Anti-reflective coating for automotive applications

Abstract

The coated article comprises a substrate, a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the substrate and comprising a metal oxide, metal alloy oxide, or a combination thereof, a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer, a third dielectric layer having a maximum thickness of 130 nm on at least a portion of the second dielectric layer and comprising a metal oxide, metal alloy oxide, or a combination thereof, a fourth dielectric layer having a thickness of at least 130 nm on at least a portion of the third dielectric layer, and the coated article transmits at least 75% of the light when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source.

Description

[Technical Field]

[0001] This application claims priority to U.S. Patent Application No. 18 / 593,298, filed on March 1, 2024, which claims the benefit of U.S. Provisional Patent Application No. 63 / 450,693, filed on March 8, 2023, the disclosures of which are incorporated herein by reference in their entirety.

[0002] The present invention generally relates to anti-reflective coatings and articles coated with anti-reflective coatings. [Background technology]

[0003] Technical considerations Substrates such as vehicle windshields sometimes require high infrared transmittance for sensors located behind the substrate (e.g., Light Detecting and Ranging (LiDAR) sensors) to accurately detect infrared radiation. However, existing substrates used in LiDAR systems reflect some of the infrared radiation, reducing the amount of infrared radiation that can be transmitted and detected by the sensor, resulting in inaccurate readings. Therefore, there is currently a need for improved substrates with enhanced anti-reflective properties for infrared radiation. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent No. 4,466,562 [Patent Document 2] U.S. Patent No. 4,671,155 [Patent Document 3] U.S. Patent Application Publication No. 2014 / 0309099 [Patent Document 4] U.S. Patent No. 4,379,040 [Patent Document 5] U.S. Patent No. 4,861,669 [Patent Document 6] U.S. Patent No. 4,898,789 [Patent Document 7] U.S. Patent No. 4,898,790 [Patent Document 8] U.S. Patent No. 4,900,633 [Patent Document 9] U.S. Patent No. 4,920,006 [Patent Document 10] U.S. Patent No. 4,938,857 [Patent Document 11] U.S. Patent No. 5,328,768 [Patent Document 12] U.S. Patent No. 5,492,750 [Patent Document 13] U.S. Patent No. 5,030,593 [Patent Document 14] U.S. Patent No. 5,030,594 [Patent Document 15] U.S. Patent No. 4,287,107 [Patent Document 16] U.S. Patent No. 3,762,988 [Patent Document 17] U.S. Patent No. 5,796,055 [Overview of the Initiative]

[0005] In one aspect of the present invention, the coated article comprises a substrate, a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the substrate and comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer and comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, a third dielectric layer having a thickness of at least 130 nm on at least a portion of the second dielectric layer and comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, a fourth dielectric layer having a thickness of at least 130 nm on at least a portion of the third dielectric layer, wherein the coated article transmits at least 75% of the light when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source.

[0006] In another aspect of the present invention, the LiDAR system comprises a first ply including a first face and a second face opposite to the first face, a second ply including a third face adjacent to the second face and a fourth face opposite to the third face, a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the first face or the fourth face, a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer, a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof, A windshield comprising a nitride, a metallic alloy nitride, or a combination thereof, a third dielectric layer having a thickness of at least 130 nm on at least a portion of a second dielectric layer, and a fourth dielectric layer having a thickness of at least 130 nm on at least a portion of the third dielectric layer, which transmits at least 75% of light when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source, and at least one LiDAR sensor positioned in close proximity to the fourth surface.

[0007] In another aspect of the present invention, the autonomous vehicle includes a LiDAR system comprising: a first ply including a first surface and a second surface opposite to the first surface; a second ply including a third surface adjacent to the second surface and a fourth surface opposite to the third surface; a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the first or fourth surface; a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer; a metal oxide; a metal alloy oxide; a metal nitride; a metal alloy nitride; or a combination thereof; a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer; a metal oxide; a gold A windshield comprising a third dielectric layer having a thickness of at least 130 nm on at least a portion of a second dielectric layer, and a fourth dielectric layer having a thickness of at least 130 nm on at least a portion of the third dielectric layer, wherein the windshield transmits at least 75% of light when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source, and at least one LiDAR sensor positioned in close proximity to the fourth surface.

[0008] Hereinafter, various non-limiting examples and embodiments of the present invention are described and specified in the following numbered clauses.

[0009] Clause 1: A coated article comprising a substrate, a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the substrate and comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer, a third dielectric layer having a maximum thickness of 130 nm on at least a portion of the second dielectric layer and comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, a fourth dielectric layer having a maximum thickness of 130 nm on at least a portion of the third dielectric layer, wherein the coated article transmits at least 75% of the light when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source.

[0010] Clause 2: The coated article according to Clause 1, wherein the substrate comprises glass having a total iron content of at most 0.02 wt%.

[0011] Clause 3: The coated article according to Clause 1 or Clause 2, wherein the first dielectric layer and the third dielectric layer contain the same material.

[0012] Clause 4: The coated article according to any one of Clauses 1 to 3, wherein the first dielectric layer and the third dielectric layer each independently contain zinc stannate, zinc oxide, tin oxide, silicon nitride, or a combination thereof.

[0013] Clause 5: The coated article according to any one of Clauses 1 to 4, wherein the second dielectric layer and the fourth dielectric layer contain the same material.

[0014] Clause 6: The coated article according to any one of Clauses 1 to 5, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon, silicon and aluminum, an alloy containing silicon, or a combination thereof.

[0015] Clause 7: The coated article according to any one of Clauses 1 to 6, wherein the second dielectric layer and the fourth dielectric layer each independently contain an oxide, a nitride, an oxynitride, or a combination thereof.

[0016] Clause 8: The coated article according to any one of Clauses 1 to 7, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon oxide, aluminum silicon oxide, or a combination thereof.

[0017] Clause 9: The coated article according to any one of Clauses 1 to 8, wherein the first dielectric layer and the second dielectric layer have a thickness within the range of 10 nm to 40 nm.

[0018] Clause 10: The coated article according to any one of Clauses 1 to 9, wherein the first dielectric layer and the second dielectric layer have a thickness within the range of 20 nm to 35 nm.

[0019] Clause 11: A coated article according to any of Clauses 1 to 10, wherein the third dielectric layer and the fourth dielectric layer have a thickness in the range of 130 nm to 180 nm.

[0020] Clause 12: A coated article according to any of Clauses 1 to 11, wherein the third dielectric layer has a thickness in the range of 145 nm to 170 nm and the fourth dielectric layer has a thickness in the range of 135 nm to 180 nm.

[0021] Clause 13: A coated article according to any of Clauses 1 to 12, wherein the first dielectric layer and the second dielectric layer are in direct contact with each other, and the third dielectric layer and the fourth dielectric layer are in direct contact with each other.

[0022] Clause 14: A coated article according to any of Clauses 1 to 13, wherein the second dielectric layer and the third dielectric layer are in direct contact with each other.

[0023] Clause 15: A coated article as described in any of Clauses 1 to 14, wherein the light has a wavelength of approximately 900 nm.

[0024] Clause 16: A coated article as described in any of Clauses 1 to 15, wherein the coated article transmits at least 80% of the light.

[0025] Clause 17: A coated article as described in any of Clauses 1 to 16, wherein the coated article transmits at least 85% of the light.

[0026] Clause 18: A coated article according to any one of Clauses 1 to 17, wherein the coated article comprises a substrate, a first dielectric layer, a second dielectric layer, a third dielectric layer, and a fourth dielectric layer.

[0027] Clause 19: A first ply comprising a first face and a second face opposite to the first face, a second ply comprising a third face adjacent to the second face and a fourth face opposite to the third face, a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, wherein a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the first face or the fourth face, a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer, a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or A LiDAR system comprising a windshield having a combination thereof, a third dielectric layer having a thickness of at least 130 nm on at least a portion of the second dielectric layer, and a fourth dielectric layer having a thickness of at least 130 nm on at least a portion of the third dielectric layer, the windshield transmitting at least 75% of light having a wavelength between 800 nm and 1,050 nm from a light source at a 60° angle, and at least one LiDAR sensor positioned in close proximity to the fourth surface.

[0028] Clause 20: The LiDAR system according to Clause 19, wherein the first ply and / or the second ply comprises glass having a total iron content of at most 0.02 wt%.

[0029] Clause 21: The LiDAR system according to Clause 19 or Clause 20, wherein the first dielectric layer and the third dielectric layer contain the same material.

[0030] Clause 22: A LiDAR system according to any of Clauses 19 to 21, wherein the first dielectric layer and the third dielectric layer each independently contain zinc stannate, zinc oxide, tin oxide, silicon nitride, or a combination thereof.

[0031] Clause 23: A LiDAR system according to any of Clauses 19 to 22, wherein the second dielectric layer and the fourth dielectric layer contain the same material.

[0032] Clause 24: A LiDAR system according to any of Clauses 19 to 23, wherein the second dielectric layer and the fourth dielectric layer each independently comprise silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof.

[0033] Clause 25: A LiDAR system according to any of Clauses 19 to 24, wherein the second dielectric layer and the fourth dielectric layer each independently comprise an oxide, nitride, oxynitride, or a combination thereof.

[0034] Clause 26: A LiDAR system according to any of Clauses 19 to 25, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon oxide, aluminum silicon oxide, or a combination thereof.

[0035] Clause 27: A LiDAR system according to any one of Clauses 19 to 26, wherein the first dielectric layer and the second dielectric layer have a thickness in the range of 10 nm to 40 nm.

[0036] Clause 28: A LiDAR system according to any one of Clauses 19 to 27, wherein the first dielectric layer and the second dielectric layer have a thickness in the range of 20 nm to 35 nm.

[0037] Clause 29: The LiDAR system according to any one of Clauses 19 to 28, wherein the third dielectric layer and the fourth dielectric layer have a thickness in the range of 130 nm to 180 nm.

[0038] Clause 30: A LiDAR system according to any one of Clauses 19 to 29, wherein the third dielectric layer has a thickness in the range of 145 nm to 170 nm and the fourth dielectric layer has a thickness in the range of 135 nm to 180 nm.

[0039] Clause 31: A LiDAR system according to any of Clauses 19 to 30, wherein the first dielectric layer and the second dielectric layer are in direct contact with each other, and the third dielectric layer and the fourth dielectric layer are in direct contact with each other.

[0040] Clause 32: A LiDAR system according to any of Clauses 19 to 31, wherein the second dielectric layer and the third dielectric layer are in direct contact with each other.

[0041] Clause 33: A LiDAR system as described in any of Clauses 19 to 32, wherein the light has a wavelength of approximately 900 nm.

[0042] Clause 34: A LiDAR system as described in any of Clauses 19 to 33, wherein the windshield transmits at least 80% of the light.

[0043] Clause 35: A LiDAR system as described in any of Clauses 19 to 34, wherein the windshield transmits at least 85% of the light.

[0044] Clause 36: A LiDAR system according to any of Clauses 19 to 35, wherein the windshield comprises a first ply, a second ply, a first dielectric layer, a second dielectric layer, a third dielectric layer, and a fourth dielectric layer.

[0045] Clause 37: Autonomous vehicle equipped with a LiDAR system, the LiDAR system comprising: a windshield comprising: a first ply comprising a first surface and a second surface opposite to the first surface; a second ply comprising a third surface adjacent to the second surface and a fourth surface opposite to the third surface; a first dielectric layer having a maximum thickness of 40 nm on at least a portion of the first or fourth surface; a second dielectric layer having a maximum thickness of 40 nm on at least a portion of the first dielectric layer; a third dielectric layer having a maximum thickness of 40 nm on at least a portion of the second dielectric layer; a third dielectric layer having a maximum thickness of 130 nm on at least a portion of the second dielectric layer; and a fourth dielectric layer having a maximum thickness of 130 nm on at least a portion of the third dielectric layer, which transmits at least 75% of the light when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source; and at least one LiDAR sensor positioned in close proximity to the fourth surface.

[0046] Clause 38: The autonomous vehicle described in Clause 37, wherein the first ply and / or the second ply comprises glass having a total iron content of at most 0.02 wt%.

[0047] Clause 39: An autonomous vehicle according to Clause 37 or Clause 38, wherein the first dielectric layer and the third dielectric layer comprise the same material.

[0048] Clause 40: An autonomous vehicle according to any of Clauses 37 to 39, wherein the first dielectric layer and the third dielectric layer each independently contain zinc stannate, zinc oxide, tin oxide, silicon nitride, or a combination thereof.

[0049] Clause 41: An autonomous vehicle according to any of Clauses 37 to 40, wherein the second dielectric layer and the fourth dielectric layer contain the same material.

[0050] Clause 42: An autonomous vehicle according to any of Clauses 37 to 41, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof.

[0051] Clause 43: An autonomous vehicle according to any of Clauses 37 to 42, wherein the second dielectric layer and the fourth dielectric layer each independently contain an oxide, nitride, oxynitride, or a combination thereof.

[0052] Clause 44: An autonomous vehicle according to any of Clauses 37 to 43, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon oxide, aluminum silicon oxide, or a combination thereof.

[0053] Clause 45: An autonomous vehicle according to any of Clauses 37 to 44, wherein the first dielectric layer and the second dielectric layer have a thickness in the range of 10 nm to 40 nm.

[0054] Clause 46: An autonomous vehicle according to any of Clauses 37 to 45, wherein the first dielectric layer and the second dielectric layer have a thickness in the range of 20 nm to 35 nm.

[0055] Clause 47: An autonomous vehicle according to any of Clauses 37 to 46, wherein the third dielectric layer and the fourth dielectric layer have a thickness in the range of 130 nm to 180 nm.

[0056] Clause 48: An autonomous vehicle according to any of Clauses 37 to 47, wherein the third dielectric layer has a thickness in the range of 145 nm to 170 nm and the fourth dielectric layer has a thickness in the range of 135 nm to 180 nm.

[0057] Clause 49: An autonomous vehicle according to any of Clauses 37 to 48, wherein the first dielectric layer and the second dielectric layer are in direct contact with each other, and the third dielectric layer and the fourth dielectric layer are in direct contact with each other.

[0058] Clause 50: An autonomous vehicle according to any of Clauses 37 to 49, wherein the second dielectric layer and the third dielectric layer are in direct contact with each other.

[0059] Clause 51: An autonomous vehicle as described in any of Clauses 37 to 50, wherein the light has a wavelength of approximately 900 nm.

[0060] Clause 52: An autonomous vehicle as described in any of Clauses 37 to 51, whose windshield transmits at least 80% of light.

[0061] Clause 53: An autonomous vehicle as described in any of Clauses 37 to 52, whose windshield transmits at least 85% of light.

[0062] Clause 54: An autonomous vehicle according to any of Clauses 37 to 53, wherein the windshield comprises a first ply, a second ply, a first dielectric layer, a second dielectric layer, a third dielectric layer, and a fourth dielectric layer.

[0063] The present invention will be described with reference to the following drawings, in which the same reference numerals throughout the drawings will identify the same parts. [Brief explanation of the drawing]

[0064] [Figure 1] This is a cross-sectional view (not to scale) of a coated article according to one aspect of the present invention. [Figure 2] This is a cross-sectional view (not to scale) of a monolithic transparent body according to another aspect of the present invention. [Figure 3] This is a cross-sectional view (not to scale) of a windshield according to another aspect of the present invention. [Figure 4] Figure 1 shows a coated article, Figure 2 shows a monolithic transparent body, or Figure 3 shows a windshield and a light source according to another aspect of the present invention. [Figure 5] This is a schematic diagram of a LiDAR system according to another embodiment of the present invention. [Figure 6] This graph shows the spectral transmittance at an incident angle of 0° for substrates with and without monolithic anti-reflective coating. [Figure 7] This graph shows the spectral transmittance at an incident angle of 0° for substrates with and without monolithic anti-reflective coating. [Modes for carrying out the invention]

[0065] Where used herein, spatial or directional terms such as “left,” “right,” “inside,” “outside,” “up,” and “down” relate to the present invention as shown in the drawings. However, the present invention can assume various alternative orientations, and therefore such terms should not be considered limiting. Furthermore, where used herein, all numerical values ​​representing dimensions, physical properties, processing parameters, amounts of components, reaction conditions, etc., used in the specification and claims are understood to be modified in all cases by the term “approximately.” Therefore, unless otherwise stated, the numerical values ​​described in the following specification and claims may vary depending on the desired properties to be obtained by the present invention. At the very least, there is no intention to limit the application of the doctrine of equivalents to the claims, and each numerical value should be interpreted by applying ordinary rounding techniques, at least in light of the reported number of significant figures. Furthermore, all ranges disclosed herein are understood to include the start and end values ​​of the ranges, and all subranges contained therein. For example, the stated range "1 to 10" should be considered to include all subranges between a minimum value of 1 and a maximum value of 10 (including endpoint values), i.e., all subranges that begin with a minimum value of 1 or greater and end with a maximum value of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. Furthermore, as used herein, the terms "formed on," "deposited on," or "provided on" mean that something is formed, deposited, or provided on a surface, but does not necessarily have to be in contact with the surface. For example, a coating layer "formed on" a substrate does not preclude the presence of one or more other coating layers or coating films of the same or different composition located between the formed coating layer and the substrate. The terms "visible region," "visible light," or "visible light spectrum" refer to electromagnetic radiation having wavelengths in the range of 380 nm to 800 nm. The terms "infrared region," "infrared radiation," or "infrared spectrum" refer to electromagnetic radiation having wavelengths in the range of greater than 800 nm to 100,000 nm.The terms “ultraviolet region,” “ultraviolet radiation,” or “ultraviolet (UV) spectrum” refer to electromagnetic energy having wavelengths in the range of 300 nm to less than 380 nm. Furthermore, all documents referenced herein, including but not limited to issued patents and patent applications, are deemed to be “incorporated by reference” in their entirety.

[0066] A "layer" can consist of one or more "films," and a "coating" or "coating stack" can consist of one or more "layers." The term "includes" is synonymous with "compose."

[0067] In the description of the present invention, certain features may be described as “particularly” or “preferred” within certain limitations (for example, “preferred,” “more preferably,” or “most preferred” within certain limitations). It is understood that the present invention is not limited to these specific or preferred limitations and encompasses the entire scope of this disclosure.

[0068] As shown in Figure 1, a coated article 10 is provided. In some non-limiting embodiments, the coated article 10 includes a substrate 18, a first dielectric layer 42 on at least a portion of the substrate 18, a second dielectric layer 44 on at least a portion of the first dielectric layer 42, a third dielectric layer 46 on at least a portion of the second dielectric layer 44, and a fourth dielectric layer 48 on at least a portion of the third dielectric layer 46. In some non-limiting embodiments, the coated article 10 transmits at least 75% of the light when in contact at 60° with light having a wavelength between 800 nm and 1050 nm from a light source.

[0069] In the broad practice of the present invention, the substrate 18 may include glass. For example, the substrate 18 may include conventional soda-lime silicate glass, borosilicate glass, or lead glass. The glass may be clear glass. "Clear glass" means glass that is not stained or colored. The glass may be annealed or heat-treated glass. As used herein, the term "heat-treated" means tempered or at least partially tempered. The glass may be conventional float glass. "Float glass" means glass formed by a conventional float process in which molten glass is deposited on a molten metal bath and controlledly cooled to form a float glass ribbon. The ribbon is then cut and / or shaped and / or heat-treated as desired. Examples of the float glass process are disclosed in U.S. Patents 4,466,562 and 4,671,155. Without limiting the present invention, examples of suitable glass for the substrate 18 are described in U.S. Patent Application Publication No. 2014 / 0309099, the disclosure of which is incorporated herein by reference in its entirety. The substrate 18 can be of any desired dimensions, e.g., length, width, shape, or thickness. In some non-limiting embodiments, the substrate 18 can be 1 mm to 10 mm thick, e.g., 1 mm to 5 mm thick, or 1.5 mm to 2.5 mm, or 1.8 mm to 2.3 mm thick. In some non-limiting embodiments, the substrate 18 can have a visible light transmittance of more than 90%, such as more than 91%, at a reference wavelength of 550 nm. The glass composition for the substrate 18 can have a total iron content (as Fe2O3) greater than zero weight percent (wt%). The glass composition for the substrate 18 can have a total iron content of up to 0.02 wt%, or up to 0.01 wt%. The glass composition for the base material 18 may have a total iron content in the range of greater than 0 wt% to 0.02 wt%, or greater than 0 wt% to 0.01 wt%. The glass composition for the base material 18 may contain tin and / or a tin-containing compound, with a tin content in the range of greater than 0.005 wt% to 5.0 wt%.Glass formed from glass compositions possessing the aforementioned properties is sometimes called "ultra-transparent" glass.

[0070] In some non-limiting embodiments, the coated article 10 includes a first dielectric layer 42 on at least a portion of the substrate 18. The first dielectric layer 42 may include a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof. Non-limiting examples of materials that may be used for the first dielectric layer 42 include zinc / tin alloy oxide, zinc oxide, tin oxide, silicon nitride, or a combination thereof. For example, the first dielectric layer 42 may include tin oxide, zinc / tin alloy oxide, or zinc stannate.

[0071] In some non-limiting embodiments, the first dielectric layer 42 can be a metal oxide such as tin oxide. The tin oxide can be deposited in an oxygen (O2) environment from a tin target or from a tin target containing other materials to improve the sputtering properties of the target. For example, the O2 flow rate (i.e., the O2 concentration in the atmosphere of the chamber where the material is deposited) can be up to 80% O2, such as 80% O2, 75% O2, or 70% O2. The remainder of the atmosphere can be an inert gas such as argon. The tin oxide can be obtained from a tin target or a tin and zinc target by magnetron sputtering vacuum deposition. For example, the tin target can contain small amounts of zinc (e.g., up to 20 wt%, up to 15 wt%, up to 10 wt%, or up to 5 wt%). In this case, the resulting tin oxide film will contain a small proportion of zinc oxide, e.g., up to 20 wt% zinc oxide, up to 10 wt% zinc oxide, or up to 5 wt% zinc oxide. A coating layer deposited from a tin target having 0-20 wt% zinc is called a “tin oxide” layer. The first dielectric layer 42 may contain tin oxide, in which case tin is substantially the only metal in the first dielectric layer 42. As used herein, “substantially uncontaining” means that the tin oxide contains less than 0.5 wt% of additional metals other than tin. The first dielectric layer 42 may contain 80 wt% tin oxide and 20 wt% zinc oxide. The first dielectric layer 42 may contain 90 wt% tin oxide and 10 wt% zinc oxide.

[0072] In some non-limiting embodiments, the first dielectric layer 42 may contain a zinc / tin alloy oxide. The zinc / tin alloy oxide can be obtained by MSVD from a zinc and tin cathode, which may contain zinc and tin in proportions of 10 wt% to 90 wt% zinc and 90 wt% to 10 wt% tin. One suitable metal alloy oxide that may be present in the first film of the first dielectric layer 42 is zinc stannate. "Zinc stannate" refers to Zn x Sn 1-x O 2-xThis means the composition is given by (Equation 1), where "x" varies in the range greater than 0 and less than 1. For example, "x" can be greater than 0 and can be any fraction or decimal in the range greater than 0 and less than 1. For example, when x = 2 / 3, Equation 1 is Zn 2 / 3 Sn 1 / 3 O 4 / 3 This is more commonly written as Zn2SnO4. A zinc stanate-containing layer or film has one or more of the form of formula 1 as its main components in the layer or film.

[0073] In some non-limiting embodiments, the first dielectric layer 42 may contain zinc oxide. Zinc oxide can be deposited from a zinc cathode containing other materials to improve the sputtering properties of the cathode. For example, the zinc cathode may contain a small amount of tin (e.g., less than 10 wt%, such as greater than 0 wt% and up to 5 wt%) to improve sputtering. In this case, the resulting zinc oxide film will contain a small proportion of tin oxide, e.g., less than 0 to 10 wt%, e.g., 0 to 5 wt% tin oxide. An oxide layer sputtered from a zinc / tin cathode having 95 wt% zinc and 5 wt% tin, or preferably 90 wt% zinc and 10 wt% tin, is called a zinc oxide-containing layer. The small amount of tin in the cathode (e.g., less than 10 wt%) is thought to form a small amount of tin oxide in the first dielectric layer 42 which mainly contains zinc oxide.

[0074] The first dielectric layer 42 may have a thickness of at least 1 nm, or at least 3 nm, or at least 5 nm, or at least 8 nm, or at least 10 nm, or at least 20 nm. The first dielectric layer 42 may have a maximum thickness of 70 nm, or at least 60 nm, or at least 50 nm, or at least 40 nm, or at least 35 nm. The first dielectric layer 42 may have a thickness in the range of 1 nm to 70 nm, or 3 nm to 60 nm, or 8 nm to 50 nm, or 10 nm to 40 nm, or 20 nm to 35 nm.

[0075] The first dielectric layer 42 may have a refractive index higher than that of the second dielectric layer 44 and the fourth dielectric layer 48. The first dielectric layer 42 may have the same refractive index as the third dielectric layer 46. In some non-limiting embodiments, the first dielectric layer 42 may have a refractive index greater than 1.75, for example greater than 1.9, for example greater than 2.0, for light with a wavelength of 900 nm. For example, the first dielectric layer 42 may have a refractive index between 1.9 and 2.1, for example about 2.0, for light with a wavelength of 900 nm.

[0076] In some non-limiting embodiments, the coated article 10 includes a second dielectric layer 44 on at least a portion of the first dielectric layer 42. The second dielectric layer 44 may be in direct contact with the first dielectric layer 42. In some non-limiting embodiments, the second dielectric layer 44 may contain silicon. For example, the second dielectric layer 44 may contain silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof. For example, the second dielectric layer 44 may contain silicon oxide, silicon-aluminum oxide, or a combination thereof. For example, the second dielectric layer 44 may contain silicon oxide or silicon-aluminum oxide. In another example, the second dielectric layer 44 may contain silicon-aluminum oxide.

[0077] The second dielectric layer 44 may have a thickness of at least 1 nm, or at least 3 nm, or at least 5 nm, or at least 8 nm, or at least 10 nm, or at least 20 nm. The second dielectric layer 44 may have a maximum thickness of 70 nm, or at least 60 nm, or at least 50 nm, or at least 40 nm, or at least 35 nm. The second dielectric layer 44 may have a thickness in the range of 1 nm to 70 nm, or 3 nm to 60 nm, or 8 nm to 50 nm, or 10 nm to 40 nm, or 20 nm to 35 nm.

[0078] The second dielectric layer 44 may have a refractive index lower than that of the first dielectric layer 42 and the third dielectric layer 46. The second dielectric layer 44 may have the same refractive index as the fourth dielectric layer 48. In some non-limiting embodiments, the second dielectric layer 44 may have a refractive index of less than 1.75, for example less than 1.7, or for example less than 1.6, for light with a wavelength of 900 nm. For example, the second dielectric layer 44 may have a refractive index between 1.4 and 1.6, for example about 1.5, for light with a wavelength of 900 nm.

[0079] In some non-limiting embodiments, the coated article 10 includes a third dielectric layer 46 on at least a portion of the second dielectric layer 44. The third dielectric layer 46 may be in direct contact with the second dielectric layer 44. The third dielectric layer 46 may contain the same material as the first dielectric layer 42 or a different material. The third dielectric layer 46 may contain a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof. Non-limiting examples of materials that may be used for the third dielectric layer 46 include zinc / tin alloy oxide (e.g., zinc stannate), zinc oxide, tin oxide, silicon nitride, or a combination thereof. For example, the third dielectric layer 46 may be a zinc / tin alloy oxide or zinc stannate.

[0080] The third dielectric layer 46 may have a thickness of at least 100 nm, or at least 110 nm, or at least 120 nm, or at least 130 nm, or at least 140 nm, or at least 145 nm. The third dielectric layer 46 may have a maximum thickness of 200 nm, or at least 190 nm, or at least 185 nm, or at least 180 nm, or at least 175 nm, or at least 170 nm. The third dielectric layer 46 may have a thickness in the range of 100 nm to 200 nm, or in the range of 110 nm to 190 nm, or in the range of 120 nm to 185 nm, or in the range of 130 nm to 180 nm, or in the range of 140 nm to 175 nm, or at least 145 nm to 170 nm.

[0081] The third dielectric layer 46 may have a refractive index higher than that of the second dielectric layer 44 and the fourth dielectric layer 48. The third dielectric layer 46 may have the same refractive index as the first dielectric layer 42. In some non-limiting embodiments, the third dielectric layer 46 may have a refractive index greater than 1.75, for example greater than 1.9, for example greater than 2.0, for light with a wavelength of 900 nm. For example, the third dielectric layer 46 may have a refractive index of about 2.0 for light with a wavelength of 900 nm.

[0082] In some non-limiting embodiments, the coated article 10 includes a fourth dielectric layer 48 on at least a portion of the third dielectric layer 46. The fourth dielectric layer 48 may be in direct contact with the third dielectric layer 46. The fourth dielectric layer 48 may contain the same material as the second dielectric layer 44 or a different material. In some non-limiting embodiments, the fourth dielectric layer 48 may contain silicon. For example, the fourth dielectric layer 48 may contain silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof. For example, the fourth dielectric layer 48 may contain silicon oxide, aluminum silicon oxide, or a combination thereof. For example, the fourth dielectric layer 48 may contain silicon oxide or aluminum silicon oxide.

[0083] The fourth dielectric layer 48 may have a thickness of at least 100 nm, or at least 110 nm, or at least 120 nm, or at least 130 nm, or at least 135 nm. The fourth dielectric layer 48 may have a thickness of up to 200 nm, or up to 195 nm, or up to 190 nm, or up to 185 nm, or up to 180 nm. The fourth dielectric layer 48 may have a thickness in the range of 100 nm to 200 nm, or in the range of 110 nm to 195 nm, or in the range of 120 nm to 190 nm, or in the range of 130 nm to 185 nm, or in the range of 130 nm to 180 nm, or in the range of 135 nm to 180 nm.

[0084] The fourth dielectric layer 48 may have a refractive index lower than that of the first dielectric layer 42 and the third dielectric layer 46. The fourth dielectric layer 48 may have the same refractive index as the second dielectric layer 44. In some non-limiting embodiments, the fourth dielectric layer 48 may have a refractive index of less than 1.75, for example less than 1.7, or for example less than 1.6, for light with a wavelength of 900 nm. For example, the fourth dielectric layer 48 may have a refractive index between 1.4 and 1.6, for example about 1.5, for light with a wavelength of 900 nm.

[0085] The dielectric layers 42, 44, 46, and 48 can be deposited by any conventional method, including but not limited to conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD). Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam deposition and vacuum sputtering (such as magnetron sputter vapor deposition (MSVD)). Other coating methods, including sol-gel deposition, may also be used, but are not limited to these. In one non-limiting embodiment, the dielectric layers 42, 44, 46, and 48 can be deposited by MSVD. Examples of MSVD coating devices and methods are well understood by those skilled in the art and are described, for example, in U.S. Patents 4,379,040, 4,861,669, 4,898,789, 4,898,790, 4,900,633, 4,920,006, 4,938,857, 5,328,768, and 5,492,750. In the MSVD method, a metal or metal alloy oxide is deposited by sputtering a metal or metal alloy-containing cathode in an oxygen-containing atmosphere, thereby depositing a metal oxide or metal alloy oxide film on the surface of a substrate.

[0086] In some non-limiting embodiments, the coated article 10 described above can be incorporated into a monolithic glazing. The term “monolithic” refers to having a single structural support or structural member, for example, having a single substrate. For example, as shown in Figure 2, the coated article 10 described above can be incorporated into a conventional monolithic permeator 100, such as for a vehicle. For clarity, specific features of such a monolithic permeator, such as seals, connectors, and release mechanisms, are not shown, nor is a finished vehicle shown. The monolithic permeator 100 includes the coated article 10, and the substrate 18 is a first ply (substrate) 118 having a first main surface 122 (surface No. 1) and a second main surface 120 (surface No. 2) attached to the body of a vehicle 125 (partially shown). The first ply 118 may be the same as the substrate 18 described above. In some non-limiting embodiments, the first main surface 122 faces the interior of the vehicle and is therefore an interior main surface, and the second main surface 120 faces the exterior of the vehicle and is therefore an exterior main surface. In some non-limiting embodiments, the first main surface 122 faces the exterior of the vehicle and is therefore an exterior main surface, and the second main surface 120 faces the interior of the vehicle and is therefore an interior main surface. In some non-limiting embodiments, the vehicle body 125 may include the doors of the automobile, or the frames in the case of the windows of the automobile.

[0087] The first dielectric layer 142 may be located on at least a portion of the first main surface 122 of the first ply 118. The first dielectric layer 142 may be the same as the first dielectric layer 42 described above. The second dielectric layer 144 may be located on at least a portion of the first dielectric layer 142. The second dielectric layer 144 may be the same as the second dielectric layer 44 described above. The third dielectric layer 146 may be located on at least a portion of the second dielectric layer 144. The third dielectric layer 146 may be the same as the third dielectric layer 46 described above. The fourth dielectric layer 148 may be located on at least a portion of the third dielectric layer 146. The fourth dielectric layer 148 may be the same as the fourth dielectric layer 48 described above.

[0088] In some non-limiting embodiments, the coated article 10 described above can be incorporated into a windshield 200. A non-limiting example of a windshield 200 incorporating the coated article 10 is shown in Figure 3.

[0089] A windshield 200 can have a visible light transmittance of over 70%. In the United States, the visible light transmittance for windshields and front side light areas is typically 70% or higher. For privacy areas such as rear seat side lights and rear windows, the visible light transmittance may be lower than that of the windshield, such as less than 70%.

[0090] As shown in Figure 3, the windshield 200 includes a first ply or first substrate 212 having a first main surface facing the exterior of the vehicle, i.e., an outer main surface 214 (surface No. 1), and a second main surface or inner main surface 216 (surface No. 2) on the opposite side. The windshield 200 also includes a second ply or second substrate 218 having an outer (first) main surface 222 (surface No. 4) and an inner (second) main surface 220 (surface No. 3). This numbering of the ply surfaces conforms to conventional practice in automotive technology. The first ply 212 and the second ply 218 can be joined in any preferred form, such as by a conventional intermediate layer 224. Although not required, a conventional edge sealant can be applied around the windshield 200 in any desired form during and / or after lamination.

[0091] The plies 212 and 218 of the windshield 200 may be made of glass. The plies 212 and 218 of the windshield 200 may be made of the same glass as the glass of the base material 18 described above.

[0092] In a non-limiting embodiment, one or both of plies 212 and 218 may have high visible light transmittance at a reference wavelength of 550 nm. "High visible light transmittance" means that for glass with a plate thickness of 2 mm to 25 mm, the visible light transmittance at 550 nm at a thickness equivalent to 5.5 mm is 85% or higher, e.g., 87% or higher, e.g., 90% or higher, e.g., 91% or higher, e.g., 92% or higher. Glasses particularly useful for the practice of the present invention are disclosed in U.S. Patents 5,030,593 and 5,030,594.

[0093] The intermediate layer 224 may be composed of any desired material and may include one or more layers or plies. The intermediate layer 224 may be a polymer or plastic material such as a multilayer thermoplastic material including polyvinyl butyral (PVB), plasticized polyvinyl chloride, or polyethylene terephthalate. Suitable intermediate layer materials are disclosed, for example, in U.S. Patents 4,287,107 and 3,762,988, but are not limited thereto. The intermediate layer 224 may also be a sound-absorbing or damping material, for example, as described in U.S. Patent 5,796,055. The intermediate layer 224 may have a sunlight-controlling coating provided on top of or incorporated within it, or may include a coloring material to reduce the transmission of solar energy.

[0094] In some non-limiting embodiments, the first dielectric layer 242 may be located on at least a portion of the main surface of one of the glass plies 212, 218, such as on the outer surface 214 of the outer glass ply 212 or the outer surface 222 of the inner glass ply 218. The first dielectric layer 242 may be the same as the first dielectric layer 42 described above. The first dielectric layer 242 may include metal oxides, metal alloy oxides, metal nitrides, metal alloy nitrides, or combinations thereof. Non-limiting examples of materials that can be used for the first dielectric layer 242 include zinc / tin alloy oxides, zinc oxides, tin oxides, silicon nitride, or combinations thereof. For example, the first dielectric layer 242 may include tin oxide, zinc / tin alloy, or zinc stannate.

[0095] In some non-limiting embodiments, the first dielectric layer 242 may contain tin oxide, as described above.

[0096] In some non-limiting embodiments, the first dielectric layer 242 may contain a zinc / tin alloy oxide. The zinc / tin alloy oxide can be obtained by MSVD from a zinc and tin cathode, which may contain zinc and tin in proportions of 10 wt% to 90 wt% zinc and 90 wt% to 10 wt% tin. One of the preferred metal alloy oxides that may be present in the first film of the first dielectric layer 242 is zinc stannate.

[0097] In some non-limiting embodiments, the first dielectric layer 242 may contain zinc oxide, as described above.

[0098] The first dielectric layer 242 may have a thickness of at least 1 nm, or at least 3 nm, or at least 5 nm, or at least 8 nm, or at least 10 nm, or at least 20 nm. The first dielectric layer 242 may have a maximum thickness of 70 nm, or at most 60 nm, or at most 50 nm, or at most 40 nm, or at most 35 nm. The first dielectric layer 242 may have a thickness in the range of 1 nm to 70 nm, or 3 nm to 60 nm, or 8 nm to 50 nm, or 10 nm to 40 nm, or 20 nm to 35 nm.

[0099] The first dielectric layer 242 may have a refractive index higher than that of the second dielectric layer 244 and the fourth dielectric layer 248. The first dielectric layer 242 may have the same refractive index as the third dielectric layer 246. In some non-limiting embodiments, the first dielectric layer 242 may have a refractive index greater than 1.75 for light with a wavelength of 900 nm. For example, the first dielectric layer 242 may have a refractive index of about 2.0 for light with a wavelength of 900 nm.

[0100] In some non-limiting embodiments, the second dielectric layer 244 may be located on at least a portion of the first dielectric layer 242. The second dielectric layer 244 may be in direct contact with the first dielectric layer 242. The second dielectric layer 244 may be the same as the second dielectric layer 44 described above. In some non-limiting embodiments, the second dielectric layer 244 may contain silicon. For example, the second dielectric layer 244 may contain silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof. For example, the second dielectric layer 244 may contain silicon oxide, aluminum silicon oxide, or a combination thereof.

[0101] The second dielectric layer 244 may have a thickness of at least 1 nm, or at least 3 nm, or at least 5 nm, or at least 8 nm, or at least 10 nm, or at least 20 nm. The second dielectric layer 244 may have a thickness of up to 70 nm, or up to 60 nm, or up to 50 nm, or up to 40 nm, or up to 35 nm. The second dielectric layer 244 may have a thickness in the range of 1 nm to 70 nm, or 3 nm to 60 nm, or 8 nm to 50 nm, or 10 nm to 40 nm, or 20 nm to 35 nm.

[0102] The second dielectric layer 244 may have a refractive index lower than that of the first dielectric layer 242 and the third dielectric layer 246. The second dielectric layer 244 may have the same refractive index as the fourth dielectric layer 248. In some non-limiting embodiments, the second dielectric layer 244 may have a refractive index of less than 1.75, for example less than 1.7, for example less than 1.6, for light with a wavelength of 900 nm. For example, the second dielectric layer 244 may have a refractive index between 1.4 and 1.6, for example about 1.5, for light with a wavelength of 900 nm.

[0103] In some non-limiting embodiments, the third dielectric layer 246 may be provided on at least a portion of the second dielectric layer 244. The third dielectric layer 246 may be in direct contact with the second dielectric layer 244. The third dielectric layer 246 may be the same as the third dielectric layer 46 described above. The third dielectric layer 246 may contain the same material as the first dielectric layer 242 or a different material. The third dielectric layer 246 may contain a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof. Non-limiting examples of materials that may be used for the third dielectric layer 246 include zinc / tin alloy oxides (e.g., zinc stannate), zinc oxide, tin oxide, silicon nitride, or a combination thereof.

[0104] The third dielectric layer 246 may have a thickness of at least 100 nm, or at least 110 nm, or at least 120 nm, or at least 130 nm, or at least 140 nm, or at least 145 nm. The third dielectric layer 246 may have a thickness of up to 200 nm, or up to 190 nm, or up to 185 nm, or up to 180 nm, or up to 175 nm, or up to 170 nm. The third dielectric layer 246 may have a thickness in the range of 100 nm to 200 nm, or in the range of 110 nm to 190 nm, or in the range of 120 nm to 185 nm, or in the range of 130 nm to 180 nm, or in the range of 140 nm to 175 nm, or in the range of 145 nm to 170 nm.

[0105] The third dielectric layer 246 may have a refractive index higher than that of the second dielectric layer 244 and the fourth dielectric layer 248. The third dielectric layer 246 may have the same refractive index as the first dielectric layer 242. In some non-limiting embodiments, the third dielectric layer 246 may have a refractive index greater than 1.75, for example greater than 1.9, for example greater than 2.0, for light with a wavelength of 900 nm. For example, the third dielectric layer 246 may have a refractive index between 1.9 and 2.1, or about 2.0, for light with a wavelength of 900 nm.

[0106] In some non-limiting embodiments, the fourth dielectric layer 248 may be located on at least a portion of the third dielectric layer 246. The fourth dielectric layer 248 may be in direct contact with the third dielectric layer 246. The fourth dielectric layer 248 may be the same as the fourth dielectric layer 48 described above. The fourth dielectric layer 248 may contain the same material as the second dielectric layer 244 or a different material. In some non-limiting embodiments, the fourth dielectric layer 248 may contain silicon. For example, the fourth dielectric layer 248 may contain silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof. For example, the fourth dielectric layer 248 may contain silicon oxide, aluminum silicon oxide, or a combination thereof.

[0107] The fourth dielectric layer 248 may have a thickness of at least 100 nm, or at least 110 nm, or at least 120 nm, or at least 130 nm, or at least 135 nm. The fourth dielectric layer 248 may have a thickness of up to 200 nm, or up to 195 nm, or up to 190 nm, or up to 185 nm, or up to 180 nm. The fourth dielectric layer 248 may have a thickness in the range of 100 nm to 200 nm, or in the range of 110 nm to 195 nm, or in the range of 120 nm to 190 nm, or in the range of 130 nm to 185 nm, or in the range of 135 nm to 180 nm.

[0108] The fourth dielectric layer 248 may have a refractive index lower than that of the first dielectric layer 242 and the third dielectric layer 246. The fourth dielectric layer 248 may have the same refractive index as the second dielectric layer 244. In some non-limiting embodiments, the fourth dielectric layer 248 may have a refractive index of less than 1.75, for example less than 1.7, for example less than 1.6, for light with a wavelength of 900 nm. For example, the fourth dielectric layer 248 may have a refractive index between 1.4 and 1.6, or about 1.5, for light with a wavelength of 900 nm.

[0109] The dielectric layers 242, 244, 246, and 248 can be deposited by any conventional method, including but not limited to conventional chemical vapor deposition (CVD) and / or physical vapor deposition (PVD). Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam deposition and vacuum sputtering (such as magnetron sputtering deposition (MSVD)). Other coating methods, including but not limited to sol-gel deposition, may also be used. In one non-limiting embodiment, the dielectric layers 242, 244, 246, and 248 can be deposited by MSVD. Examples of MSVD coating devices and methods are well understood by those skilled in the art and are described, for example, in U.S. Patents 4,379,040, 4,861,669, 4,898,789, 4,898,790, 4,900,633, 4,920,006, 4,938,857, 5,328,768, and 5,492,750. In the MSVD method, a metal or metal alloy oxide is deposited by sputtering a metal or metal alloy-containing cathode in an oxygen-containing atmosphere, thereby depositing a film of metal oxide or metal alloy oxide on the surface of a substrate. In some non-limiting embodiments, dielectric layers 242, 244, 246, and 248 are deposited over the entire or substantially the entire surface, i.e., not deposited to form separate coated areas. The dielectric layers 242, 244, 246, and 248 can be deposited on a flat substrate, which can then be bent or molded into any conventional shape by heating or other means. Alternatively, the dielectric layers 242, 244, 246, and 248 can also be deposited on a curved surface, i.e., on a substrate that has already been bent or molded.

[0110] Referring to Figure 4, the coated article 10, monolithic transparent body 100, or windshield 200 may be positioned (e.g., installed) at an angle θ with respect to the x-axis. The angle θ of the coated article 10, monolithic transparent body 100, or windshield 200 may be between 0° and 90° with respect to the x-axis. For example, the angle θ of the coated article 10, monolithic transparent body 100, or windshield 200 may be 10°, 20°, 30°, 40°, 50°, 60°, 70°, 80°, or 90° with respect to the x-axis. The coated article 10, monolithic transparent body 100, or windshield 200 may be in contact with light 62 from the light source 60. When light 62 contacts the coated article 10, monolithic transparent body 100, or windshield 200, the angle of incidence θ with respect to the normal n of the coated article 10, monolithic transparent body 100, or windshield 200 is... I This depends on the angle at which the coated article 10, the monolithic permeator 100, or the windshield 200 is positioned. For example, if the coated article 10, the monolithic permeator 100, or the windshield 200 is positioned at an angle of 30°, the angle of incidence with respect to the normal n of the coated article 10, the monolithic permeator 100, or the windshield 200 will be approximately 60°.

[0111] The light source 60 may be configured to bring light 62 in the infrared spectrum (i.e., infrared radiation) into contact with the coated article 10, the monolithic transparent body 100, or the windshield 200. For example, the light 62 from the light source 60 may have wavelengths in the range of 800 nm to 1050 nm, or 825 nm to 1000 nm, or 850 nm to 950 nm, or 875 nm to 925 nm. For example, the light 62 from the light source 60 may have a wavelength of about 900 nm.

[0112] When a coated article 10, monolithic transparent body 100, or windshield 200 comes into contact with light 62 from a light source 60, it may transmit more light 62 than the same coated article 10, monolithic transparent body 100, or windshield 200, except that it lacks the first dielectric layers 42, 142, 242, the second dielectric layers 42, 142, 244, the third dielectric layers 46, 146, 246, and the fourth dielectric layers 48, 148, 248. For example, a coated article 10, monolithic transparent body 100, or windshield 200 may transmit at least 1%, at least 2%, or at least 3% more light 62 when in contact with light 62 from a light source 60, compared to the same coated article 10, monolithic transparent body 100, or windshield 200 except that it lacks the first dielectric layers 42, 142, 242, the second dielectric layers 44, 144, 244, the third dielectric layers 46, 146, 246, and the fourth dielectric layers 48, 148, 248. A coated article 10, monolithic transparent body 100, or windshield 200 may transmit at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% of the light 62 from a light source 60 when in contact with light 62 from a light source 60. The light 62 from the light source 60 may have a wavelength within the range of 800 nm to 1050 nm, or within the range of 825 nm to 1000 nm, or within the range of 850 nm to 950 nm, or within the range of 875 nm to 925 nm. For example, the light 62 from the light source 60 may have a wavelength of approximately 900 nm.

[0113] Referring to Figure 5, the LiDAR system 300 may include the aforementioned windshield 200. LiDAR is a technique in which near-infrared light (e.g., a wavelength of 905 nm) is emitted by a light source 60, reflected from an object 52, and the reflected light 72 is detected by a photodetector 70. The elapsed time for the light to travel back and forth from the light source 60 to the photodetector 70 makes it possible to calculate the distance to the object 52. When many light rays 62 are used in succession, this makes it possible to generate a spatial "map" of the surroundings. LiDAR's ability to rapidly map the surroundings in real time is an enabling technology for autonomous vehicles. To maximize the signal-to-noise ratio of the LiDAR system 300, it is necessary to maximize the intensity of the light 62 incident on the reflecting object 52, as well as maximize the reflected light 72 that reaches the photodetector 70. Reflectance loss occurs at the interface between the passenger compartment and the inward-facing surface of the windshield 200, and at the interface between the external environment and the outward-facing surface of the windshield 200. These reflectivity losses can be reduced by employing a first dielectric layer 242, a second dielectric layer 244, a third dielectric layer 246, and a fourth dielectric layer 248 on the surface of the windshield 200.

[0114] The LiDAR sensor 50 may be positioned behind the windshield 200. The LiDAR sensor 50 may include the aforementioned light source 60 and photodetector 70. The LiDAR sensor 50 may be configured to bring light 62 from the light source 60 into contact with the windshield 200.

[0115] Light 62 from the light source 60 of the LiDAR sensor 50 may pass through (i.e., transmit through) the windshield 200 and exit from the other side of the windshield 200. The light 62 that has passed through the windshield 200 may come into contact with an object 52 located on the opposite side of the windshield 200 from the perspective of the LiDAR sensor 50. If the object 52 comes into contact with the light 62, it may reflect the light 62 back towards the windshield 200 as reflected light 72. The reflected light 72 then passes through (i.e. transmits through) the windshield 200 and returns towards the LiDAR sensor 50, where the reflected light 72 may be detected by the photodetector 70.

[0116] The LiDAR system 300 shown in Figure 5 may be implemented in a variety of applications. For example, the LiDAR system 300 in Figure 5 may be implemented in an autonomous vehicle. As used herein, “vehicle” may refer to any means of transport, including but not limited to passenger cars, automobiles, semi-trucks, motorcycles, bicycles, buses, trains, subways, aircraft, airplanes, helicopters, spacecraft, ships, boats, underwater vehicles (e.g., submarines), golf carts, forklifts, etc.

[0117] The windshield 200 may form the windshield of the autonomous vehicle, and at least one LiDAR sensor 50 may be positioned in close proximity to the fourth surface 214 of the windshield 200 inside the passenger compartment of the autonomous vehicle. The LiDAR system 300 may be implemented in the autonomous vehicle to detect objects 52 around the autonomous vehicle and build a spatial map of the surroundings. Non-limiting examples of objects 52 that the LiDAR system 300 may detect include other vehicles, pedestrians, obstacles, barriers, and hazards on the road. The LiDAR system 300 in Figure 5 may be implemented in the autonomous vehicle to pinpoint the location of objects 52 and enable the autonomous vehicle to maneuver to avoid the objects 52.

[0118] The following examples illustrate various embodiments of the present invention. However, it should be understood that the present invention is not limited to these specific embodiments.

[0119] Example Five 99.06 cm (39 inches) × 129.54 cm (51 inches) STARPHIRE® glass substrates each having a nominal thickness of 2.1 mm were coated with a four-layer antireflective (AR) coating. The four-layer structure had the following layer structure and nominal / target thicknesses: (1 - the layer closest to the substrate) Zn52 - Sn48 oxide (i.e., zinc stannate) 22 nm, (2) Si85 - Al15 oxide 23 nm, (3) Zn52 - Sn48 oxide (i.e., zinc stannate) 164 nm, (4 - the layer farthest from the substrate) Si85 - Al15 oxide 141 nm. The coating was deposited using an MSVD pilot coater in five consecutive coater loads using the MSVD process.

[0120] Prior to depositing the coating on the 99.06 cm (39 inches) × 129.54 cm (51 inches) substrate, a continuous “color shot” sample was made where a coating was deposited on a 10.16 cm (4 inches) × 10.16 cm (4 inches) STARPHIRE® glass substrate having a thickness of 2.1 mm. After each color shot, the coated samples were heat treated in a Thermolyne box furnace to simulate the thermal bending / annealing process used in the manufacture of automotive windshields. For each sample after heat treatment, using a Hunter PRO spectrophotometer, the film-side reflectance (R f ) and glass-side reflectance (R g ) at an angle of incidence near the nominal value (8°), and the transmittance (T) at normal incidence were measured. Then, the measured reflectances (R f and R g ) and the transmittance spectrum were fitted to an optical model using the MSVD layer control software. Then, the MSVD layer control software presented recommendations on which layer of the four coating layers and by how much the thickness needed to be adjusted to apply the coating as desired.

[0121] Figure 6 plots the spectral transmittance at an incident angle of zero degrees (0°) for a 2.1 mm STARPHIRE® glass sample without monolithic coating and a STARPHIRE® glass sample with monolithic anti-reflective coating using substrate from the same lot. As shown in Figure 6, the STARPHIRE® glass with anti-reflective coating exhibits higher transmittance than the uncoated STARPHIRE® glass at almost all wavelengths above approximately 580 nm. In particular, the STARPHIRE® glass with anti-reflective coating exhibits 3.1% higher transmittance than the uncoated STARPHIRE® glass at a wavelength of 905 nm (Figure 7).

[0122] Table 1 below provides the transmittance (unpolarized) at 905 nm for STARPHIRE® glass with monolithic anti-reflective coating and STARPHIRE® glass without coating, as predicted by the optical model, at two incident angles: (1) 0 degrees and (2) 60 degrees. As shown in Table 1, the model predicts that at 905 nm and an incident angle of 0 degrees, STARPHIRE® glass with anti-reflective coating has a 3.2% higher transmittance than STARPHIRE® glass without coating, which is consistent with the measurement that the transmittance observed under these conditions is 3.1% higher, as shown in Figure 6. Table 1 further shows that the optical model also predicts that at 905 nm and an incident angle of 60°, which is an appropriate incident angle for windshields installed in vehicles, STARPHIRE® glass with monolithic anti-reflective coating has a 3.5% higher transmittance than STARPHIRE® glass without monolithic coating. [Table 1]

[0123] Table 2 below shows the corresponding transmittances of the laminated configurations predicted by the optical model, including (1) an anti-reflective coated or uncoated STARPHIRE® glass inner ply, (2) a 0.7 mm polyvinyl butyral (PVB) interlayer, and (3) an uncoated STARPHIRE® glass outer ply, at the same wavelengths and angles of incidence as reported in Table 1. The difference in transmittance between the laminated configuration using the anti-reflective coated STARPHIRE® glass ply and the laminated configuration using the uncoated STARPHIRE® glass ply is the same as that shown in Table 1. Table 2 is included to show the absolute transmittances of the two different laminated configurations predicted by the optical model. [Table 2]

Claims

1. Coated articles, Substrate and A first dielectric layer comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, having a maximum thickness of 40 nm on at least a portion of the substrate, A second dielectric layer having a maximum thickness of 40 nm is provided on at least a portion of the first dielectric layer, A third dielectric layer comprising a metal oxide, metal alloy oxide, metal nitride, metal alloy nitride, or a combination thereof, having a thickness of at least 130 nm on at least a portion of the second dielectric layer, A fourth dielectric layer having a thickness of at least 130 nm is placed on at least a portion of the third dielectric layer. A coated article comprising the above, wherein when the coated article is in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source, the coated article transmits at least 75% of the light.

2. The coated article according to claim 1, wherein the substrate comprises glass having a total iron content of at most 0.02 wt%.

3. The coated article according to claim 1, wherein the first dielectric layer and the third dielectric layer comprise the same material.

4. The coated article according to claim 1, wherein the first dielectric layer and the third dielectric layer each independently contain zinc stannate, zinc oxide, tin oxide, silicon nitride, or a combination thereof.

5. The coated article according to claim 1, wherein the second dielectric layer and the fourth dielectric layer comprise the same material.

6. The coated article according to claim 1, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon, silicon and aluminum, a silicon-containing alloy, or a combination thereof.

7. The coated article according to claim 6, wherein the second dielectric layer and the fourth dielectric layer each independently comprise an oxide, a nitride, an oxynitride, or a combination thereof.

8. The coated article according to claim 7, wherein the second dielectric layer and the fourth dielectric layer each independently contain silicon oxide, aluminum silicon oxide, or a combination thereof.

9. The coated article according to claim 1, wherein the first dielectric layer and the second dielectric layer have a thickness in the range of 10 nm to 40 nm.

10. The coated article according to claim 9, wherein the first dielectric layer and the second dielectric layer have a thickness in the range of 20 nm to 35 nm.

11. The coated article according to claim 1, wherein the third dielectric layer and the fourth dielectric layer have a thickness in the range of 130 nm to 180 nm.

12. The coated article according to claim 11, wherein the third dielectric layer has a thickness in the range of 145 nm to 170 nm, and the fourth dielectric layer has a thickness in the range of 135 nm to 180 nm.

13. The coated article according to claim 1, wherein the first dielectric layer and the second dielectric layer are in direct contact with each other, and the third dielectric layer and the fourth dielectric layer are in direct contact with each other.

14. The coated article according to claim 13, wherein the second dielectric layer and the third dielectric layer are in direct contact with each other.

15. The coated article according to claim 1, wherein the light has a wavelength of about 900 nm.

16. The coated article according to claim 1, wherein the coated article transmits at least 80% of the light.

17. The coated article according to claim 1, wherein the coated article transmits at least 85% of the light.

18. The coated article, The aforementioned substrate, The first dielectric layer, The second dielectric layer, The third dielectric layer, and The fourth dielectric layer A coated article according to claim 1, comprising the above.

19. A first ply having a first surface and a second surface opposite to the first surface, A second ply comprising a third surface adjacent to the second surface and a fourth surface opposite to the third surface, A first dielectric layer having a maximum thickness of 40 nm, comprising a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof, on at least a portion of the first surface or the fourth surface. A second dielectric layer having a maximum thickness of 40 nm is placed on at least a portion of the first dielectric layer. A third dielectric layer comprising a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof, having a thickness of at least 130 nm on at least a portion of the second dielectric layer, and A fourth dielectric layer having a thickness of at least 130 nm is placed on at least a portion of the third dielectric layer. A windshield comprising a windshield that, when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source, transmits at least 75% of the said light, At least one LiDAR sensor positioned in close proximity to the fourth surface and A LiDAR system equipped with [this feature].

20. An autonomous vehicle equipped with a LiDAR system, wherein the LiDAR system is A first ply having a first surface and a second surface opposite to the first surface, A second ply comprising a third surface adjacent to the second surface and a fourth surface opposite to the third surface, A first dielectric layer having a maximum thickness of 40 nm, comprising a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof, on at least a portion of the first surface or the fourth surface. A second dielectric layer having a maximum thickness of 40 nm is placed on at least a portion of the first dielectric layer. A third dielectric layer comprising a metal oxide, a metal alloy oxide, a metal nitride, a metal alloy nitride, or a combination thereof, having a thickness of at least 130 nm on at least a portion of the second dielectric layer, and A fourth dielectric layer having a thickness of at least 130 nm is placed on at least a portion of the third dielectric layer. A windshield comprising a windshield that, when in contact at 60° with light having a wavelength between 800 nm and 1,050 nm from a light source, transmits at least 75% of the said light, At least one LiDAR sensor positioned in close proximity to the fourth surface and An autonomous vehicle equipped with [the following features].

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