in the range of 30 nm to 40 nm. The thickness 443 of the third low-refractive-index material layer 363 can be 30 nm, 31 nm, 32 nm, 33 nm, 34 nm, 35 nm, 36 nm, 37 nm, 38 nm, 39 nm, or 40 nm, or within any range defined by any two of these values ​​(e.g., 31 nm to 37 nm, 44 nm to 36 nm, etc.). A fourth high-refractive-index material layer 384 is disposed directly on the third low-refractive-index material layer 363 and has a thickness 444 in the range of 130 nm to 150 nm. The thickness of the fourth high-refractive-index material layer 384 can be 130 nm, 131 nm, 132 nm, 133 nm, 134 nm, 135 nm, 136 nm, 137 nm, 138 nm, 139 nm, 140 nm, 141 nm, 142 nm, 143 nm, 144 nm, 145 nm, 146 nm, 147 nm, 148 nm, 149 nm, or 150 nm, or within any range defined by any two of these values ​​(e.g., 133 nm to 148 nm, 134 nm to 146 nm, etc.). A fifth low-refractive-index material terminal layer 40 is disposed directly on the fourth high-refractive-index material layer 384 and has a thickness 445 in the range of 90 nm to 110 nm.The thickness 445 of the fifth terminal layer 40 can be 90 nm, 91 nm, 92 nm, 93 nm, 94 nm, 95 nm, 96 nm, 97 nm, 98 nm, 99 nm, 100 nm, 101 nm, 102 nm, 103 nm, 104 nm, 105 nm, 106 nm, 107 nm, 108 nm, 109 nm, or 110 nm, or within any range defined by any two of these values ​​(e.g., 92 nm to 109 nm, 104 nm to 108 nm, etc.). An example of a five-layer embodiment is illustrated in Example 1 below.

[0138] In another, more specific embodiment, the multilayer coating 14 has four cycles 34 1至4In this case, nine layers 36, 38, and 40 are included, thus providing eight layers 36 and 38 and a ninth terminal layer 40 thereon. A first low-refractive-index material layer 361 is disposed directly on the first main surface 16 of the substrate 12 and has a thickness 441 in the range of 175 nm to 225 nm. The thickness 441 of the first low-refractive-index material layer 361 can be 175 nm, 180 nm, 185 nm, 190 nm, 195 nm, 200 nm, 205 nm, 210 nm, 215 nm, 220 nm, or 225 nm, or in any range defined by any two of these values ​​(e.g., 200 nm to 210 nm, 180 nm to 195 nm, etc.). A second high-refractive-index material layer 382 is disposed directly on the first low-refractive-index material layer 361 and has a thickness 442 in the range of 5 nm to 25 nm. The thickness 442 of the second high-refractive-index material layer 382 can be 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, or 25 nm, or within any range defined by any two of these values ​​(e.g., 6 nm to 12 nm, 18 nm to 21 nm, etc.). The third low-refractive-index material layer 363 is disposed directly on the second high-refractive-index material layer 382 and has a thickness 443 in the range of 35 nm to 60 nm. The thickness 443 of the third low-refractive-index material layer 363 can be 30 nm, 31 nm, 32 nm, 33 nm, 34 nm, 35 nm, 36 nm, 37 nm, 38 nm, 39 nm, 40 nm, 41 nm, 42 nm, 43 nm, 44 nm, 45 nm, 46 nm, 47 nm, 48 nm, 49 nm, 50 nm, 51 nm, 52 nm, 53 nm, 54 nm, 55 nm, 56 nm, 57 nm, 58 nm, 59 nm, or 60 nm, or within any range defined by any two of these values ​​(e.g., 31 nm to 37 nm, 44 nm to 36 nm, etc.). The fourth high-refractive-index material layer 384 is disposed directly on the third low-refractive-index material layer 363 and has a thickness 444 in the range of 20 nm to 30 nm.The thickness 444 of the fourth high-refractive-index material layer 384 can be 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, or 30 nm, or within any range defined by any two of these values ​​(e.g., 22 nm to 29 nm, 21 nm to 24 nm, etc.). The fifth low-refractive-index material layer 365 is disposed directly on the fourth high-refractive-index material layer 384 and has a thickness 445 in the range of 10 nm to 25 nm. The thickness 445 of the fifth low-refractive-index material layer 365 can be 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, or 25 nm, or within any range defined by any two of these values ​​(e.g., 11 nm to 15 nm, 12 nm to 24 nm, etc.). A sixth high-refractive-index material layer 386 is disposed directly on the fifth low-refractive-index material layer 365 and has a thickness 446 in the range of 75 nm to 110 nm. The thickness 446 of the sixth high-refractive-index material layer 386 can be 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, or 110 nm, or within any range defined by any two of these values ​​(e.g., 80 nm to 90 nm, 85 nm to 105 nm, etc.). A seventh low-refractive-index material layer 367 is disposed directly on the sixth high-refractive-index material layer 386 and has a thickness 447 in the range of 5 nm to 20 nm. The thickness 447 of the seventh low-refractive-index material layer 367 can be 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, or 20 nm, or within any range defined by any two of these values ​​(e.g., 6 nm to 11 nm, 8 nm to 19 nm, etc.). The eighth high-refractive-index material layer 388 is disposed directly on the seventh low-refractive-index material layer 367 and has a thickness 448 in the range of 15 nm to 30 nm. The thickness 448 of the eighth high-refractive-index material layer 388 can be 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm or 30 nm or within any range defined by any two of these values ​​(e.g., 16 nm to 29 nm, 20 nm to 28 nm).A ninth low-refractive-index material termination layer 40 is disposed directly on the eighth high-refractive-index material layer 388 and has a thickness 449 in the range of 90 nm to 115 nm. The thickness 449 of the ninth low-refractive-index material termination layer 40 can be 90 nm, 92 nm, 94 nm, 96 nm, 98 nm, 100 nm, 102 nm, 104 nm, 106 nm, 108 nm, 110 nm, 112 nm, 114 nm, or 115 nm, or within any range defined by any two of these values ​​(e.g., 92 nm to 110 nm, 104 nm to 112 nm, etc.). An example of a nine-layer embodiment is illustrated in Example 3 below.

[0139] In a more specific embodiment, the multilayer coating 14 has eight cycles 34 1至8In this case, seventeen layers 36, 38, and 40 are included, thus providing sixteen layers 36 and 38 and a seventeenth terminal layer 40 thereon. A first low-refractive-index material layer 361 is disposed directly on the first main surface 16 of the substrate 12 and has a thickness 441 in the range of 175 nm to 225 nm. The thickness 441 of the first low-refractive-index material layer 361 can be 175 nm, 180 nm, 185 nm, 190 nm, 195 nm, 200 nm, 205 nm, 210 nm, 215 nm, 220 nm, or 225 nm, or within any range defined by any two of these values ​​(e.g., 200 nm to 210 nm, 180 nm to 195 nm, etc.). A second high-refractive-index material layer 382 is disposed directly on the first low-refractive-index material layer 361 and has a thickness 442 in the range of 15 nm to 25 nm. The thickness 442 of the second high-refractive-index material layer 382 can be 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, or 25 nm, or within any range defined by any two of these values ​​(e.g., 16 nm to 22 nm, 18 nm to 21 nm, etc.). The third low-refractive-index material layer 363 is disposed directly on the second high-refractive-index material layer 382 and has a thickness 443 in the range of 30 nm to 40 nm. The thickness 443 of the third low-refractive-index material layer 363 can be 30 nm, 31 nm, 32 nm, 33 nm, 34 nm, 35 nm, 36 nm, 37 nm, 38 nm, 39 nm, or 40 nm, or within any range defined by any two of these values ​​(e.g., 31 nm to 37 nm, 32 nm to 36 nm, etc.). A fourth high-refractive-index material layer 384 is disposed directly on the third low-refractive-index material layer 363 and has a thickness 444 in the range of 130 nm to 160 nm. The thickness 444 of the fourth high-refractive-index material layer 384 can be 130 nm, 135 nm, 140 nm, 145 nm, 150 nm, 155 nm, or 160 nm, or within any range defined by any two of these values ​​(e.g., 135 nm to 145 nm, 140 nm to 155 nm, etc.). A fifth low-refractive-index material layer 365 is disposed directly on the fourth high-refractive-index material layer 384 and has a thickness 445 in the range of 25 nm to 40 nm.The thickness 445 of the fifth low-refractive-index material layer 365 can be 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, 31 nm, 32 nm, 33 nm, 34 nm, 35 nm, 36 nm, 37 nm, 38 nm, 39 nm, or 40 nm, or within any range defined by any two of these values ​​(e.g., 26 nm to 38 nm, 32 nm to 36 nm, etc.). The sixth high-refractive-index material layer 386 is disposed directly on the fifth low-refractive-index material layer 365 and has a thickness 446 in the range of 10 nm to 20 nm. The thickness 446 of the sixth high-refractive-index material layer 386 can be 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, or 20 nm, or within any range defined by any two of these values ​​(e.g., 12 nm to 16 nm, 14 nm to 18 nm, etc.). A seventh low-refractive-index material layer 367 is disposed directly on the sixth high-refractive-index material layer 386 and has a thickness 447 in the range of 140 nm to 175 nm. The thickness 447 of the seventh low-refractive-index material layer 367 can be 140 nm, 145 nm, 150 nm, 155 nm, 160 nm, 165 nm, 170 nm, or 175 nm, or within any range defined by any two of these values ​​(e.g., 145 nm to 165 nm, 150 nm to 170 nm, etc.). An eighth high-refractive-index material layer 388 is disposed directly on the seventh low-refractive-index material layer 367 and has a thickness 448 in the range of 10 nm to 20 nm. The thickness 448 of the eighth high-refractive-index material layer 388 can be 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, or 20 nm, or within any range defined by any two of these values ​​(e.g., 11 nm to 18 nm, 13 nm to 19 nm). The ninth low-refractive-index material layer 369 is disposed directly on the eighth high-refractive-index material layer 388 and has a thickness 449 in the range of 24 nm to 40 nm. The thickness 449 of the ninth low-refractive-index material layer 369 can be 24 nm, 26 nm, 28 nm, 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, or 40 nm, or within any range defined by any two of these values ​​(e.g., 24 nm to 36 nm, 26 nm to 32 nm, etc.). Tenth high-refractive-index material layer 38. 10 It is directly disposed on the ninth low-refractive-index material layer 369 and has a thickness 44 in the range of 130 nm to 160 nm. 10 The tenth high-refractive-index material layer 3810 Thickness 44 10 It can be 130 nm, 135 nm, 140 nm, 145 nm, 150 nm, 155 nm, or 160 nm, or within any range defined by any two of these values ​​(e.g., 135 nm to 155 nm, 140 nm to 160 nm, etc.). Eleventh low-refractive-index material layer 36 11 Directly placed on the tenth high refractive index material layer 38 10 Above, and having a thickness of 44 in the range of 30 nm to 40 nm. 11 Eleventh low-refractive-index material layer 36 11 Thickness 44 11 It can be 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, or 40 nm, or within any range defined by any two of these values ​​(e.g., 32 nm to 38 nm, 34 nm to 40 nm, etc.). Twelfth high-refractive-index material layer 38 12 Directly placed in the eleventh low-refractive-index material layer 36 11 Above, and having a thickness of 44 in the range of 10 nm to 20 nm. 12 The twelfth high-refractive-index material layer 38 12 Thickness 44 12 It can be 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, or 20 nm, or within any range defined by any two of these values ​​(e.g., 12 nm to 18 nm, 14 nm to 16 nm, etc.). Thirteenth low-refractive-index material layer 36 13 Directly placed in the twelfth high refractive index material layer 38 12 Above, and having a thickness of 44 in the range of 105 nm to 135 nm. 13 Thirteenth low-refractive-index material layer 36 13 Thickness 44 13 It can be 105 nm, 110 nm, 115 nm, 120 nm, 125 nm, 130 nm, or 135 nm, or within any range defined by any two of these values ​​(e.g., 110 nm to 130 nm, 115 nm to 135 nm, etc.). Fourteenth high-refractive-index material layer 38 14 Directly placed in the thirteenth low-refractive-index material layer 36 13 Above, and having a thickness of 44 in the range of 10 nm to 20 nm. 14 The fourteenth high-refractive-index material layer 38 14 Thickness 44 14It can be 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, or 20 nm, or within any range defined by any two of these values ​​(e.g., 10 nm to 14 nm, 16 nm to 20 nm, etc.). Fifteenth low-refractive-index material layer 36 15 Directly placed in the fourteenth high refractive index material layer 38 14 Above, and having a thickness of 44 in the range of 35 nm to 50 nm. 15 The fifteenth low-refractive-index material layer 36 15 Thickness 44 15 It can be 35 nm, 36 nm, 38 nm, 40 nm, 42 nm, 44 nm, 46 nm, 48 nm, or 50 nm, or within any range defined by any two of these values ​​(e.g., 36 nm to 50 nm, 38 nm to 42 nm, etc.). Sixteenth high-refractive-index material layer 38 16 Directly placed in the fifteenth low-refractive-index material layer 36 15 Above, and having a thickness of 44 in the range of 120 nm to 150 nm. 16 The sixteenth high-refractive-index material layer 38 16 Thickness 44 16 It can be 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, or 150 nm, or within any range defined by any two of these values ​​(e.g., 120 nm to 145 nm, 135 nm to 145 nm, etc.). The seventeenth low-refractive-index material termination layer 40 is directly disposed on the sixteenth high-refractive-index material layer 38. 16 Above, and having a thickness of 44 in the range of 90 nm to 110 nm. 17 The thickness of the seventeenth low-refractive-index material terminal layer 40 is 44. 17 It can be 90 nm, 92 nm, 94 nm, 96 nm, 98 nm, 100 nm, 102 nm, 104 nm, 106 nm, 108 nm, or 110 nm, or within any range defined by any two of these values ​​(e.g., 92 nm to 98 nm, 96 nm to 108 nm, etc.). An example of a seventeen-layer embodiment is illustrated in Example 1 below.

[0140] Article 10 has a primary surface 48. The primary surface 48 of article 10 is provided by a low-refractive-index material terminal layer 40 of multilayer coating 14 (e.g., a ninth terminal layer 40 of multilayer coating 14 consisting of nine layers 36, 38, 40). In addition, article 10 also has a second primary surface 50, which is the second primary surface of the substrate when there is no coating on the second primary surface 18 of the substrate 12.

[0141] Article 10, having the multilayer coating 14 of this disclosure disposed on substrate 12, exhibits beneficial anti-reflective properties. Specifically, in embodiments, article 10 exhibits a primary surface average reflectance of less than or equal to 0.900% (e.g., less than or equal to 0.550% in the entire wavelength range of 600 nm to 750 nm). In embodiments, article 10 exhibits a primary surface average reflectance of 0.363% to 0.900%, 0.363% to 0.590%, or 0.363% to 0.550% in the entire wavelength range of 600 nm to 750 nm. In embodiments, article 10 exhibits a primary surface average reflectance of 0.363% to 1.00% in the entire wavelength range of 600 nm to 750 nm. In the embodiment, article 10 exhibits an average reflectance of its primary surface 48 of 0.363%, 0.364%, 0.366%, 0.368%, 0.370%, 0.372%, 0.374%, 0.376%, 0.378%, 0.380%, 0.382%, 0.384%, or 0.385% or within any range defined by any two of these values ​​(e.g., 0.363% to 0.385%, 0.368% to 0.378%, etc.). This low reflectance across the entire wavelength range is important for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0142] As the name suggests, "average reflectance of principal surface 48" is the average reflectance of article 10 at its principal surface 48. The average reflectance of principal surface 48 is determined relative to an angle of incidence (AOI) of 5 degrees (for incident irradiation) orthogonal to principal surface 48 of article 10. "Average reflectance" refers to the average amount of incident irradiation power reflected by the material within the stated wavelength range. Reflections from the principal surface 48 of article 10 can be isolated by removing reflections from the second principal surface 50 of article 10 (e.g., by using a refractive index matching oil coupled to an absorber or other known methods on the second principal surface 50).

[0143] In one embodiment, article 10 exhibits an average reflectance of less than or equal to 2.5% of its principal surface 48 over the entire wavelength range of 400 nm to 450 nm. In another embodiment, article 10 exhibits an average reflectance of less than or equal to 2.0% of its principal surface 48 over the entire wavelength range of 400 nm to 450 nm. In yet another embodiment, article 10 exhibits an average reflectance of its principal surface 48 in the range of 1.80% to 4.40%, 1.80% to 2.60%, 1.80% to 2.10%, or 1.80% to 1.83% over the entire wavelength range of 400 nm to 450 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0144] In one embodiment, article 10 exhibits a primary surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 450 nm to 600 nm. In another embodiment, article 10 exhibits a primary surface average reflectance of less than or equal to 1.08% over the entire wavelength range of 450 nm to 600 nm. In yet another embodiment, article 10 exhibits a primary surface average reflectance of 0.703% to 1.40%, 0.703% to 1.08%, or 0.703% to 0.907% over the entire wavelength range of 450 nm to 600 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0145] In one embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 0.670% over the entire wavelength range of 600 nm to 650 nm. In another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 0.650% over the entire wavelength range of 600 nm to 650 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 0.570% over the entire wavelength range of 600 nm to 650 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 in the range of 0.324% to 0.407%, 0.324% to 0.570%, 0.324% to 0.650%, or 0.324% to 0.670% over the entire wavelength range of 600 nm to 650 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0146] In one embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.15% over the entire wavelength range of 750 nm to 800 nm. In another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.00% over the entire wavelength range of 750 nm to 800 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 0.730% over the entire wavelength range of 750 nm to 800 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 in the range of 0.441% to 1.15%, 0.441% to 1.00%, 0.441% to 0.730%, or 0.441% to 0.633% over the entire wavelength range of 750 nm to 800 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0147] In one embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.10% over the entire wavelength range of 800 nm to 850 nm. In another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.00% over the entire wavelength range of 800 nm to 850 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 in the range of 0.453% to 1.10%, 0.453% to 1.00%, 0.453% to 0.850%, or 0.453% to 0.566% over the entire wavelength range of 800 nm to 850 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0148] In one embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.40% over the entire wavelength range of 850 nm to 900 nm. In another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.30% over the entire wavelength range of 850 nm to 900 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.05% over the entire wavelength range of 850 nm to 900 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 in the range of 0.540% to 1.40%, 0.540% to 1.30%, or 0.540% to 1.05% over the entire wavelength range of 850 nm to 900 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0149] In one embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 2.20% over the entire wavelength range of 900 nm to 950 nm. In another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 2.08% over the entire wavelength range of 900 nm to 950 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 of less than or equal to 1.18% over the entire wavelength range of 900 nm to 950 nm. In yet another embodiment, article 10 exhibits an average reflectance of the main surface 48 in the range of 0.690% to 2.20%, 0.690% to 2.08%, or 0.690% to 1.18% over the entire wavelength range of 900 nm to 950 nm. This low reflectance over the entire wavelength range can be beneficial for solar panel applications, and article 10 achieves this low reflectance due to the multilayer coating 14.

[0150] In one embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 3.50% over the entire wavelength range of 950 nm to 1000 nm. In another embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 3.00% over the entire wavelength range of 950 nm to 1000 nm. In yet another embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 2.50% over the entire wavelength range of 950 nm to 1000 nm. In yet another embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 1.30% over the entire wavelength range of 950 nm to 1000 nm. In yet another embodiment, article 10 exhibits an average reflectance of the principal surface 48 in the range of 1.25% to 3.50%, 1.25% to 3.44%, 1.25% to 3.00%, 1.25% to 2.50%, or 1.25% to 1.30% over the entire wavelength range of 950 nm to 1000 nm. Low reflectivity across the entire wavelength range can be beneficial for solar panel applications, and the article 10 achieves this low reflectivity due to the multilayer coating 14.

[0151] In one embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 5.19% over the entire wavelength range of 1000 nm to 1050 nm. In another embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 4.25% over the entire wavelength range of 1000 nm to 1050 nm. In yet another embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 4.00% over the entire wavelength range of 1000 nm to 1050 nm. In yet another embodiment, article 10 exhibits an average reflectance of the principal surface 48 of less than or equal to 1.40% over the entire wavelength range of 1000 nm to 1050 nm. In yet another embodiment, article 10 exhibits an average reflectance of the principal surface 48 in the range of 0.660% to 5.19%, 0.660% to 4.25%, 0.660% to 4.00%, or 0.660% to 1.40% over the entire wavelength range of 1000 nm to 1050 nm. Low reflectivity across the entire wavelength range can be beneficial for solar panel applications, and the article 10 achieves this low reflectivity due to the multilayer coating 14.

[0152] In an embodiment, article 10 exhibits a primary surface average reflectance of 5.0%, 10.0%, 15.0%, 17.0%, 20.0%, 30.0%, or 40.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, or 1700 nm to 1800 nm. In another embodiment, article 10 exhibits a primary surface average reflectance of 5.0% or higher over the entire wavelength range of 1100 nm to 1800 nm. This high reflectance across the entire wavelength range is advantageous for solar panel applications by reducing panel heating due to infrared irradiation, and article 10 achieves this high reflectance due to the multilayer coating 14.

[0153] In an embodiment, article 10 exhibits a primary surface average reflectance of 48 greater than or equal to 4%, 13% or greater than or equal to 13%, or 20% or greater than or equal to 20% over the entire wavelength range of 300 nm to 350 nm. In another embodiment, article 10 exhibits a primary surface average reflectance of 48 in the range of 4.0% to 40.3%, 13% to 40.3%, or 23.5% to 40.3% over the entire wavelength range of 300 nm to 350 nm. Actively reflecting photons associated with the 300 nm to 350 nm wavelength range can be beneficial because such wavelengths reduce the transmittance of the polymer layer encapsulating photovoltaic cells in solar panel applications. Therefore, blocking such photons can result in higher power generation over time. Article 10 achieves this high reflectance due to the multilayer coating 14.

[0154] In one embodiment, article 10 exhibits an average transmittance greater than or equal to 95% across the entire wavelength range of 600 nm to 850 nm. In another embodiment, article 10 exhibits an average transmittance greater than or equal to 95% across the entire wavelength range of 550 nm to 900 nm. In yet another embodiment, article 10 exhibits an average transmittance greater than or equal to 95% across the entire wavelength range of 500 nm to 950 nm. In yet another embodiment, article 10 exhibits an average transmittance greater than or equal to 95% across the entire wavelength range of 600 nm to 850 nm.

[0155] In one embodiment, article 10 exhibits an average transmittance of less than or equal to 64% across the entire wavelength range of 300 nm to 350 nm. In another embodiment, article 10 exhibits an average transmittance of less than or equal to 55% across the entire wavelength range of 300 nm to 350 nm. In yet another embodiment, article 10 exhibits an average transmittance of less than or equal to 15% across the entire wavelength range of 300 nm to 350 nm. Finally, article 10 exhibits an average transmittance in the range of 10% to 64% across the entire wavelength range of 300 nm to 350 nm. In the embodiments, article 10 exhibits an average transmittance through article 10% to 350 nm over the entire wavelength range of 300 nm to 350 nm, or 10.4%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 61.6%, or 65%, or in any range defined by any two of these values ​​(e.g., 15% to 40%, 20% to 50%, etc.).

[0156] All transmittance values ​​mentioned herein are reported as average transmittance values ​​across both surfaces with an incident angle of 0 degrees and no coating on the second primary surface 50 of article 10 (e.g., the second primary surface 18 of substrate 12). The reflectance of the uncoated second primary surface of a substrate having a glass composition is typically about 4%. Therefore, the maximum possible average transmittance across both surfaces of article 10 with substrate 12 having a glass composition and the second primary surface 18 uncoated is approximately 96%. The average transmittance across both surfaces is the average of the transmittance across the entire stated wavelength range.

[0157] In addition to exhibiting beneficial anti-reflective properties, the article 10 having the multilayer coating 14 of this disclosure also exhibits beneficial scratch resistance properties. For example, the multilayer coating 14 exhibits a maximum hardness greater than or equal to 6 GPa measured according to the Glasswell indenter hardness test in the indentation depth range of 0 to 125 nm. In an embodiment, the multilayer coating 14 exhibits a maximum hardness greater than or equal to 8 GPa measured according to the Glasswell indenter hardness test in the indentation depth range of 0 to 125 nm.

[0158] As used in this article, “Bottleneck indenter hardness test” involves measuring the hardness of a material surface by pressing a diamond Bottleneck indenter into the material surface. The Glassbury indenter hardness test involves pressing a diamond Glassbury indenter into the main surface 48 of the article 10 or the surface of the multilayer coating 14 to form an indentation depth of approximately 100 nm, approximately 500 nm, or approximately 1000 nm. The maximum hardness is generally measured from this indentation along the entire range of indentation depth using methods described in the following literature (e.g., maximum hardness measured at any depth within the ranges of 0 to 100 nm, 0 to 125 nm, 0 to 500 nm, or 0 to 1000 nm, including any subranges selected within these ranges): Oliver, WC; Pharr, GM. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. *Journal of Materials Research*, Vol. 7, No. 6, 1992, 1564-1583; and Oliver, WC; Pharr, GM. Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology. *Journal of Materials Research*, Vol. 19, No. 1, 2004, 3-20. As used in this article, hardness refers to the maximum hardness, not the average hardness.

[0159] Typically, in nanoindentation measurement methods for coatings with a hardness higher than that of the underlying substrate 12 (e.g., using a Bose diamond indenter), the measured hardness may initially appear to increase due to the development of a plastic zone at shallow indentation depths, and then continue to increase, reaching a maximum or flat zone at deeper indentation depths. Thereafter, due to the influence of the underlying substrate 12, the hardness begins to decrease at even deeper indentation depths. The same effect is observed when using a substrate 12 with a hardness higher than that of the coating; however, due to the influence of the underlying substrate 12, the hardness increases at deeper indentation depths.

[0160] The specific hardness response of the multilayer coating 14 and its layers can be selected by choosing the indentation depth range and hardness values ​​at certain indentation depths, independent of the underlying substrate 12. When measuring the hardness of the multilayer film (when mounted on the substrate 12) with a Glass-Baumann diamond indenter, the permanent deformation zone (plastic zone) of the material is related to the material's hardness. During indentation, the elastic stress field extends far beyond this permanent deformation zone. As the indentation depth increases, the apparent hardness and modulus are affected by the interaction of the stress field with the underlying substrate 12. The influence of the substrate 12 on hardness occurs at deeper indentation depths (i.e., typically at depths greater than approximately 10% of the multilayer coating 14). Furthermore, complicating matters further, a specific minimum load is required to induce full plasticity during indentation. Before this specific minimum load, the hardness exhibits an overall increasing trend.

[0161] At small indentation depths (which can also be characterized by small loads) (e.g., at most about 50 nm), the apparent hardness of the material appears to increase sharply relative to the indentation depth. This small range of indentation depths does not represent a true hardness indicator but rather reflects the development of the aforementioned plastic zone, which is related to the finite radius of curvature of the indenter. At intermediate indentation depths, the apparent hardness approaches its maximum level. At deeper indentation depths, the influence of the substrate 12 becomes more pronounced with increasing indentation depth. Once the indentation depth exceeds approximately 30% of the total thickness 46 of the multilayer coating 14, the hardness may begin to decrease sharply.

[0162] In an embodiment, the thickness 44 of at least one high-refractive-index material layer 38 of the multilayer coating 14 is greater than 80 nm. The thickness 44 of at least one high-refractive-index material layer 38 of the multilayer coating 14 can be in the range of 80 nm to 150 nm. The thickness 44 of at least one high-refractive-index material layer 38 of the multilayer coating 14 can be 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, or 150 nm, or within any range defined by any two of these values ​​(e.g., 90 nm to 110 nm, 110 nm to 130 nm, etc.). It is believed that having such a thickness 44 for at least one high-refractive-index material layer 38 of the multilayer coating 14 contributes to the multilayer coating 14 exhibiting the maximum hardness value described herein. Similarly, placing at least one high-refractive-index material layer 38 of the multilayer coating 14 having such a thickness 44 within the outermost (e.g., furthest from the substrate 12) 300 nm of the total thickness 46 of the multilayer coating 14 contributes to the multilayer coating 14 exhibiting the maximum hardness value described herein.

[0163] In one embodiment, the outermost (e.g., furthest from the substrate 12) 300 nm of the total thickness 46 of the multilayer coating 14 has at least 40% high refractive index material. In another embodiment, the outermost (e.g., furthest from the substrate 12) 300 nm of the total thickness 46 of the multilayer coating 14 has at least 45% high refractive index material. In yet another embodiment, the outermost (e.g., furthest from the substrate 12) 300 nm of the total thickness 46 of the multilayer coating 14 has at least 50% high refractive index material. It is believed that including such a percentage of high refractive index material in the outer 300 nm of the total thickness 46 of the multilayer coating 14 contributes to the multilayer coating 14 exhibiting the maximum hardness value described herein.

[0164] In an embodiment, article 10 further includes an antifouling coating 52 located on the multilayer coating 14. The thickness 54 of the antifouling coating 52 is in the range of 0.5 nm to 10 nm. Such a thin thickness 54 has minimal impact on the antireflective properties of the multilayer coating 14, and the thickness 44 of the low refractive index material (SiO2) terminal layer 40 in the example below can be reduced by a reduction in the value of the thickness 54 of the antifouling coating 52 to compensate for the addition of the antifouling coating 52 thereon.

[0165] The antifouling coating 52 exhibits hydrophobic, hydrophilic, or completely hydrophobic properties. The properties exhibited by the antifouling coating 52 vary depending on its composition, as will be discussed further below. The decision regarding which properties the antifouling coating 52 should exhibit can depend on local weather conditions, such as humidity, rainfall frequency, and snowfall frequency.

[0166] Regarding composition, in the embodiments, the antifouling coating 52 comprises a silane or siloxane material. Example silane materials include fluorosilane materials and fluorine-free silanes, which may be preferred from a cost and environmental perspective (eliminating the need for so-called "permanent chemicals" such as perfluorinated alkyl and polyfluorinated alkyl substances (PFAS)). Example silane materials that may be fluorine-free are shown in Table 1 below.

[0167]

[0168]

[0169] In Table 1 above and elsewhere in this document, “PMDS” means polydimethylsiloxane, “PEO” means polyethylene oxide, “CA” means contact angle, “DIM” means diiodomethane, and “OA” means oleic acid. “Polarity,” “Dispersion,” and “Total” are surface energies, and the total is the sum of the polar and dispersive components. In the embodiments, the antifouling coating 52 comprises a single layer of silane coating material, such as one of the materials listed in Table 1 above.

[0170] In the embodiments, the antifouling coating 52 comprises at least two materials: (1) a silicon-containing matrix layer and (2) a hydrophobic or hydrophilic surface-modifying material. Our recent experiments have shown that this combination of (1) a silicon-containing matrix layer and (2) a hydrophobic or hydrophilic surface-modifying material can improve the durability of surface functionalization under repeated wear-type events.

[0171] A silicon-containing matrix layer can provide high-density silanols. In embodiments, the thickness of the silicon-containing matrix layer ranges from 5 nm to 200 nm (e.g., 5 nm to 10 nm). Suitable silicon-containing matrix layers include films deposited from hydrosilsesquioxanes (HSQ) or polysiloxanes by spin casting, dip coating, or spraying and cured by thermal or UV or ion bombardment. Alternatively, suitable silicon-containing matrix layers also include films deposited by physical vapor deposition (PVD) using ion-assisted evaporation of organically modified cage-like silsesquioxanes. Organic substituents at the vertices of the multioctahedral silsesquioxanes promote vaporization and form leaving groups upon reaction with the ion beam. Suitable organic groups include vinyl, methyl, phenyl, isobutyl, and dimethylsilyl groups. Suitable ion sources include gateless sources (such as end-Hall sources), gated sources, and radio frequency (RF) and inductively coupled plasma (ICP) plasma sources. All these matrix materials are smooth, thus exhibiting a surface roughness (R0) when deposited on substrates with the same or less roughness. a < 0.5 nm. In addition, these materials exhibit a refractive index close to that of silicon dioxide, a high silanol concentration, and an elastic modulus in the range of 15 GPa to 70 GPa.

[0172] Hydrophobic or hydrophilic surface modifiers can include perfluorinated, hydrocarbon, polydimethylsiloxane (PDMS), polyethylene glycol (PEG), or polyethylene oxide (PEO) surface modifiers to form hydrophobic or hydrophilic surfaces. Both types of surfaces have been shown to help prevent dust accumulation in photovoltaic applications. Functionalization is achieved by condensing reactive groups on the surface modifier with silanol groups in the silicon-containing matrix layer. Suitable reactive head groups include mono-, di-, or trifunctional alkoxysilyl groups, silyl halides, or aminosilyl groups. Functionalization can be performed simultaneously with the deposition of the silicon-containing matrix material, or it can be achieved by sequentially depositing the silicon-containing matrix layer and the surface modifier. In the examples, the thickness of the surface modifier ranges from 0.5 nm to 10 nm. Suitable hydrophobic surface modifiers include: fluorinated materials, such as perfluoropolyether silanes, perfluoroalkyl silanes, and perfluoropolyoctahedral silsesquioxanes; hydrocarbons, including alkyl, olefin, and aromatic compounds having six to 36 carbon atoms; and polyorganosiloxanes, including polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, and polysiloxanes containing mixtures of methyl, ethyl, and phenyl groups. Suitable hydrophilic surface modifiers include PEG-silanes, PEG-PDMS diblock copolymers, and PEO-functionalized silanes.

[0173] Antifouling coatings exhibiting fully hydrophobic properties 52 include those with small contact hysteresis (meaning a small difference between the advancing and retreating contact angles). Some of these coatings are also referred to as "liquid" coatings. These coatings have been shown to easily induce ice, mud, and other types of contaminants to slide off surfaces using only gravity and slight surface tilt (common in solar panel applications). The contact hysteresis exhibited by such coatings can be less than 5 degrees, less than 2 degrees, or even less than 1 degree. Examples of such fully hydrophobic coatings include PDMS polymer brushes with carefully controlled grafting and thickness parameters (e.g., brush thickness in the range of approximately 2 nm to 6 nm or, for example, 3 nm to 5 nm).

[0174] Now for reference Figures 6 to 9 The solar panel 100 includes an article 10 and an array of photovoltaic (PV) cell units 102 disposed below the article 10. Specifically, the array of PV cell units 102 is disposed below the second main surface 50 of the article 10. During use of the solar panel 100, photons 104 from the sun 106 enter the solar panel 100 through the article 10 and impact the array of PV cell units 102. The type of PV cell unit 102 is not particularly limited, but in a preferred embodiment, the PV cell unit 102 is a monocrystalline silicon PV cell unit.

[0175] During daytime hours, the primary surface 48 of the article 10 faces the sun 106. The second primary surface 50 of the article 10 (e.g., the second primary surface 18 of the substrate 12) faces inward toward the solar panel 100 in the opposite direction to the primary surface 48 of the article 10. The array of PV cell cells 102 faces the second primary surface 18 of the article 10.

[0176] In an embodiment, the solar panel 100 further includes a backsheet 108. An array of PV cell cells 102 is disposed between the article 10 and the backsheet 108. The backsheet 108 may have a glass composition. The glass composition of the backsheet 108 may be the same as, but not necessarily the same as, the composition of the substrate 12 of the article 10. For example, the glass composition of the backsheet 108 may be substantially free of alkali ions (e.g., this means that no alkali ions are intentionally added to the formulation of the glass composition). Further, the backsheet 108 may also include the multilayer coating 14 of this disclosure to reduce reflection and increase the abundance of photons 104 that pass through the backsheet 108 and strike the PV cell cells 102. The backsheet 108 may also contain a reflective polymer material or a metallic material.

[0177] The backsheet 108 has an inner main surface 110, an outer main surface 112, and a thickness 114 between the inner main surface 110 and the outer main surface 112. The inner main surface 110 faces the array of PV cell cells 102. The outer main surface 112 faces outward away from the solar panel 100. The thickness 114 of the backsheet 108 can be less than or equal to 2 mm. For example, the thickness 114 can be 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, or 2.0 mm, or within any range defined by any two of these values ​​(e.g., 0.3 mm to 1.0 mm, 0.5 mm to 0.9 mm, 0.6 mm to 1.3 mm, etc.). It was also envisioned that the thickness of the back panel 108 114 would be less than 0.3 mm.

[0178] Sandwiching the array of PV cell cells 102 between the article 10 and the backplate 108 having a glass composition allows the array of PV cell cells 102 to receive photons 104 that are transmitted through the article 10 and the backplate 108. This arrangement should theoretically increase the power generation of the solar panel 100 compared to the arrangement receiving photons 104 that are transmitted only through the article 10 and not the backplate 108.

[0179] A first polymer layer 116 can be disposed between the article 10 and the array of PV cell 102. Similarly, a second polymer layer 118 can be disposed between the backplate 108 and the array of PV cell 102. The first polymer layer and the second polymer layers 116 and 118 can reduce ions (e.g., Na+). + K + Ions migrate from the article 10 and backsheet 108 to the PV cell 102, respectively. This ion migration may lead to potential-induced degradation, i.e., a decrease in the efficiency of the PV cell 102. The first polymer layer and the second polymer layers 116, 118 may be formed of a transparent polymer (such as ethylene-vinyl acetate (EVA)). The first polymer layer and the sending polymer layers 116, 118 may encapsulate the PV cell 102.

[0180] In one embodiment, the solar panel 100 also includes a frame 120. When the solar panel 100 is horizontally oriented such that the main surface 48 of the article 10 is horizontal and facing upwards, the frame 120 defines a top 122 and a bottom 124 of the solar panel 100, wherein, excluding wiring that may extend from the solar panel 100, the top 122 is the highest portion of the solar panel 100, and the bottom 124 is the lowest portion of the solar panel 100. In a more detailed example, the frame 120 includes a sidewall 126, a C-shaped channel 128 adjacent to the sidewall 126, and a projection 130 extending inwardly relative to the sidewall 126. The C-shaped channel 128 is disposed at or near the top 122 of the frame 120, and the projection 130 is disposed at or near the bottom 124 of the frame 120. The projection 130 forms a plane 132 that is generally parallel to the outer main surface 112 of the back panel 108. The article 10, the PV cell 102 and the backplate 108 are all coupled to each other as a package 134. The sidewall 126 extends around the periphery 136 of the package 134, wherein the periphery 136 of the package 134 is fixed within the C-shaped channel 128 of the frame 120.

[0181] The article 10 having a multilayer coating 14 and the solar panel 100 comprising the article address the problems mentioned in the background art in several ways. First, the multilayer coating 14 having at least one high-refractive-index material layer 38 imparts durability to the article 10. The durability of typical porous SiO2 antireflective coatings is suboptimal. Porosity of SiO2 is necessary to reduce the refractive index of SiO2 and thus reduce reflection. However, the porosity of SiO2 reduces the durability of the coating. In contrast, the multilayer coating 14 of this disclosure may not be porous and includes at least one high-refractive-index material layer 38, which imparts hardness to the multilayer coating 14 and thus enhances durability. Enhanced durability is manifested in a maximum hardness of at least 6 GPa or even higher than 8 GPa or 10 GPa, as shown in the following Examples 1 to 4 according to the described Glass indenter hardness test. Typical porous SiO2 antireflective coatings exhibit a maximum hardness of less than 4 GPa or in the range of 1 GPa to 3 GPa, as measured in conjunction with the following Comparative Example 2. Compared to solar panels with cover glass containing a typical porous SiO2 coating, solar panel 100 comprising an article 10 having the multilayer coating 14 of this disclosure will exhibit greater resistance to wear and tear caused by cleaning, greater resistance to abrasion from sand particles, and greater resistance to moisture and other forms of environmental degradation. Therefore, compared to solar panels containing a typical porous SiO2 coating, solar panel 100 comprising an article 10 having the multilayer coating 14 of this disclosure will exhibit a longer lifespan and higher power generation over time, during which the multilayer coating 14 provides anti-reflective properties.

[0182] Secondly, compared to the suboptimal antireflective properties exhibited by articles with typical porous SiO2 coatings, the article 10 with multilayer coating 14 exhibits better antireflective properties. The multilayer coating 14 of this disclosure can be spectrally tuned to optimize for wavelengths in the 600 nm to 900 nm range, particularly the 600 nm to 750 nm range (this is the richest wavelength range for photons 104 reaching the Earth's surface from the Sun 106 (see again)). Figure 1 The corresponding anti-reflective properties of photon 104. Typical porous SiO2 coatings cannot be adjusted in a similar manner. Therefore, a solar panel 100 including an article 10 with a multilayer coating 14 of this disclosure should be able to increase power generation.

[0183] Furthermore, compared to articles with a typical porous SiO2 coating, the article 10 with a multilayer coating 14 exhibits better reflectivity for photons 104 associated with wavelengths greater than or equal to 1100 nm. As mentioned, the energy of each photon 104 associated with a wavelength greater than or equal to 1100 nm is less than the bandgap energy of the silicon semiconductor material used in the PV cell 102. Instead, these photons 104 can be absorbed in the layers of the solar panel 100 (such as polymer or metal layers), and the absorption of photons 104 generates heat that can be conducted throughout the solar panel 100. The generated heat may reduce the efficiency of the PV cell 102. Therefore, it would be beneficial to prevent these photons 104 from reaching the PV cell 102 by reflection. Compared to a typical porous SiO2 coating, the multilayer coating 14 of this disclosure reflects more of these photons 104, thereby reducing the number of photons 104 reaching the polymer and metal components that can absorb these photons.

[0184] Furthermore, compared to articles with a typical porous SiO2 coating, the article 10 with a multilayer coating 14 exhibits better reflectivity for photons 104 associated with wavelengths in the 300 nm to 350 nm range. As mentioned, photons 104 associated with wavelengths in this range can degrade the polymer layers 116, 118 encapsulating the PV cell 102. Therefore, it would be beneficial to prevent these photons 104 from reaching the PV cell 102 by reflection. Compared to a typical porous SiO2 coating, the multilayer coating 14 of this disclosure reflects more of these photons 104, thereby reducing the number of photons 104 reaching the polymer layers 116, 118.

[0185] Example

[0186] Comparative Example 1 - For Comparative Example 1, a typical soda-lime glass substrate, used as a cover glass in a solar panel but without a coating, was obtained. The reflectivity of the first surface of the glass panel (“1-side”) was measured as a function of wavelength. Additionally, the transmittance through the entire substrate (referred to as “2-side” transmittance) was measured. The measurements were then averaged over different wavelength ranges. The results are shown in Table 2 below.

[0187]

[0188]

[0189] The typical first-surface reflectance of an uncoated glass substrate is approximately 4%. The substrate in this comparative example is an example of a cover glass for a solar panel, where the typical porous SiO2 anti-reflective coating has been removed during outdoor use through cycles of abrasion, weathering, and cleaning. In the wavelength range of 600 nm to 900 nm, the transmittance of the glass substrate exceeds 91%, indicating that without the anti-reflective coating, the glass substrate would significantly reduce the number of usable photons reaching the PV cell. This transmittance level was measured with air interfaces (without polymer binders such as EVA) on both surfaces of the glass substrate. This was done to facilitate measurements at the component level and to be consistent with the transmittance reported for all coated examples below. It should be noted that for all coated examples, the coating was applied only to one surface of the glass, meaning that the maximum possible two-sided transmittance value for a one-sided coated glass example is approximately 96%, as the uncoated surface of the glass has approximately 4% reflectance.

[0190] Comparative Example 2 – For Comparative Example 2, a soda-lime glass substrate identical to that in Comparative Example 1 was obtained, but this time with a porous SiO2 antireflective coating. The reflectivity of the main surface of the article (“1-side”) as a function of wavelength was measured. Additionally, the transmittance through the entire article (referred to as “2-side” transmittance) was measured. The measurements were then averaged over different wavelength ranges. The results are shown in Table 3 below.

[0191]

[0192]

[0193] The results revealed that, across the entire wavelength range of 600 nm to 900 nm, the porous SiO2 coating increased the transmittance of the fabrication from just over 91% to between 94.4% and 94.8%. As mentioned, when used as cover glass for solar panels, the transmittance decreases due to the removal of the porous SiO2 coating.

[0194] In addition, the nanoindentation hardness of the coated surface of Comparative Example 2 was measured using a Glass indenter hardness test, and the results showed a range of 1 to 3 GPa, which corresponds to a relatively low resistance to scratch and abrasion events, such as those commonly encountered in solar applications due to sand particles.

[0195] Comparative Example 3 – For Comparative Example 3, an article with a multilayer coating (but not the multilayer coating of this disclosure) was modeled to determine the primary surface reflectivity and transmittance through the article, as in the previous two comparative examples. Comparative Example 3 (and all other modeling examples herein) was modeled using optical transfer matrix simulation, using input parameters (refractive index and extinction coefficient versus wavelength) from experimentally fabricated and measured sputtered thin film materials. This modeling approach has been found to be in good agreement with the optical properties of multilayer films fabricated in many previous experiments. The design of the article consisting of a substrate (alkali aluminosilicate glass composition) and a multilayer coating is shown in Table 4 below.

[0196]

[0197] "Incident" refers to the model's assumption that the material (in this case, air) is positioned above the main surface of the article. Similarly, "outcrystallization" refers to the model's assumption that the material (in this case, air) is positioned below the second main surface of the article (provided by the substrate). Layers 1 to 5 refer to layers in a multilayer coating.

[0198] The model calculates the reflectivity of the main surface of the article (“surface 1”) as a function of wavelength. Additionally, the model calculates the transmittance through the entire article (referred to as “surface 2” transmittance). The calculations are then averaged over different wavelength ranges. The results are shown in Table 5 below.

[0199]

[0200]

[0201] Compared to Comparative Example 2 (porous SiO2 coating), the multilayer coating of Comparative Example 3 exhibits higher transmittance through the article across the entire wavelength range of 450 nm to 600 nm. However, compared to Comparative Example 2 (porous SiO2 coating), the multilayer coating of Comparative Example 3 exhibits lower transmittance through the article across the entire wavelength range of 600 nm to 1100 nm. Therefore, Comparative Example 3 demonstrates that not all multilayer coatings with repetitive cycles of low-refractive-index and high-refractive-index material layers improve antireflective performance compared to typical porous SiO2 coatings.

[0202] Example 1 - For Example 1, an article having the multilayer coating of this disclosure is modeled as described above to determine the primary surface reflectivity and transmittance through the article, as in the previous two comparative examples. The design of the article consisting of a substrate (a chemically strengthened alkali aluminosilicate glass composition) and a multilayer coating is shown in Table 6 below.

[0203]

[0204] Among other reasons, the multilayer coating of Example 1 is noteworthy for: (i) the total thickness is in the range of 350 nm to 1400 nm, (ii) the thickness of the first low-refractive-index material layer (layer 1) is in the range of 50 nm to 250 nm, and (iii) the combined thickness of the low-refractive-index material layers accounts for more than 55% (68.2%) of the total thickness of the multilayer coating. The thickness of the multilayer coating of Comparative Example 3 (338.4 nm) is less than the former's thickness range. The thickness of layer 1 in the Comparative Example (25 nm) is less than the latter's thickness range. The combined thickness of the low-refractive-index material layers in Comparative Example 3 is 46.3% of the total thickness of the multilayer coating.

[0205] The model calculates the reflectivity of the main surface of the article (“surface 1”) as a function of wavelength. Additionally, the model calculates the transmittance through the entire article (referred to as “surface 2” transmittance). The calculations are then averaged over different wavelength ranges. The results are shown in Table 7 below.

[0206]

[0207] Unlike the multilayer coating of Comparative Example 3, the article with the multilayer coating of Example 1 exhibits a lower principal surface reflectance across the entire wavelength range of 600 nm to 900 nm compared to the porous SiO2 coating of Comparative Example 2. This lower reflectance results in higher transmittance through the article in the 600 nm to 900 nm range compared to the articles of Comparative Examples 2 and 3. The principal surface average reflectance exhibited by the article of Example 1 across the entire wavelength range of 600 nm to 650 nm is almost half that exhibited by Comparative Example 2. Furthermore, the principal surface average reflectance (23.5%) exhibited by the article of Example 1 across the entire wavelength range of 300 nm to 350 nm is more than seven times that exhibited by the article of Comparative Example 2 across the same wavelength range (3.2%). Furthermore, the average reflectance of the main surface of the article of Example 1 (9.8% to 17.9%) over the entire wavelength range of 1200 nm to 1800 nm is more than 5 to 7 times that of the article of Comparative Example 2 (1.7% to 2.5%) over the same wavelength range.

[0208] Figure 10The reproduced figure plots the main surface reflectance as a function of wavelength for Comparative Examples 1-3 and Example 1. The figure reveals that the multilayer coating of Example 1 exhibits lower reflectance across the entire critical wavelength range (e.g., from 550 nm to approximately 875 nm) for solar panel applications compared to the porous SiO2 coating of Comparative Example 2. Furthermore, the figure reveals that the multilayer coating of Example 1 exhibits significantly higher reflectance at wavelengths above 1100 nm, where silicon PV cell cells are unusable, compared to the porous SiO2 coating of Comparative Example 2.

[0209] The multilayer coating in Example 1 is further noteworthy because of the high refractive index material layer 2 (SiN). x The thickness of layer 2 is 140 nm, which is greater than 80 nm. Furthermore, layer 2 lies within the outermost 300 nm of the total thickness of the multilayer coating. Still further, within the outermost 300 nm of the total thickness of the multilayer coating, 52.7% is a high-refractive-index material (SiN). x This is greater than 40%.

[0210] Example 2 - For Example 2, an article having the multilayer coating of this disclosure is modeled as described above to determine the primary surface reflectivity and transmittance through the article, as in the previous two comparative examples. The design of the article consisting of a substrate (a chemically strengthened alkali aluminosilicate glass composition) and a multilayer coating is shown in Table 8 below.

[0211]

[0212]

[0213] Among other reasons, the multilayer coating of Example 2 is noteworthy for the following reasons: (i) the total thickness is in the range of 350 nm to 1400 nm (specifically 1276.9 nm), (ii) the thickness of the first low-refractive-index material layer (layer 1) is in the range of 50 nm to 250 nm (specifically 206.7 nm), and (iii) the combined thickness of the low-refractive-index material layers accounts for more than 55% (specifically 59.8%) of the total thickness of the multilayer coating.

[0214] The model calculates the reflectivity of the main surface of the article (“surface 1”) as a function of wavelength. Additionally, the model calculates the transmittance through the entire article (referred to as “surface 2” transmittance). The calculations are then averaged over different wavelength ranges. The results are shown in Table 9 below.

[0215]

[0216]

[0217] Unlike the multilayer coating of Comparative Example 3, the article with the multilayer coating of Example 2 exhibits lower principal surface reflectance across the entire wavelength range of 600 nm to 900 nm and in the wavelength range of 950 nm to 1050 nm compared to the porous SiO2 coating of Comparative Example 3. This lower reflectance results in higher transmittance through the article in these wavelength ranges compared to the articles of Comparative Examples 2 and 3. The average principal surface reflectance exhibited by the article of Example 2 across the entire wavelength range of 800 nm to 850 nm is almost half that of the average principal surface reflectance exhibited by Comparative Example 2. The average principal surface reflectance across the entire wavelength range of 1000 nm to 1050 nm is less than half that of the average principal surface reflectance exhibited by Comparative Example 2. Furthermore, the average principal surface reflectance (40.3%) exhibited by the article of Example 2 across the entire wavelength range of 300 nm to 350 nm is more than 12 times that of the average principal surface reflectance (3.2%) exhibited by the article of Comparative Example 2 across the same wavelength range. Furthermore, the average reflectance of the main surface of the article of Example 2 (15.8% to 55.7%) over the entire wavelength range of 1200 nm to 1800 nm is more than 9 to 22 times that of the average reflectance of the main surface of the article of Comparative Example 2 (1.7% to 2.5%) over the same wavelength range.

[0218] Figure 11 The reproduced figure plots the main surface reflectance as a function of wavelength for comparative Examples 1 and 2, and Example 2. The figure reveals that the multilayer coating of Example 2 exhibits lower reflectance across the entire critical wavelength range (e.g., from 550 nm to approximately 875 nm) for solar panel applications than the porous SiO2 coating of Comparative Example 2. Furthermore, the figure reveals that the multilayer coating of Example 2 exhibits significantly higher reflectance at wavelengths above 1100 nm, where silicon PV cell cells are unusable, compared to the porous SiO2 coating of Comparative Example 2.

[0219] The multilayer coating in Example 2 is further noteworthy because of the high refractive index material layer 2 (SiN). x The thickness of layer 2 is 138.5 nm, which is greater than 80 nm. Furthermore, layer 2 lies within the outermost 300 nm of the total thickness of the multilayer coating. Still further, within the outermost 300 nm of the total thickness of the multilayer coating, 51.1% is a high-refractive-index material (SiN). x This is greater than 40%.

[0220] Example 3 - For Example 3, an article having the multilayer coating of this disclosure is modeled as described above to determine the primary surface reflectivity and transmittance through the article, as in the previous two comparative examples. The design of the article consisting of a substrate (a chemically strengthened alkali aluminosilicate glass composition) and a multilayer coating is shown in Table 10 below.

[0221]

[0222] Among other reasons, the multilayer coating of Example 3 is noteworthy for the following reasons: (i) the total thickness is in the range of 350 nm to 1400 nm (specifically 544.0 nm), (ii) the thickness of the first low-refractive-index material layer (layer 1) is in the range of 50 nm to 250 nm (specifically 207.5 nm), and (iii) the combined thickness of the low-refractive-index material layers accounts for more than 55% of the total thickness of the multilayer coating (specifically 71.5%).

[0223] The model calculates the reflectivity of the main surface of the article (“surface 1”) as a function of wavelength. Additionally, the model calculates the transmittance through the entire article (referred to as “surface 2” transmittance). The calculations are then averaged over different wavelength ranges. The results are shown in Table 11 below.

[0224]

[0225]

[0226] Unlike the multilayer coating of Comparative Example 3, the article having the multilayer coating of Example 3 exhibits lower principal surface reflectance across the entire wavelength range of 600 nm to 950 nm and across the entire wavelength range of 1000 nm to 1050 nm compared to the porous SiO2 coating of Comparative Example 3. This lower reflectance results in higher transmittance through the article in these wavelength ranges compared to the articles of Comparative Examples 2 and 3. The average principal surface reflectance exhibited by the article of Example 3 across the entire wavelength range of 800 nm to 900 nm is almost half that exhibited by the average principal surface reflectance of Comparative Example 2. Furthermore, the average principal surface reflectance (28.7%) exhibited by the article of Example 3 across the entire wavelength range of 300 nm to 350 nm is almost nine times that exhibited by the article of Comparative Example 2 across the same wavelength range (3.2%). Furthermore, the average reflectance of the main surface of the article of Example 3, which is 7.1% to 23.5% over the entire wavelength range of 1200 nm to 1800 nm, is more than 4 to 9 times that of the article of Comparative Example 2, which is 1.7% to 2.5% over the same wavelength range.

[0227] What makes the multilayer coating in Example 3 even more noteworthy is that the thickness of the high-refractive-index material layer 4 (TiO2) is 95.9 nm, which is greater than 80 nm. Furthermore, layer 4 is located within the outermost 300 nm of the total thickness of the multilayer coating. Moreover, within the outermost 300 nm of the total thickness of the multilayer coating, 48.6% is the high-refractive-index material (TiO2), which is greater than 40%.

[0228] Example 4 - For Example 4, an article having the multilayer coating of this disclosure is modeled as described above to determine the primary surface reflectivity and transmittance through the article, as in the previous two comparative examples. The design of the article consisting of a substrate (this time a low-iron sodium-calcium glass composition) and a multilayer coating is shown in Table 12 below.

[0229]

[0230] Among other reasons, the multilayer coating of Example 4 is noteworthy for the following reasons: (i) the total thickness is in the range of 350 nm to 1400 nm (specifically 540.3 nm), (ii) the thickness of the first low-refractive-index material layer (layer 1) is in the range of 50 nm to 250 nm (specifically 207.0 nm), and (iii) the combined thickness of the low-refractive-index material layers accounts for more than 55% (specifically 71.7%) of the total thickness of the multilayer coating.

[0231] The model calculates the reflectivity of the main surface of the article (“surface 1”) as a function of wavelength. Additionally, the model calculates the transmittance through the entire article (referred to as “surface 2” transmittance). The calculations are then averaged over different wavelength ranges. The results are shown in Table 13 below.

[0232]

[0233]

[0234] Unlike the multilayer coating of Comparative Example 3, the article with the multilayer coating of Example 4 exhibits a lower principal surface reflectance across the entire wavelength range of 600 nm to 1000 nm compared to the porous SiO2 coating of Comparative Example 3. This lower reflectance results in higher transmittance through the article in these wavelength ranges compared to the articles of Comparative Examples 2 and 3. The average principal surface reflectance exhibited by the article of Example 4 across the entire wavelength range of 800 nm to 850 nm is almost half that of Comparative Example 2. Both Examples 3 and 4 utilize TiO2 relative to SiN... xA higher refractive index resulted in lower reflectivity than in Example 1 over certain wavelength ranges. Furthermore, the article of Example 4 exhibited a principal surface average reflectivity (29.9%) over the entire wavelength range of 300 nm to 350 nm, which is more than nine times that of the article of Comparative Example 2, which exhibited a principal surface average reflectivity (3.2%) over the same wavelength range. Additionally, the article of Example 3 exhibited a principal surface average reflectivity (7.2% to 23.3%) over the entire wavelength range of 1200 nm to 1800 nm, which is four to nine times that of the article of Comparative Example 2, which exhibited a principal surface average reflectivity (1.7% to 2.5%) over the same wavelength range.

[0235] Figure 12 The reproduced figures plot the main surface reflectance as a function of wavelength for comparative examples 1 and 2, and examples 3 and 4. The figures reveal that the multilayer coatings of examples 3 and 4 exhibit lower reflectance across the entire critical wavelength range (e.g., from 550 nm to approximately 975 nm) for solar panel applications than the porous SiO2 coating of comparative example 2. Furthermore, the figures reveal that the multilayer coatings of examples 3 and 4 exhibit significantly higher reflectance at wavelengths above 1100 nm, which are unusable in silicon PV cell cells, than the porous SiO2 coating of comparative example 2.

[0236] What makes the multilayer coating in Example 4 even more noteworthy is that the thickness of the high-refractive-index material layer 4 (TiO2) is 91.3 nm, which is greater than 80 nm. Furthermore, layer 4 is located within the outermost 300 nm of the total thickness of the multilayer coating. Moreover, within the outermost 300 nm of the total thickness of the multilayer coating, 47.7% is the high-refractive-index material (TiO2), which is greater than 40%.

[0237] Comparison of hardness modeling in Example 3 and Examples 1-4 - through experimental measurements of SiO2 and SiN xThe hardness of sputtered TiO2 monolayer films was measured, and these measured monolayer hardness values ​​were used as input to a finite element model to calculate the hardness of the multilayer coatings in Examples 3 and 1-4. This experimental-modeling approach has been found to be in excellent agreement with experimentally measured hardness values ​​from fully multilayer coating stacks in the past. Finite element modeling of the hardness was performed using the commercial finite element software ABAQUS v2019. To reduce computation time, an axisymmetric model was used, assuming a half-angle of 70.3° at the tip of the conical indenter, resulting in a contact area to depth ratio similar to that of a glassy diamond indenter. The model included the properties of individual layers and the substrate in the multilayer coating. The material was assumed to behave ideally elastoplastically according to the von Mises yield criterion. Material properties were selected for each individual layer in the multilayer coating based on known hardness and modulus curves measured for monolayer coatings. The output of the finite element modeling was a load-displacement curve, which was then used to calculate the hardness versus depth curve. To extract the variation of hardness with nanoindentation depth, a continuous stiffness measurement (CSM) was simulated. To this end, small-amplitude vibrations were applied to the modeled indenter tip during the loading phase. For the simulation, the tip displacement history was defined by a user-defined “amplitude” curve in ABAQUS to apply a very small (~1 nm or less) harmonic unloading. The maximum time increment was limited in such a way that the history output could have a high sampling rate to capture all these 1 nm “unloading” portions throughout the loading phase. The hardness response was then calculated using the Oliver-Pharr method described in the following references: Oliver, WC; Pharr, GM, An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. *Journal of Materials Research*, 1992, 7, 1564–1583; and Oliver, WC; Pharr, GM, Measurement of hardness and elastic modulus by instrumented indentation: Advances in understanding and refinements to methodology. *Journal of Materials Research*, 2004, 19, 3–20. Both references are incorporated herein by reference.The hardness values ​​for comparison between Example 1 and the models in Examples 1 through 4 are shown in Table 13 below. The hardness values, along with H, are reported at indentation depths of 20 nm, 40 nm, 100 nm, and 125 nm. max (This represents the maximum hardness at any indentation depth). While the hardness of Comparative Example 3 is similar to that of Examples 1-4, it lacks the desired spectral characteristics, particularly in the 600 nm to 800 nm wavelength range, which is important for solar energy applications. Examples 1-4 do indeed possess the desired spectral characteristics, and their hardness values ​​are significantly higher than those of the porous SiO2 coating in Comparative Example 2 (whose measured hardness ranges from 1 GPa to 3 GPa). Examples 1-4 exhibit hardness values ​​greater than 7 GPa at all reported depths, and greater than 8 GPa at depths of 100 nm or greater, and H... max The value is greater than 8 GPa. This is due to the specific sputtered SiN used. x The films have high hardness, therefore the hardness values ​​of Examples 1 and 2 are even higher, with the hardness and H values ​​at depths of 100 nm and 125 nm being particularly high. max Values ​​greater than 10 GPa or even greater than 11 GPa. For example, “H at 20 nm” in Table 14 below refers to the hardness at a depth of 20 nm.

[0238]

[0239] Comparing the energy generation efficiency of Examples 1 to 3 and Examples 1 to 4 – To evaluate the optical performance of the multilayer coatings of this disclosure from the perspective of energy generation efficiency of solar cell units or modules, the expected short-circuit current density J of a standard PV module employing these multilayer coatings was calculated. sc This model takes into account both the spectral composition of sunlight (using AM 1.5G photon flux, see again) and... Figure 1 The model also considers the electro-conversion efficiency of the crystalline silicon solar module as a function of wavelength, and the influence of each modeled component. The module model is in... Figure 13The following diagram illustrates the process. In all cases, the thicknesses of the glass substrate, EVA, SiNx, and Si layer are 2.0 mm, 0.5 mm, 76.3 nm, and 300 μm, respectively. It is assumed that the EVA / SiNx / Si thin film interface has a square pyramidal texture. The Si layer consists of an emitter (n-doped Si), a space charge region (depletion layer), and a base (p-doped Si) with thicknesses of 0.5 μm, 1.0 μm, and 298.5 μm, respectively. The internal quantum efficiency (IQE) of the Si layer is calculated as described in the following reference: Yang, WJ et al. (2007), “Internal Quantum Efficiency for Solar Cells”, *Solar Energy*, 82, 106-110, which is incorporated herein by reference. In the IQE calculation, the Si layer is considered planar except that the emitter surface recombination velocity is 1E5 cm / s, where the parameters are the same as those described therein. The total transmittance T(λ) in the Si cell is determined by calculating the reflection and absorption losses in each module layer based on the complex refractive index (for normal incidence). In the case of multilayer coatings, the reflectance calculated for each example is used. The internal absorptivity of the glass layers remains constant and is based on the measured transmittance and absorptivity of commercial low-iron soda-lime glass used for PV cover glass applications. The external quantum efficiency (EQE(λ)) of the cell is calculated as a product: T(λ) x IQE(λ). The short-circuit current density is then obtained by integrating the following product relative to the wavelength from 0 to 1: EQE(λ) x AM1.5G photon flux (s). -1 m -2 nm -1 )x Elementary charge q (C).

[0240] Table 15 below shows the results of the model. Compared to the module with an uncoated substrate (Comparative Example 1), the module with a single porous SiO2 coating (Comparative Example 2) has a higher J... sc The change is 3.31%. For a suitable approximation, these changes are equivalent to changes in module efficiency. The predicted module efficiency of Example 1 is similar to that of Comparative Example 2. However, the multilayer coating of Example 1 exhibits significantly higher hardness and durability compared to the porous SiO2 coating of Comparative Example 2, and thus imparts a longer lifespan to the solar panel components due to higher reflectivity in certain wavelength ranges compared to the porous SiO2 coating of Comparative Example 2. As previously mentioned, the hardness of Comparative Example 3 is similar to that of Examples 1 to 4, but its spectral characteristics are suboptimal, resulting in lower solar power generation, as shown in Table 15. sc The calculations are shown. It is predicted that J in Examples 2 to 4... scThe coating exhibits a 3.64% increase in reflectivity compared to Comparative Example 1, exceeding that of Comparative Example 2, and also demonstrates significantly higher hardness and reflectivity for certain undesirable wavelengths that affect lifespan. Therefore, the multilayer coating of this disclosure is competitive or advantageous in terms of energy generation efficiency, coating durability, and the lifespan of solar panel components compared to well-optimized porous SiO2 coatings used in the PV industry.

[0241]

[0242] The antireflective coatings and articles described in this disclosure are optimized for use in solar cell units and solar panel applications. These applications can include standard utility-scale or residential rooftop solar, and can also include emerging applications such as solar panels on cars, trucks, or boats (also known as vehicle-integrated photovoltaics); opaque, translucent, or transparent solar panels integrated into building windows, facades, awnings, etc. (also known as building-integrated photovoltaics); parking canopies or parking covers; and solar cell units integrated into mobile devices such as tablets or laptops, external batteries, and mobile phones. The antireflective coatings and articles of the present invention can also be used in non-solar applications, particularly those that can benefit from the simultaneous transmission of visible and near-infrared light, such as display cover glass, camera lens cover glass, information display optics, and sensor cover glass for smartwatches, mobile phones, and augmented reality glasses applications. For example, modern mobile phone displays and cameras designed for visible light wavelengths of 400-700 nm can also integrate light emitters or sensors that operate in the 750-950 nm wavelength window, for which the coatings and articles of the present invention are applicable.

[0243] Many variations and modifications may be made to the above embodiments / aspects of this disclosure without substantially departing from the spirit and principles thereof. All such modifications and variations are intended to be included within the scope of this disclosure and protected by the appended claims.

Claims

1. An article comprising: A substrate, the substrate comprising a first main surface and a second main surface; and A multilayer coating disposed on the first main surface of the substrate, the multilayer coating comprising at least one period of a low-refractive-index material layer and a high-refractive-index material layer. The article described therein exhibits a primary surface average reflectance of less than or equal to 0.550% over the entire wavelength range of 600 nm to 750 nm.

2. The article of claim 1, wherein... The substrate further comprises a glass composition or a glass-ceramic composition.

3. The article of claim 2, wherein The glass composition is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition.

4. The article of claim 1 to 3, wherein The refractive index of the low-refractive-index material is in the range of 1.40 to 1.60, and The refractive index of the high refractive index material is in the range of 1.70 to 2.

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5. The article of claim 1 to 4, wherein The low refractive index material is or contains SiO2, doped SiO2, Al2O3, GeO2, SiO, or AlO. x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, and The high refractive index material is or contains AlN or SiN. x AlO x N y SiO x N y Or TiO2.

6. The article of manufacture according to any one of claims 1 to 5, wherein The multilayer coating includes a first low-refractive-index material layer that is in direct contact with the first main surface, and the thickness of the first low-refractive-index material layer is in the range of 50 nm to 250 nm.

7. The article of manufacture according to any one of claims 1 to 6, wherein The multilayer coating also includes a total thickness in the range of 350 nm to 1400 nm.

8. The article of manufacture according to any one of claims 1 to 6, wherein The multilayer coating also includes a total thickness in the range of 350 nm to 800 nm.

9. The article of manufacture according to any one of claims 1 to 6, wherein The multilayer coating also includes a total thickness in the range of 350 nm to 650 nm.

10. The article of manufacture according to any one of claims 7 to 9, wherein The combined thickness of the low-refractive-index material layer accounts for more than 55% of the total thickness of the multilayer coating.

11. The article of claim 10, wherein The combined thickness of the low-refractive-index material layer is in the range of 65% to 75% of the total thickness of the multilayer coating.

12. The article of manufacture according to any one of claims 1 to 11, wherein The article exhibits a primary surface average reflectance of less than or equal to 2.0% over the entire wavelength range of 400 nm to 450 nm.

13. The article of manufacture according to any one of claims 1 to 12, wherein The article exhibits a primary surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 450 nm to 600 nm.

14. The article of manufacture according to any one of claims 1 to 13, wherein The article exhibits a primary surface average reflectance of less than or equal to 0.730% over the entire wavelength range of 750 nm to 800 nm.

15. The article of manufacture according to any one of claims 1 to 14, wherein The article exhibits a primary surface average reflectance of less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm.

16. The article of manufacture according to any one of claims 1 to 15, wherein The article exhibits a primary surface average reflectance of less than or equal to 1.05% over the entire wavelength range of 850 nm to 900 nm.

17. The article of manufacture according to any one of claims 1 to 16, wherein The article exhibits a primary surface average reflectance of less than or equal to 2.20% over the entire wavelength range of 900 nm to 950 nm.

18. The article of manufacture according to any one of claims 1 to 17, wherein The article exhibits a primary surface average reflectance of less than or equal to 3.00% over the entire wavelength range of 950 nm to 1000 nm.

19. The article of manufacture according to any one of claims 1 to 18, wherein The article exhibits a primary surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 1000 nm to 1050 nm.

20. The article of manufacture according to any one of claims 1 to 19, wherein The article exhibits a primary surface average reflectance greater than or equal to 5.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

21. The article of manufacture according to any one of claims 1 to 20, wherein The multilayer coating exhibits a maximum hardness of 6 GPa or greater, measured by the Berkovich Indenter Hardness Test in the range of indentation depth from 0 to 125 nm.

22. The article of manufacture according to any one of claims 1 to 20, wherein The multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa, measured in the indentation depth range of 0 to 125 nm according to the Glass indenter hardness test.

23. The article of manufacture according to any one of claims 1 to 22, further comprising An antifouling coating located on the multilayer coating, The antifouling coating contains silane or siloxane materials, and The antifouling coating described therein exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

24. The article of manufacture according to any one of claims 1 to 22, further comprising: An antifouling coating located on the multilayer coating, The antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and The antifouling layer described therein exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

25. An article comprising: A substrate, the substrate comprising a first main surface and a second main surface; and A multilayer coating disposed on the first main surface of the substrate, the multilayer coating comprising (i) at least four layers, (ii) a repeating period of a low-refractive-index material layer and a high-refractive-index material layer, (iii) a total thickness in the range of 350 nm to 1400 nm, and (iv) a first low-refractive-index material layer disposed directly on the first main surface of the substrate, the thickness of the first low-refractive-index material layer being in the range of 50 nm to 250 nm. The combined thickness of the low-refractive-index material layer accounts for more than 55% of the total thickness of the multilayer coating.

26. The article of manufacture according to claim 25, wherein The substrate further comprises a glass composition or a glass-ceramic composition.

27. The article of claim 26, wherein The glass composition of the substrate is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition.

28. The article of manufacture according to any one of claims 25 to 27, wherein The substrate contains a compressive stress region at or near the first main surface.

29. The article of manufacture according to any one of claims 25 to 28, wherein The thickness of the substrate is in the range of 0.1 mm to 5.0 mm.

30. The article of manufacture according to any one of claims 25 to 29, wherein The refractive index of the low-refractive-index material is in the range of 1.40 to 1.60, and The refractive index of the high refractive index material is in the range of 1.70 to 2.

50.

31. The article of manufacture according to any one of claims 25 to 30, wherein The low refractive index material is or contains SiO2, doped SiO2, Al2O3, GeO2, SiO, or AlO. x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, and The high refractive index material is or contains AlN or SiN. x AlO x N y SiO x N y Or TiO2.

32. The article of manufacture according to any one of claims 25 to 31, wherein The low-refractive-index material layer accounts for 65% to 75% of the total thickness of the multilayer coating.

33. The article of manufacture according to any one of claims 25 to 32, wherein The multilayer coating includes A first low-refractive-index material layer is directly disposed on the first main surface of the substrate, the thickness of the first layer being in the range of 175 nm to 225 nm. A second high-refractive-index material layer is directly disposed on the first layer, the thickness of the second layer being in the range of 15 nm to 25 nm. A third low-refractive-index material layer is directly disposed on the second layer, the thickness of the third layer being in the range of 30 nm to 40 nm. A fourth high-refractive-index material layer is directly disposed on the third layer, the thickness of the fourth layer being in the range of 130 nm to 150 nm, and A fifth low-refractive-index material layer is directly disposed on the fourth layer, the thickness of the fifth layer being in the range of 90 nm to 110 nm.

34. The article of manufacture according to any one of claims 25 to 32, wherein The multilayer coating includes A first low-refractive-index material layer is directly disposed on the first main surface of the substrate, the thickness of the first layer being in the range of 175 nm to 225 nm. A second high-refractive-index material layer is directly disposed on the first layer, the thickness of the second layer being in the range of 5 nm to 15 nm. A third low-refractive-index material layer is directly disposed on the second layer, the thickness of the third layer being in the range of 35 nm to 60 nm. A fourth high-refractive-index material layer is directly disposed on the third layer, the thickness of the fourth layer being in the range of 20 nm to 30 nm. A fifth low-refractive-index material layer is directly disposed on the fourth layer, the thickness of the fifth layer being in the range of 10 nm to 25 nm. A sixth high-refractive-index material layer is directly disposed on the fifth layer, the thickness of the sixth layer being in the range of 75 nm to 110 nm. A seventh low-refractive-index material layer is directly disposed on the sixth layer, the thickness of the seventh layer being in the range of 5 nm to 20 nm. An eighth high-refractive-index material layer is directly disposed on the seventh layer, the thickness of the eighth layer being in the range of 15 nm to 30 nm, and A ninth low-refractive-index material layer is directly disposed on the eighth layer, the thickness of the ninth layer being in the range of 90 nm to 115 nm.

35. The article of manufacture according to any one of claims 25 to 32, wherein The multilayer coating includes A first low-refractive-index material layer is directly disposed on the first main surface of the substrate, the thickness of the first layer being in the range of 175 nm to 225 nm. A second high-refractive-index material layer is directly disposed on the first layer, the thickness of the second layer being in the range of 15 nm to 25 nm. A third low-refractive-index material layer is directly disposed on the second layer, the thickness of the third layer being in the range of 30 nm to 40 nm. A fourth high-refractive-index material layer is directly disposed on the third layer, the thickness of the fourth layer being in the range of 130 nm to 160 nm. A fifth low-refractive-index material layer is directly disposed on the fourth layer, the thickness of the fifth layer being in the range of 25 nm to 40 nm. A sixth high-refractive-index material layer is directly disposed on the fifth layer, the thickness of the sixth layer being in the range of 10 nm to 20 nm. A seventh low-refractive-index material layer is directly disposed on the sixth layer, the thickness of the seventh layer being in the range of 140 nm to 175 nm. An eighth high-refractive-index material layer is directly disposed on the seventh layer, the thickness of the eighth layer being in the range of 10 nm to 20 nm. A ninth low-refractive-index material layer is directly disposed on the eighth layer, the thickness of the ninth layer being in the range of 25 nm to 40 nm. A tenth high-refractive-index material layer is directly disposed on the ninth layer, the thickness of the tenth layer being in the range of 130 nm to 160 nm. An eleventh low-refractive-index material layer is directly disposed on the tenth layer, the thickness of the eleventh layer being in the range of 30 nm to 40 nm. A twelfth high-refractive-index material layer is directly disposed on the eleventh layer, the thickness of which is in the range of 10 nm to 20 nm. A thirteenth low-refractive-index material layer is directly disposed on the twelfth layer, the thickness of which is in the range of 105 nm to 135 nm. A fourteenth high-refractive-index material layer is directly disposed on the thirteenth layer, the thickness of which is in the range of 10 nm to 20 nm. A fifteenth low-refractive-index material layer is directly disposed on the fourteenth layer, the thickness of the fifteenth layer being in the range of 35 nm to 50 nm. A sixteenth high-refractive-index material layer is directly disposed on the fifteenth layer, the thickness of the sixteenth layer being in the range of 120 nm to 155 nm, and A seventeenth low-refractive-index material layer is directly disposed on the sixteenth layer, the thickness of the seventeenth layer being in the range of 90 nm to 110 nm.

36. The article of manufacture according to any one of claims 25 to 35, wherein The article exhibits a primary surface average reflectance of less than or equal to 0.550% over the entire wavelength range of 600 nm to 750 nm.

37. The article of manufacture according to any one of claims 25 to 36, wherein The product exhibits the following characteristics: The primary surface average reflectance is less than or equal to 2.0% across the entire wavelength range of 400 nm to 450 nm. The principal surface average reflectance is less than or equal to 1.40% across the entire wavelength range of 450 nm to 600 nm. The principal surface average reflectance is less than or equal to 0.730% across the entire wavelength range of 750 nm to 800 nm. The principal surface average reflectance is less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm. The average reflectance of the principal surface is less than or equal to 1.05% across the entire wavelength range of 850 nm to 900 nm. The principal surface average reflectance is less than or equal to 2.20% across the entire wavelength range of 900 nm to 950 nm. The principal surface average reflectance is less than or equal to 3.00% over the entire wavelength range of 950 nm to 1000 nm, and The primary surface average reflectance is less than or equal to 1.40% across the entire wavelength range of 1000 nm to 1050 nm.

38. The article of manufacture according to any one of claims 25 to 37, wherein The article exhibits a primary surface average reflectance greater than or equal to 5.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

39. The article of manufacture according to any one of claims 25 to 38, wherein The multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa, measured in the indentation depth range of 0 to 125 nm according to the Glass indenter hardness test.

40. The article of manufacture according to any one of claims 25 to 38, wherein The multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa, measured in the indentation depth range of 0 to 125 nm according to the Glass indenter hardness test.

41. The article of manufacture according to any one of claims 25 to 40, further comprising: An antifouling coating located on the multilayer coating, The antifouling coating contains silane or siloxane materials, and The antifouling coating described therein exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

42. The article of manufacture according to any one of claims 25 to 40, further comprising: An antifouling coating located on the multilayer coating, The antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and The antifouling layer described therein exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

43. A solar panel comprising: Article, the article comprising: A substrate, the substrate comprising a first main surface and a second main surface; and A multilayer coating is disposed on the first main surface of the substrate, the multilayer coating comprising a repeating cycle of a low refractive index material layer and a high refractive index material layer; The article described above exhibits a principal surface average reflectance of less than or equal to 0.550% over the entire wavelength range of 600 nm to 750 nm; and A photovoltaic (PV) cell array, wherein the PV cell array is disposed below the second main surface of the substrate.

44. The solar panel of claim 43, further comprising: Back panel, The PV cell array is disposed between the backplate and the article.

45. The solar panel of claim 44, further comprising: The package includes the article of manufacture, the PV cell array, and the backsheet; and The frame includes (i) a sidewall extending around the periphery of the package, (ii) a C-shaped channel adjacent to the sidewall, the periphery of the package being secured within the C-shaped channel, and (iii) a protrusion extending inward relative to the sidewall and forming a plane substantially parallel to the outer main surface of the backplate opposite to the PV cell array.

46. ​​The solar panel according to any one of claims 43 to 45, wherein The substrate further comprises a glass composition or a glass-ceramic composition.

47. The solar panel according to claim 46, wherein The glass composition of the substrate is an alkali aluminosilicate glass composition, a soda-lime glass composition, or an alkaline earth borosilicate glass composition.

48. The solar panel according to any one of claims 43 to 47, wherein The refractive index of the low-refractive-index material is in the range of 1.40 to 1.60, and The refractive index of the high refractive index material is in the range of 1.70 to 2.

50.

49. The solar panel according to any one of claims 43 to 48, wherein The low refractive index material is or contains SiO2, doped SiO2, Al2O3, GeO2, SiO, or AlO. x N y SiO x N y Si u Al y O x N y MgO, MgF2, BaF2, CaF2, DyF3, YbF3, YF3, and CeF3, and The high refractive index material is or contains AlN or SiN. x AlO x N y SiO x N y Or TiO2.

50. The solar panel according to any one of claims 43 to 49, wherein The multilayer coating includes a first low-refractive-index material layer that is in direct contact with the first main surface, and the physical thickness of the first low-refractive-index material layer is in the range of 50 nm to 250 nm.

51. The solar panel according to any one of claims 43 to 50, wherein The multilayer coating also includes a total thickness in the range of 350 nm to 1400 nm.

52. The solar panel according to claim 51, wherein... The combined thickness of the low-refractive-index material layer accounts for more than 55% of the total thickness of the multilayer coating.

53. The solar panel according to claim 51, wherein... The combined thickness of the low-refractive-index material layer accounts for 65% to 75% of the total thickness of the multilayer coating.

54. The solar panel according to any one of claims 43 to 53, wherein The article exhibits a primary surface average reflectance of less than or equal to 2.0% over the entire wavelength range of 400 nm to 450 nm.

55. The solar panel according to any one of claims 43 to 54, wherein The article exhibits a primary surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 450 nm to 600 nm.

56. The solar panel according to any one of claims 43 to 55, wherein The article exhibits a primary surface average reflectance of less than or equal to 0.730% over the entire wavelength range of 750 nm to 800 nm.

57. The solar panel according to any one of claims 43 to 56, wherein The article exhibits a primary surface average reflectance of less than or equal to 0.850% over the entire wavelength range of 800 nm to 850 nm.

58. The solar panel according to any one of claims 43 to 57, wherein The article exhibits a primary surface average reflectance of less than or equal to 1.05% over the entire wavelength range of 850 nm to 900 nm.

59. The solar panel according to any one of claims 43 to 58, wherein The article exhibits a primary surface average reflectance of less than or equal to 2.20% over the entire wavelength range of 900 nm to 950 nm.

60. The solar panel according to any one of claims 43 to 59, wherein The article exhibits a primary surface average reflectance of less than or equal to 3.00% over the entire wavelength range of 950 nm to 1000 nm.

61. The solar panel according to any one of claims 43 to 60, wherein The article exhibits a primary surface average reflectance of less than or equal to 1.40% over the entire wavelength range of 1000 nm to 1050 nm.

62. The solar panel according to any one of claims 43 to 61, wherein The article exhibits a primary surface average reflectance greater than or equal to 5.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

63. The solar panel according to any one of claims 43 to 62, wherein The multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa, measured in the indentation depth range of 0 to 125 nm according to the Glass indenter hardness test.

64. The solar panel according to any one of claims 43 to 63, wherein The multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa, measured in the indentation depth range of 0 to 125 nm according to the Glass indenter hardness test.

65. The solar panel according to any one of claims 43 to 64, wherein The article also includes an antifouling layer located on the multilayer coating. The antifouling coating contains silane or siloxane materials, and The antifouling coating exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

66. The solar panel according to any one of claims 43 to 64, wherein The article also includes an antifouling coating located on the multilayer coating. The antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and The antifouling layer exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

67. An article comprising: A substrate, the substrate comprising a first main surface and a second main surface; and A multilayer coating is disposed on the first main surface of the substrate, the multilayer coating comprising a repeating cycle of a low-refractive-index material layer and a high-refractive-index material layer. The multilayer coating exhibits a maximum hardness greater than or equal to 6 GPa, measured by a Glasswell indenter hardness test in the range of 0 to 125 nm indentation depth. The article described therein exhibits a primary surface average reflectance of less than or equal to 0.900% over the entire wavelength range of 650 nm to 750 nm.

68. The article of claim 67, wherein... The product exhibits the following characteristics: The principal surface average reflectance is less than or equal to 2.50% across the entire wavelength range of 400 nm to 450 nm. The principal surface average reflectance is less than or equal to 0.650% over the entire wavelength range of 600 nm to 650 nm. The average reflectance of the principal surface is less than or equal to 1.00% across the entire wavelength range of 750 nm to 800 nm. The primary surface average reflectance is less than or equal to 1.00% over the entire wavelength range of 800 nm to 850 nm, and The primary surface average reflectance is less than or equal to 1.30% across the entire wavelength range of 850 nm to 900 nm.

69. The article of manufacture according to any one of claims 67 to 68, wherein The product exhibits the following characteristics: The principal surface average reflectance is less than or equal to 2.50% over the entire wavelength range of 950 nm to 1000 nm, and The primary surface average reflectance is less than or equal to 4.00% across the entire wavelength range of 1000 nm to 1050 nm.

70. The article of manufacture according to any one of claims 67 to 69, wherein The product exhibits the following characteristics: The primary surface average reflectance is greater than or equal to 17.0% in one or more of the following wavelength ranges: 1100 nm to 1200 nm, 1200 nm to 1300 nm, 1300 nm to 1400 nm, 1400 nm to 1500 nm, 1500 nm to 1600 nm, 1600 nm to 1700 nm, and 1700 nm to 1800 nm.

71. The article of manufacture according to any one of claims 67 to 70, wherein The multilayer coating exhibits a maximum hardness greater than or equal to 8 GPa, measured in the indentation depth range of 0 to 125 nm according to the Glass indenter hardness test.

72. The article of manufacture according to any one of claims 67 to 71, further comprising: An antifouling coating located on the multilayer coating, The antifouling coating contains silane or siloxane materials, and The antifouling coating described therein exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

73. The article of manufacture according to any one of claims 67 to 71, further comprising: An antifouling coating located on the multilayer coating, The antifouling coating comprises (i) a silicon-containing matrix layer and (ii) a hydrophobic or hydrophilic surface-modifying material, and The antifouling layer described therein exhibits hydrophobic, hydrophilic, or completely hydrophobic properties.

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