TWI706921B - Optical coating method, apparatus and product - Google Patents

Abstract

This disclosure is directed to an improved process for making glass articles having optical coating and easy to clean coating thereon, an apparatus for the process and a product made using the process. In particular, the disclosure is directed to a process in which the application of the optical coating and the easy to clean coating can be sequentially applied using a single apparatus. Using the combination of the coating apparatus and the substrate carrier described herein results in a glass article having both optical and easy to clean coating that have improved scratch resistance durability and optical performance, and in addition the resulting articles are "shadow free."

Description

Optical coating method, device and product

This application is part of the continuous case of U.S. Non-Provisional Patent Application No. 13/690829 filed on November 30, 2012, titled "Optical Coating Method, Apparatus and Product". It asserts the priority of U.S. Provisional Patent Application No. 61/709423, which was filed on October 4, 2012, entitled "Optical Coating Method, Apparatus and Product (Optical Coating Method, Apparatus and Product)", and the foregoing The content of the case is for reference and is incorporated herein by reference in its entirety, and this application is also the U.S. Non-Provisional Patent Application No. 13/690,904 filed on November 30, 2012, with the title "The production is optical and easy "Process for Making of Glass Articles with Optical and Easy-To-Clean Coatings" is part of the continuous case. The content of the case is for reference and is incorporated herein in its entirety.

The present invention is directed to a manufacturing process for making glass products, with optical coating and easy-to-clean (ETC) coating on the glass products, a device for performing the manufacturing process, and a product manufactured using the manufacturing process. In particular, the present invention is directed to a process in which optical coating and ETC coating can be applied sequentially using the same device.

Glass, especially chemically strengthened glass, has become a material option for many, if not most, window screens of consumer electronic products. For example, chemically strengthened glass is particularly popular with "touch" screen products, whether it is small objects such as mobile phones, music players, e-book readers and electronic notebooks, or computers, ATMs, Airport self-service check-in counters or other large objects similar to electronic objects. Many of these objects need to be coated with antireflective (AR) coatings on the glass in order to reduce visible light reflection from the glass and thereby improve contrast and readability, for example, when using the device under direct sunlight. However, some shortcomings of AR coating are its surface contamination sensitivity and poor durability against scratches, which means that AR coating becomes easily scratched during use, such as being wiped or dusted by the user’s fingers. dirt. Fingerprints and stains are very obvious on AR coating and are not always easy to remove. As a result, it is highly desirable that the glass surface of any touch device is easy to clean, and this can be achieved by coating ETC coating on the glass surface.

The existing process for making glass products with both anti-reflection and ETC coating requires different equipment to coat the coating, and therefore requires a separate manufacturing process. The basic procedure is to coat anti-reflective ("AR") coatings on glass products, for example, using chemical vapor deposition ("CVD") or physical vapor deposition ("PVD") methods. In the conventional manufacturing process, an optically coated product, for example, a product with AR coating, will be transferred from the optical coating device to another device to coat the ETC coating on top of the AR coating. When these processes can produce products with both anti-reflective coating and ETC coating, they require separate processes and require additional processing, so there will be higher yield loss. This may result in poor reliability of the final product, due to contamination caused by additional processing between AR coating and ETC coating procedures. For example, using the conventional two-step coating process of placing ETC on the optical coating leads to products that are easily scratched in touch screen applications. In addition, although the AR coating surface can be cleaned before applying the ETC coating, this involves an additional step in the manufacturing process. All extra steps increase the cost of the product. As a result, the two types of coating require other alternative methods and devices to use the same basic procedures and equipment for coating, thereby reducing manufacturing costs. The advantages of the process disclosed in this article and the products obtained are described in the following paragraphs and claims.

In one or more embodiments, the present invention provides a substrate carrier for holding a substrate in a coating process. The substrate carrier may include a substrate carrier base including a retention surface, a bottom surface and a substrate retention area, and the substrate retention area is arranged on the retention surface. The substrate stagnation area may have an area smaller than the stagnation surface. The substrate carrier may also include a plurality of magnetic beams coupled to the bottom surface of the substrate carrier base, and the plurality of magnetic beams are positioned outside the periphery of the substrate stagnation area. In one or more embodiments, the adhesive material may be positioned on the retention surface in the retention area of the substrate, and it is used to detachably fix at least one substrate to be coated on the retention surface. The adhesive material may include pressure sensitive adhesive. In a variation, the adhesive material may include acrylic adhesives, rubber adhesives and/or silicone adhesives. Alternatively, a polymer film can be positioned between the retention surface and the adhesive material.

The substrate carrier may include a plurality of pins for supporting the substrate positioned on the stagnant surface. Optionally, the substrate carrier may include a spring system including a retractable latch, the retractable latch is appropriately positioned by the spring, and when the substrate is positioned on the stagnant surface, the spring biases the retractable latch to contact the substrate; and The carrier base extends a plurality of side stoppers for a certain distance, so that when the substrate is positioned on the plurality of pins, the tops of the plurality of side stoppers are located below the top surface of the substrate. In a variation, the substrate carrier may include an outer cover provided with a retractable latch pin inside, wherein the retractable latch pin is properly positioned by a spring. When the substrate is positioned on the stagnant surface, the retractable latch pin is biased outward from the outer cover. Place and contact the substrate; and when the substrate is positioned on the stagnant surface, a plurality of movable pins for holding the edge of the substrate. In another variation, the positions of the plurality of pins can be adjusted to accommodate substrates of different shapes and sizes.

In yet another variation, the present invention provides a coating device for coating a substrate. The coating device may include a vacuum chamber and a rotating dome positioned in the vacuum chamber and containing a magnetic material. The plasma source can be positioned inside the vacuum chamber and the plasma source is oriented substantially vertically to guide the plasma to the bottom surface of the rotating dome, wherein the plasma source is positioned below the rotating dome and spins on the axis of the rotating dome To the ground outwards, the plasma emitted from the plasma source is incident on the bottom surface of the rotating dome from at least one outer edge of the rotating dome to at least one center of the rotating dome. In one or more embodiments, the distance between the rotation axis of the rotating dome and the plasma source is greater than the distance between the protruding periphery of the rotating dome and the plasma source. The coating device may include at least one thermal evaporation source positioned in the vacuum chamber.

The coating device may optionally include at least one e-beam source positioned in the vacuum chamber, and the electron beam source is oriented to guide the electron beam to the coating source material positioned in the vacuum chamber. The coating device may include a second electron beam source positioned in the vacuum chamber. The second electron beam source may be oriented to guide the second electron beam to the coating source material positioned in the vacuum chamber.

In another option, the coating device may include at least one shadow mask that can be adjustably positioned inside the vacuum chamber. The shield can be adjusted between an extended position and a retracted position. The extended position means that at least one shield is positioned between the at least one electron beam source and the rotating dome, and the retracted position means that at least one shield is not positioned on the at least one electron beam. Between the beam source and the rotating dome. In one or more embodiments, a second mask may be included. In such embodiments, the second shield may be positioned between the second electron beam source and the rotating dome.

The coating device may include a rotating dome, which includes an opening in the center of the top of the rotating dome; a transparent glass plate covering the opening of the rotating dome; and a monitor positioned in the opening in the transparent glass plate, which is used for Monitor the deposition rate of the coating material deposited in the vacuum chamber. The optical fiber can be positioned above the transparent glass plate, wherein when the transparent glass plate is coated to determine the reflectance change of the transparent glass plate and therefore the coating thickness of the transparent glass plate is determined, the optical fiber collects the light reflected from the transparent glass plate.

In yet another embodiment, the present invention provides a coating device for coating a substrate. The coating device may include a vacuum chamber and a rotating dome positioned in the vacuum chamber. The rotating dome can be constructed using magnetic materials. The device may also include at least one substrate carrier for fixing to the rotating dome. The at least one substrate carrier may include a substrate carrier base including a retention surface, a bottom surface and a substrate retention area, and the substrate retention area is disposed on the retention surface. A plurality of magnetic beams can be coupled to the bottom surface of the substrate carrier base and the plurality of magnetic beams are positioned outside the periphery of the substrate stagnation area. The adhesive material can be positioned on the stagnant surface in the stagnant zone of the substrate, and is used to detachably fix at least one substrate to be coated. The coating device may include a plasma source positioned inside the vacuum chamber, and the plasma source is oriented substantially vertically to guide the plasma to the bottom surface of the rotating dome, wherein the plasma source is positioned below the rotating dome and the rotating dome The rotating shaft is radially outward, so that the plasma emitted from the plasma source is incident on the bottom surface of the rotating dome from at least one outer edge of the rotating dome to at least one center of the rotating dome. In a variation, the distance between the rotating shaft of the rotating dome and the plasma source is greater than the distance between the protruding periphery of the rotating dome and the plasma source. The coating device may include a first electron beam source and a second electron beam source. The first electron beam source is positioned in the vacuum chamber and oriented to guide the first electron beam to the first coating source material positioned in the vacuum chamber. The two electron beam sources are positioned in the vacuum chamber and oriented to guide the second electron beam to the second coating source material positioned in the vacuum chamber. The first coating source material can exhibit a high refractive index and the second coating source material can exhibit a low refractive index or a medium refractive index. The coating device may include at least one shield that is adjustable and positionable inside the vacuum chamber. The shield can be adjusted between an extended position and a retracted position. The extended position means that at least one shield is positioned between at least one of the first electron beam source and the second electron beam source and the rotating dome, and the retracted position is at least A mask is not positioned between the first electron beam source or the second electron beam source and the rotating dome.

The additional features and advantages of the method described in this article will be clarified in the following detailed description, and some parts of it will be obvious to those skilled in the art from this description, or by implementing the embodiments described in this article, Including the following detailed description, claim items and attached drawings, and be recognized.

It should be understood that the above general description and the subsequent detailed description both describe various embodiments and are intended to provide an overview and structure of the nature and characteristics of the requested subject. The accompanying drawings are included to provide further understanding of the various embodiments, and are incorporated into and constitute this specification. The drawings illustrate various embodiments described herein, and together with this description are used to explain the principles and operations of the requested subject.

Now, reference will be made to various embodiments of glass products coated with optical coatings and easy-to-clean coatings, and methods and apparatuses for forming such glass products. The examples are shown in the accompanying drawings. If possible, the same component symbols will be used in all drawings to represent the same or similar parts. An embodiment of the coating device is schematically depicted in Fig. 1A. The coating device usually includes a vacuum chamber with a magnetic dome positioned therein. The coating device also includes an electron beam source, a thermal evaporation source and a plasma source. The glass substrate to be coated can be magnetically attached to the bottom surface of the dome and use an electron beam source and a thermal vapor deposition source to be coated with optical coating and ETC coating. In an embodiment, a plasma source can be used to densify the deposited optical coating material. Various embodiments of devices and methods for sequentially applying optical coatings and ETC coatings to glass substrates will be described in detail herein with reference to the accompanying drawings.

In this article, the terms "process" and "method" can be used interchangeably. In addition, the terms "shadowless" and "shadow free" in this article mean that the optical coating is uniformly deposited on the entire surface of the glass substrate, so that when there is a difference in the coating deposited using the methods and devices described in this article When the glass product is inspected, the observable shadow system on the glass product with the optical coating prepared by the conventional optical coating method and device cannot be observed. When the area of the substrate being coated covers the substrate surface and cannot be deposited by the optical coating material, the shadows observed in the conventional coated glass products will appear. Such shadows are often observed in the vicinity of the following components: components used to hold the substrate being coated in place during the coating process or used on the substrate carrier to transport the carrier and components being coated in and out Components of the coating machine.

The terms "glass product" and "glass substrate" are used interchangeably herein and generally refer to any glass object coated with the methods and devices described herein.

The present invention is directed to a process in which, for example, optical coatings such as AR coatings containing alternating thin layers of high and low refractive index materials and ETC coatings such as perfluoroalkylsilane coatings (perfluoroalkylsilane coating) can both be in sequential steps (meaning , First coat the optical coating, and then coat the ETC coating on the optical coating) Use substantially the same procedure to coat the glass substrate without exposing the product to any time during the coating process of optical coating and ETC coating In the air or surrounding atmosphere. Reliable ETC coating provides lubrication to the surface of glass, transparent conductive coating (TCC) and optical coating. In addition, the abrasion resistance of glass and optical coatings will be more than 10 times better than conventional coating processes or AR coatings without ETC coating (using an in-situ, single-step process, where the coating is applied sequentially , As illustrated in Figures 10, 11 and 17B) better than 100-1000 times. Using this kind of technology, the ETC coating can be regarded as a part of the optical coating during design, and by this, the ETC coating will not change the desired optical performance. The glass products described in this article have no shadows on the entire optical coating surface of the glass.

A particular example of in-situ manufacturing is the box coater schematically depicted in Figure 1A. The box coater is equipped with an e-beam source for optical coating, a thermal evaporation source for ETC coating materials, as well as surface cleaning before coating and optical coating compression during coating ( The ion beam or plasma source of optical coating impaction is used to increase the coating density and the flatness of the coating surface.

The optical coating is composed of high, medium or low refractive index materials. Exemplary high refractive index materials have a refractive index greater than or equal to 1.7 and less than or equal to 3.0, including ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , Y ₂ O ₃ , Si ₃ N _4. SrTiO ₃ , WO ₃ ; an exemplary medium refractive index material system Al ₂ O _{3 with a} refractive index n greater than or equal to 1.5 and less than 1.7; and an exemplary low refractive index material system having a refractive index greater than or equal to 1.3 and less than or The refractive index n equal to 1.6 includes SiO ₂ , MgF ₂ , YF ₃ , and YbF ₃ . The optical coating stack deposited on the substrate includes at least one material/thin layer that provides a specific optical function. In most cases, a high and a low refractive index material can be used to design complex optical filters (including AR coatings), such as HfO ₂ as a high refractive index material and SiO ₂ as a low refractive index material. TCC (tow-component coating) materials suitable for coating include ITO (indium tin oxide), AZO (Al doped zinc oxide), IZO (Zn stabilized indium oxide) , Zinc stabilized indium oxide), In ₂ O ₃ and similar binary and ternary oxide compounds.

In the embodiment, the optical coating is coated on the glass substrate using PVD coating (sputtered or thermally evaporated IAD-EB covering optical coating with ETC coating). PVD is a "cold" process in which the substrate temperature is lower than 100 ^o C. Therefore, the strength of the chemically strengthened or strengthened glass coated with the coating is not degraded.

In the embodiments described herein, the optical and ETC coated glass products used to make the de-shadows described herein can be ion exchange glass or non-ion exchange glass. Exemplary glasses include silica glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass and soda lime glass. ). The glass product has a thickness ranging from 0.2 mm to 1.5 mm, and has a length and width suitable for the intended purpose. Therefore, the length and width of glass products can range from mobile phones to tablets, or larger.

The optical coating referred to in this article includes anti-reflection coating (AR coating), bandpass filter coating, edge neutral mirror coating and beam splitter, multilayer highly reflective coating and edge filter (edge filter) , As described in the third edition of "Thin Film Optical Filters (Thin Film Optical Filters)" published in 2001 by H. Angus Macleod, Physics Publishing Research, Bristol and Philadelphia. Applications using such optical coatings include displays, camera lenses, telecommunications components, instruments, medical devices, photochromic and electrochromic devices, photovoltaic devices, and other components and devices.

Alternate thin layers of high and low refractive index materials can be used to form optical coatings, such as anti-reflection or anti-glare for ultraviolet ("UV"), visible light ("VIS") or infrared ("IR") applications. Optical coatings can be deposited using different methods. The PVD method (that is, ion assisted, electron beam deposition) used to deposit optical coatings is used as an exemplary method herein. The optical coating includes at least one layer of high refractive index material H and at least one layer of low refractive index material L. The multilayer coating is composed of multiple alternating high and low refractive index layers, such as HL, HL, HL, etc. or LH, LH, LH, etc. A pair of HL layer (or LH layer) is called "cycle" or "coating cycle". The medium refractive index material M can be used to replace all or part of the low refractive index material in the low refractive index layer. The term "index" used in this article refers to the refractive index of the material. In multilayer coating, the number of cycles can vary widely depending on the intended product function. For example, for AR coating, the number of cycles can be in the range of greater than or equal to 2 and less than or equal to 20. The optional final covering layer of SiO ₂ can also be deposited on top of the AR coating as the final layer. Different techniques can be used to deposit ETC materials on top of the optical coating without exposing the optical coating to the surrounding atmosphere. Different techniques include, without limitation, thermal evaporation, chemical vapor deposition (CVD) or atomic Layer deposition (ALD).

The optical coating deposited on the glass substrate described herein may be a multilayer optical coating containing at least one period of high refractive index material and low refractive index material. The high refractive index material can be selected from ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , Y ₂ O ₃ , Si ₃ N ₄ , SrTiO ₃ and WO ₃ . However, it should be understood that other suitable high refractive index materials can also be used. The low refractive index material can be selected from the group consisting of SiO ₂ , MgF ₂ , YF ₃ and YbF ₃ . However, it should be understood that other suitable low refractive index materials can also be used. In some embodiments, the low refractive index material may be replaced by a medium refractive index material, such as Al ₂ O ₃ or other suitable medium refractive index materials.

In one embodiment, the present invention is directed to a process in which in the first step, the multilayer optical coating is deposited on the glass substrate, and then in the second step, the ETC coating is in the same chamber as the optical coating. It is thermally evaporated and deposited. In another embodiment, the multilayer optical coating is deposited on the glass substrate in a chamber, and then the ETC coating is thermally vaporized and deposited on top of the multilayer optical coating in the second chamber, by providing a multilayer optical coating substrate The coating between the multilayer optical coating and the ETC coating is transported from the first chamber to the second chamber without exposure to air in series. The coating technology used may include, but is not limited to, PVD, CVD/PECVD and ALD coating technology. Depending on the size of the chamber or multiple chambers and the size of the substrate to be coated, one or more substrates can be coated in a single chamber at the same time.

Multilayer optical coatings are usually oxide coatings, in which lanthanide series oxides, such as La, Nb, Y, Gd or other lanthanide series metals, are coated with high refractive index, and SiO _{2 is} coated with low refractive index. The ETC material can be, for example, fluorinated silanes, typical perfluorocarbon alkyl perfluorocarbon silanes with the chemical formula (R _F ) _X SiX _4-x , where R _f is a linear C ₆ -C ₃₀ perfluorocarbon alkyl group, X=Cl or -OCH ₃ -and X=2 or 3. The fluorocarbon has a carbon chain with a length in the range of greater than or equal to 3 nm and less than or equal to 50 nm. Fluorocarbons can be obtained from the following manufacturers on the market, including, but not limited to, Dow Corning (such as fluorocarbons 2604 and 2634), 3M (such as ECC-1000 and 4000), Daikin, Canon, Tang (South Korea) ), Ceko (South Korea), Cooltech (such as DURALON UltraTec) and Evonik.

FIG. 1A schematically depicts the coating device 100 and different operating elements of the device according to one or more embodiments described herein. The coordinate axis system is for reference. In the front view, x is from side to side (meaning from left to right), y is from front to back (meaning in and out of the page), and z is from bottom to top. The coating device 100 usually includes a vacuum chamber 102. Inside the vacuum chamber 102 is a rotating dome 110 with a lip 161 (depicted in Figure 3A). The lip 161 is a frame 160 supporting the dome 110 (further shown in Figure 3A). 3B) part. The dome includes a plurality of substrate carriers 130 magnetically attached to the bottom surface of the dome, as shown in FIG. 2. The plasma source 118 is located in the vacuum chamber 102 below the dome 110 and is usually directed upward to emit ions or plasma to the bottom surface of the dome 110. After the optical coating material is deposited and/or deposited, the plasma source is used to make the optical coating material compact, thereby increasing the hardness of the completed optical coating. In particular, the ions or plasma emitted from the plasma source impact the coating during the deposition process and/or after the coating layer has been coated, resulting in densification of the deposited material. Densification of the deposited optical coating can improve the scratch resistance of the optical coating. For example, in some embodiments, the deposited optical coating will have at least twice the scratch reliability or scratch resistance compared to an optical coating deposited without a plasma source. The plasma source 118 may be used with a neutralizer 121, as described in more detail herein with respect to FIG. 21A.

The coating device further includes an electron beam source 120 and an electron beam mirror 122 located under the dome 110. The electron beam mirror 122 is used to guide the electron beam from the electron beam source to the optical coating material being coated on the glass substrate, In order to vaporize optical materials. A mask 125 for allowing uniform coating of the entire dome is located under the dome 110. The shape and position of the mask 125 can be adjusted so that the mask is "tunable" to achieve the desired coating uniformity. The shield 125 is positioned on the support 125a, so that the position of the shield 125 can be adjusted vertically along the support 125a, as indicated by the double arrow dashed line. The position of the mask 125 on the support 125a can be adjusted as needed to prevent the mask from blocking the glass substrate on the bottom surface of the dome 110 from being irradiated by the plasma source 118 or plasma when the optical coating is applied. Although Figure 1A depicts a single electron beam source 120, it should be understood that multiple groups of electron beam sources can also be used to minimize the time required to change from one coating material to another, for example from Nb ₂ O ₅ to SiO _2. It is transformed back again, which is based on the number of layers required to deposit individual material layers for optical coatings. For example, in some embodiments, the coating device may include greater than or equal to 2 groups and less than or equal to 6 groups of electron beam sources. When using multiple sets of electron beam sources, each set of electron beam sources can be guided to a separate container (meaning boat 126, described further herein) that holds the material to be coated.

The coating device 100 further includes an optical coating carrier 124 having a plurality of boats 126, and the boats 126 contain optical coating materials. The boat 126 is used as a separate source container containing different materials for depositing the optical coating layer. The optical coating carrier 124 is positioned in the vacuum chamber 102, so that the electron beam emitted from the electron beam source 120 can be reflected by the electron beam mirror 122 to the optical coating material contained in the boat 126, thereby coating the optical Material gasification. The boat 126 contains different optical coating materials so that only one coating material (for example, high refractive index material, low refractive index material or medium refractive index material) is coated at a time. After reaching an appropriate thickness of a coating material, the corresponding boat top cover (not shown) is closed and the boat top cover containing the different coating materials to be coated is opened. In this way, high refractive index materials, low refractive index materials or medium refractive index materials can be coated in turn to form optical coating materials with desired optical properties.

The coating device 100 also includes at least one thermal evaporation source 128 for thermally vaporizing the ETC coating material to accelerate the deposition of the coating material on the glass substrate fixed on the bottom surface of the dome 110. The at least one thermal evaporation source 128 is positioned in the vacuum chamber 102 below the dome 110. In one or more embodiments, the ETC coating is formed by steel wool-filled copper crucible (steel wool-filled copper crucible) (not shown) or porous ceramic-filled copper crucible (not shown) ) And provided in the vacuum chamber 102. The use of steel wool provides uniform heating of ETC materials and increases the surface area of vaporization. The use of steel wool also provides a more controllable deposition rate for ETC coating on the substrate.

Still referring to FIG. 1A, the dome 110 is made of magnetism or a lightweight material containing a magnetic material, such as, but not limited to, aluminum containing a metal component or other suitable magnetic materials. The dome 110 can be rotated clockwise or counterclockwise. In the center of the top of the dome there is an opening 164 (depicted in Figure 3B) and a transparent glass plate 116 is placed on the bottom surface of the dome to cover the opening. The transparent glass plate 116 may include an opening 116a as depicted in the enlarged view of the transparent glass plate 116 in FIG. 1B. The quartz monitor 114 is housed in and penetrates the transparent glass plate 116. The optical fiber 112 is positioned above the transparent glass plate 116, as shown. The quartz monitor 114 controls the deposition rate of the optical material by the signal fed back to the electron beam power supply, so that the deposition rate of the coating material can be kept substantially stable. The optical fiber 112 is positioned above the transparent glass plate 116 to prevent itself from being deposited by material in the vacuum chamber 102. The optical fiber measures the reflectivity to determine when the deposition of each layer of the coating material should stop, because the target design thickness has been reached.

Figure 1C is an enlarged view of the circled area of the transparent glass plate 116 in Figure 1A, showing the relative orientation of the optical fiber 112, the quartz monitor 114, and the transparent glass plate 116. The quartz monitor 114 is positioned in the middle of the transparent glass plate 116 and passes through the opening 116a. The optical fiber 112 is positioned on the side of the quartz monitor 114. The light emitted from the optical fiber 112 passes through the transparent glass plate 116 and is reflected back because the surface of the transparent glass plate is coated. The arrow adjacent to %R schematically depicts the reflection of light from the surface 116b of the transparent glass plate when the transparent glass plate is being coated. The reflection is enhanced as the thickness of the coating film coated on the surface 116b of the transparent glass plate increases. The light reflected from the surface 116b of the transparent glass plate is guided back to an optical sensor (not shown) coupled with a controller (not shown) of the electron beam source. The output of the optical sensor (representing the thickness of the coated optical coating and/or ETC coating) is used by the controller to determine the deposition thickness of the coating. In this way, the reflected light can be used to control the deposition thickness of individual layers, coating cycles and the entire optical coating as well as the deposition thickness of the ETC coating.

The top of the dome 110 is attached to the vacuum shield rotating shaft 117 indicated by double parallel dashed lines. The vacuum shield rotating shaft 117 has a vacuum sealed bearing 119 attached to the vacuum shield rotating shaft for rotating the vacuum shield rotating shaft 117 and the dome 110. Therefore, it should be understood that the vacuum shielded rotating shaft 117 is vacuum sealed to the top of the dome 110. The vacuum shield rotating shaft 117 is driven by an external motor (not shown) located outside the vacuum chamber 102. In one embodiment, the dome 110 can be rotated in a rotation frequency range from about 20 rpm to about 120 rpm. In another embodiment, the rotation frequency range is between about 40 rpm and about 83 rpm.

Fig. 2 schematically depicts the block 110a of the dome 110. As shown in FIG. 2, a plurality of substrate carriers 130 are magnetically attached to the dome 110. The substrate carrier 130 is used to fix the glass substrate for coating in the coating device 100.

FIG. 3A is an oblique top side view of the block 110a of the dome 110, which shows the lip 161 and a plurality of substrate carriers 130 magnetically attached to the dome 110. Figure 3B is an illustration of the frame 160 used to support a plurality of blocks 110a. The frame 160 has an outer lip 161 (as depicted in FIG. 3A), an inner side edge (no number) that is adjacent to the opening 164 and a vacuum shielding rotating shaft 117 (not shown) that can be attached to and radially from the inner edge A plurality of spokes 162 extending outward. The spokes 162 are wide enough to accommodate the side edges of the dome block at 168 as shown.

Figure 17A is a simple diagram of another embodiment of the coating device, which is used to deposit optical coating and ETC coating on a substrate. In this embodiment, the coating device includes a mask 127 covering selected areas of the dome to improve the uniformity of the optical coating deposited on the substrate. The bracket used to adjustably support the mask 127 is not depicted in Figure 17A. In the coating apparatus shown in Figure 17A, the plasma source is an ion source 118a. Since the ion source 118a and the electron beam source 120 used to vaporize the optical coating material are located on different sides of the vacuum chamber, the ion source will not be blocked by the mask, so it can improve the hardening of the deposited optical coating material by the ion source 118a The effect. The ion source is used to make the optical coating material close to the bulk density, thereby increasing the hardness of the optical coating and improving the scratch reliability/scratch resistance of the optical coating.

FIG. 21A schematically depicts another embodiment of a coating apparatus 500 for depositing optical coating and ETC coating on a substrate. The cross-sectional view of the coating device 500 is schematically depicted in FIG. 21B. In this embodiment, the coating device 500 includes a vacuum chamber 102 having a rotating dome 110, and the rotating dome 110 includes a magnetic material, as described with respect to FIG. 1. The rotating dome is coupled to the vacuum shielded rotating shaft 117 arranged in the vacuum sealed bearing 119 to facilitate the rotation of the dome in the vacuum chamber. The dome also includes a transparent glass plate 116 with a quartz monitor 114 and an optical fiber 112, which are commonly used to monitor and control the deposition rate of the coating on the substrate. The substrate is attached to the dome, as opposed to As described in Figures 1A-1C.

The coating device 500 also includes an optical coating carrier 124 having a plurality of boats 126, and the boats 126 contain optical coating materials. The boat 126 is used to contain separate source containers for different materials for depositing the optical coating layer on the substrate, and the substrate is fixed on the bottom surface of the dome 110. The boat 126 contains different optical coating materials so that only one coating material (for example, high refractive index material, low refractive index material or medium refractive index material) is coated at a time. In this embodiment, the coating device 500 includes a first electron beam source 120 a, a second electron beam source 120 b, and an electron beam mirror 122. The first electron beam source 120a, the second electron beam source 120b, and the electron beam mirror 122 are arranged so that the electron beams emitted from each electron beam source are guided to the electron beam mirror 122 and then directed from the electron beam mirror 122 to the The single optical coating material in the boat 126 on the optical coating carrier 124 can vaporize the optical coating material together. It has been found that the use of multiple electron beam sources for co-vaporizing a single optical coating material can enhance the thickness uniformity of the resulting coating deposited on the substrate. Additionally or alternatively, the first electron beam source 120a emits the first electron beam to the electron beam mirror 122, so that the first electron beam is guided back to the first optical coating material contained in the boat 126 and the second electron beam source 120b emits the second electron beam to the electron beam mirror 122, so that the second electron beam is redirected back to the second optical coating material contained in a different boat 126. In one or more embodiments, the first optical coating material is different from the second optical coating material. In an embodiment, the first optical coating material includes a high refractive index material and the second optical coating material includes a medium or low refractive index material. In an embodiment, more than one mirror may be used, such that one mirror (not shown) redirects the first electron beam and the second mirror (not shown) redirects the second electron beam.

In this embodiment, the coating device 500 further includes a first cover 125 that is adjustably positionable inside the vacuum chamber 102 and a second cover 129 that has a fixed position inside the vacuum chamber 102. The first shield is adjustable between an extended position (depicted in Figure 21A) and a retracted position (not shown). The extended position is where the first shield 125 is positioned on at least one of the electron beam sources and the rotation circle Between the tops, the retracted position is that the first shield is not positioned between the rotating dome and any electron beam source. In particular, in an embodiment, the first shield 125 may include a first position 180 coupled to an actuator 175 such as an electric motor or the like, which rotates the first shield 125 from the extended position to the retracted position . In an embodiment, the first shield 125 may include a second position 181 pivotally connected to the first position 180. When the first mask is rotated to the retracted position (that is, when the first mask is rotated downward in the clockwise direction in Figure 21A), the second position 181 can be folded to the first position 180.

In the cross-sectional view of the coating apparatus 500 schematically depicted in FIG. 21B, when the first mask 125 is in the extended position, it is positioned between the first electron beam source 120a and the bottom surface of the dome 110 (not shown) between. The second shield 129 is fixedly positioned between the electron beam source 120b and the bottom surface of the dome 110 (not shown). The first mask 125 can be extended or retracted depending on the type of optical coating material being deposited. For example, when Nb ₂ O _{5 is} deposited, the first mask 125 may be in the retracted position. However, when SiO _{2 is} deposited, the first mask 125 may be in the extended position. The mask is used to improve the thickness uniformity of the deposited optical coating, regardless of where the substrate is on the dome. In particular, referring to Figure 22, the deposition thickness of the coating material deposited from the point source 400 usually varies according to the relationship Cos ⁿ (θ)/R ² , where n is related to materials and process parameters and R is the evaporation source and The distance between the coated substrate 140, and θ is the angle between the vertical normal 402 to the point source and the normal 404 of the surface of the coated substrate 140, as shown in FIG. 22. Therefore, the position of the plasma source, the position of the electron beam source, and the shape and diameter of the dome will each affect the thickness of the coating film deposited on the substrate. The contour line 410 depicted in FIG. 22 schematically depicts the material deposition thickness at a given distance R from the point source 400. Each separated location on a particular curve will have approximately the same thickness of the deposited material. Given the potential variation in the thickness of the deposited coating, the uniformity mask positioned inside the vacuum chamber is appropriately shaped and positioned to provide a uniform coating thickness for the substrates positioned in different areas of the dome by acting on the dome When the substrate rotates in the vacuum chamber, it is achieved by providing a mask that intermittently shields the substrate from the coating material.

In addition, the coating device 500 also includes at least one thermal evaporation source 128. The thermal evaporation source 128 is used to vaporize the ETC coating material to accelerate the deposition of the coating material on the substrate fixed on the bottom surface of the dome 110. The at least one thermal evaporation source 128 is positioned in the vacuum chamber 102 below the dome 110. In the embodiment, the liquid ETC coating material is placed in a copper crucible filled with steel wool or a copper crucible filled with porous ceramic materials. The crucible is heated by the thermal evaporation source 128 to vaporize the ETC coating material, and then the ETC coating material is deposited on the substrate on the bottom surface of the rotating dome 110.

The coating device 500 also includes a plasma source such as an ion beam source. As described with reference to Figure 1A above, the plasma source 118 is located in the vacuum chamber 102, below the dome 110 and is usually directed upward to emit ions or plasma to the bottom surface of the dome 110, thereby enabling the coating to The optical coating film attached to the substrate at the bottom of the dome becomes dense and/or hardened. In the embodiment described herein, the plasma source is vertically oriented and positioned inside the vacuum chamber 102 such that the plasma source 118 is located radially outward from the rotation axis 171 of the spin dome 110 and from the plasma source 118 The injected plasma is incident on the bottom surface of the rotating dome 110 from at least one center of the dome to at least one outer edge 172 of the rotating dome. For example, in the embodiment, the plasma source 118 is positioned so that the distance S between the rotating shaft 171 of the rotating dome 110 and the plasma source 118 is greater than the plasma source 118 to the protruding periphery 173 (that is, the rotating circle The distance S'between the periphery of the cylinder restricted by the rotation of the top 110. In addition, the path between the plasma source 118 and the bottom surface of the dome 110 is not blocked (for example, blocked by a mask or the like), which increases the amount of plasma incident on the bottom surface of the dome 110. The positioning of the plasma source 118 in this manner reduces the average distance between the plasma source and the bottom surface of the dome, which therefore improves the density of the coating applied to the substrate attached to the bottom of the dome. The increased density of optical coating materials improves the scratch resistance of the coating. In an embodiment, the coating device 500 may also include a neutralizer 121, and the neutralizer 121 is positioned to project an electron cloud into the plasma path emitted from the plasma source 118. In particular, the plasma emitted from the plasma source 118 may include charged ions (for example, Ar ⁺¹ ions, O ⁺¹ ions, and/or O ⁺² ions), which are accelerated by the anode toward the substrate. Once the charged ions reach the substrate, they may repel the same charged ions, thus eliminating the effect of plasma assisted deposition. To overcome this problem, the neutralizer 121 is used to guide the electron cloud into the plasma path emitted from the plasma source 118. The neutralizer 121 includes an electron emitter such as a hot filament and/or a high-pass/high-rate electron emitting element. In some embodiments, the electron emitter may include a hollow cathode. The electron cloud emitted from the neutralizer interacts with the charged ions in the plasma, thereby neutralizing the charge (for example, Ar ⁺¹ ion → Ar ⁰ , O ⁺¹ ion → O ₂ , etc.).

Refer now to FIGS. 4A and 4B, which schematically depict a substrate carrier 130 for carrying a single-sized substrate. As shown in Figure 4A, the substrate carrier 130 has a non-magnetic substrate carrier base 131, a retention surface 131a for detachably fixing the substrate to be coated, a bottom surface 131b positioned on the opposite side of the retention surface 131a, and The carrier is magnetically attached to the dome 110 and a plurality of magnetic bars 134 for biasing the substrate carrier from the dome by a certain distance. In one or more embodiments, the substrate is detachably fixed on the retention surface 131a of the substrate carrier. Various mechanisms can be used to detachably fix the substrate carrier to the stagnant surface. In the embodiment depicted in FIGS. 4A and 4B, the substrate carrier 130 may also include a plurality of pins 136 (shown in FIG. 4B) and a spring system 132 for supporting the surface of the substrate 140. The spring system 132 generally includes a retractable pin 138a suitably positioned by a spring 133 (schematically depicted as an arrow) and a plurality of fixed pins 138b, the spring 133 biasing the retractable pin 138a in the direction indicated by the arrow. The pins 138a and 138b are used to hold the substrate 140 (indicated by the dashed line) in an appropriate position on the substrate carrier 130 when the glass substrate is being coated. In particular, when the substrate 140 is positioned on the stagnant surface 131a of the substrate carrier 130, a part of the edge of the substrate abuts the pin 138b and the spring system 132 is arranged to bias the pin 138a to contact the opposite side of the substrate, thereby detachably holding The substrate is held between the pins 138a, 138b. In one embodiment, the pins 138a and 138b are arranged on the substrate carrier base 131 so that no part of the pins extends beyond the surface of the substrate, thereby improving the uniformity of the coating thickness on the entire coating surface of the glass substrate. In another embodiment (discussed further herein with respect to FIG. 5), the pins are constructed and arranged on the substrate carrier base 131 to minimize the variation in the thickness of the coating film applied on the substrate. Fig. 4B is a side view of Fig. 4A, which shows the base plate 140, a plurality of magnets 134 and the side stopper 150. The base plate 140 is supported on the pin 136, which extends from the stagnant surface 131a into the non-magnetic The substrate carrier base 131 is a certain distance; the magnetic ray 134 extends from below the retention surface 131a of the substrate carrier 130 and passes through the substrate for a distance beyond the bottom surface 131b; the side stopper 150 extends from the non-magnetic substrate carrier base 131 to the distance The top surface 140a of the substrate 140 is at a distance, and the substrate 140 is detachably fixed on the stagnant surface 131a. The side stopper 150 orients the glass substrate on the non-magnetic substrate carrier base 131 without affecting the coating of the coating, thereby avoiding "shadows" on the surface of the glass substrate. In particular, the top surface 140a of the glass substrate will be coated with an optical coating and the coating surface is easy to clean. The size of the side stopper 150 is such that the side stopper 150 does not extend beyond the top surface 140a of the base 140, and the base 140 is detachably fixed on the stagnant surface 131a. For a glass substrate with a thickness of 5 mm, the top of the side stopper 150 will be located within a range of 2-3 mm below the top surface 140a of the substrate 140. The opening (no number) in the middle of the substrate carrier can reduce the weight of the carrier.

Although FIGS. 4A and 4B show a specific arrangement of the magnetic ray 134 in the substrate carrier base 131, it should be understood that other arrangements can also be considered. For example, in an embodiment, the magnetic ray 134 may be arranged in the substrate carrier base 131 to minimize the effect of the magnetic ray magnetic field on the coating process, such as mutually exclusive ions and/or specific patterns deposited on the substrate. Referring to FIG. 4C, the substrate carrier base 131 has a substrate retention area 141 (schematically depicted by a dotted line) on the substrate retention surface opposite to the bottom surface 131b. The area of the substrate stagnation area 141 is smaller than the area of the substrate stagnation surface, and the magnetic ray 134 is positioned on the bottom surface 131 b of the substrate carrier base 131 and outside the periphery 142 of the substrate stagnation area 141. Placing the magnetic beams 134 outside the periphery 142 of the substrate stagnation area 141 can reduce the effect of the magnetic field of each magnetic beam 134 on the coating process. In the embodiments described herein, the magnetic beam can be of an appropriate size to meet the size and weight of the substrate held on the stagnant surface of the substrate. For example, a larger magnetic beam can be used with a substrate carrier base sized to hold a larger substrate, while a smaller magnetic beam can be used with a substrate carrier base sized to hold a smaller substrate.

Refer now to FIG. 15, which depicts an adjustable substrate carrier 130a similar to the fixed substrate carrier 130 shown in FIG. 4A. The adjustable substrate carrier 130a has a non-magnetic substrate carrier base 131 including a plurality of magnetic beams 134. The magnetic beam 134 attaches the adjustable substrate carrier to the dome of the coating device. The adjustable substrate carrier 130a also includes one or more mechanisms or adhesive aids for detachably fixing one or more substrates to the substrate carrier 130a, or more specifically, to the retention of the substrate carrier Surface 131a. In the embodiment shown in Fig. 15, the mechanism or the adhesive aid includes a plurality of pins 136 extending from the retention surface 131a of the substrate carrier, which are used to support the detachable fixed on the adjustable substrate carrier 130a. The surface of the glass substrate. The mechanism or adhesive aid may include a housing 138aa that is positioned adjacent to the edge of the adjustable substrate carrier 130a and accommodates the retractable plug 138a (depicted as partially extending out of the housing). The housing 138aa includes a spring (not shown) positioned in the housing 138aa. The spring system biases the retractable plug 138a outward from the housing 138aa. The adjustable substrate carrier 130a may optionally include a side stop 150a (not shown in FIG. 15) for orienting the glass substrate on the adjustable substrate carrier 130a. In the embodiment depicted in FIG. 15, the adjustable substrate carrier 130a further includes a plurality of movable pins 139 for holding the edge of the glass substrate. The movable plug 139 is positioned in the rail 137 to accelerate the adjustable positioning of the movable plug 139 relative to the adjustable substrate carrier 130a. The combination of the movable plug 139 and the retractable plug 138a can use a single carrier to carry substrates of different sizes. One substrate or several substrates can be held by the pins and the selective side stopper 150a in the same manner as described above with respect to FIGS. 4A and 4B, in order to form an anti-shading coating on the substrate. In addition, the magnet 134 can be positioned outside the periphery of the substrate stagnation area, as described above with respect to FIG. 4C.

Refer now to FIG. 20A, which schematically depicts another embodiment of the substrate carrier 130b. In this embodiment, the substrate carrier 130 uses a layer of adhesive material 143 disposed on the retention surface 131a in the substrate retention area to detachably accommodate the substrate to be coated. The use of adhesive eliminates the need for mechanical fasteners that may cause variations in coating thickness. The adhesive material 143 usually includes a pressure-sensitive contact adhesive. Suitable materials may include, but are not limited to, acrylic adhesives, rubber adhesives, silicone adhesives, and/or similar pressure-sensitive adhesives. Alternatively, the substrate may be held on the retention surface 131a using electrostatic charges, for example, when the electrostatically charged film is positioned on the retention surface 131a and used as a bonding material. These materials allow the substrate to be firmly attached to the substrate carrier 130b during the coating process, and particularly to the retention surface 131a, but also allow the substrate to be easily removed from the substrate carrier 130b after the coating is completed. The magnet 134 can be positioned outside the periphery of the substrate stagnation area, as described above with respect to FIG. 4C. Furthermore, the use of a layer of adhesive material 143 on the stagnant surface can use a single size substrate carrier to carry substrates of different sizes and/or shapes and also allows multiple substrates to be attached to a single substrate carrier.

Referring now to the cross-sectional view of the substrate carrier 130b depicted in Figure 20B, the adhesive material 143 is positioned above the polymer film 144 in the embodiment, and then the polymer film 144 is adhered to the retention surface of the substrate carrier base 131 On 131a. In an embodiment, the polymer film may be a thermoplastic polymer film, such as a polyethylene film or a polyester polymer film.

In some embodiments, the polymer film may be a polymer film that can be statically charged. In these embodiments, a separate adhesive material is not required because the electrostatic charging film is used as an adhesive for detachably holding the substrate on the retention surface 131a. Suitable electrostatic charging films include, but are not limited to, Visqueen film produced by British Polyethylene Industries Limited (British Polyethylene Industries Limited).

The substrate carriers 130, 130a, and 130b have a non-magnetic substrate carrier base 131 and a plurality of magnetic bars 134 for holding the carrier on the dome 110 and for biasing the carrier by a certain distance from the dome. The use of these magnetic carriers is an improvement for dome carriers used for coating optical elements such as lenses. For example, FIG. 16A illustrates a conventional dome carrier 300 having a plurality of openings 302 for positioning the lens to be coated. When the lens is coated, it is placed in the opening of the carrier. However, in this conventional design, it is difficult to coat the inner and outer sides of the dome equally. It is also difficult to keep the coating material away from the uncoated lens surface. In addition, when the dome is heated, the coated portion can move relative to the opening of the dome, causing the dome to cool and break after coating. For example, FIG. 16B shows the lens 304 sliding down from a support shoulder 306 in the opening 302 of the dome carrier. Obviously, if the carrier cools faster than the lens 304, the contraction of the carrier will cause the lens to break. In the present application, because the substrate carrier is offset from the dome by a magnetic beam that holds the carrier to the dome, heat transfer is minimized and no cracking occurs when the dome is cooled. In addition, only the side of the glass product that is coated is easily affected by the coating material, because the contamination of the carrier/substrate is close to the inner surface of the dome. As a result, the reasons mentioned above in the conventional dome vehicle can be avoided.

Referring now to FIG. 5, which schematically depicts a cross-sectional view of an embodiment of the plug pins 138a, 138b, the glass substrate 140 is held against the plug pins by the force of the retractable plug 138a against the glass substrate. These pins can be used in a substrate carrier, as illustrated schematically in Figures 4A and 15. In particular, the glass substrate has a shaped edge fitted between the head 138h of the plug pins 138a and 138b and the rest of the plug body. The edge of the glass substrate can be chamfered, such as round, bull nosed, or other contours as shown in 141. When the substrate 140 is engaged with the pins 138a and 138b, the top surface 140a of the glass substrate is located 2-3 mm below the top of the pins 138a and 138b. In this figure, the symbol 140b represents the bottom surface of the substrate 140.

Referring now to FIGS. 4A and 6, the substrate 140 is loaded on the substrate carrier 130 and the combination of the substrate 140 and the substrate carrier 130 is magnetically attached to the bottom surface of the dome 110. When the substrate carrier 130 and the substrate 140 (dotted line) are loaded onto the dome 110 for coating, the retractable pin 138a is positioned perpendicular to the direction of rotation of the dome 110 as shown by the arrow; that is, the pin is compared to The fixing pin 138b is closer to the opening of the top T of the dome 110. When the substrate carrier is positioned in this way, the optical coating is uniformly deposited on the entire surface of the glass substrate 140 to form a "shadow-free" or "shadow-free" coated substrate 140. These terms, "no shadow" or "deshadow", refer to the following facts if: (1) The retractable pin 138a is not positioned on the dome 110, as described and shown in Figure 6, and (2) The top surface 140a of the glass substrate 140 is located less than 1 mm below the head 138h of the pin 138a, and (3) The top of the side stopper 150 is not lower than the top surface 140a; The deposition of the optical coating on these components and other components holding the substrate will be uneven. As a result, the optical coating will be thinner near the components and thicker away from the components. The result is non-uniform optical deposition or "shadows" that will be noticed by product users. Such shadows can be avoided using the device and method described in the present invention. Such shadows can also be avoided by using a substrate carrier that does not include any elements that protrude beyond the top surface of the substrate positioned on the carrier, such as a substrate carrier that uses a layer of adhesive material to detachably attach the substrate to the stagnant surface of the substrate , As depicted in Figure 20A.

Referring again to Figure 1A, once the adjustable substrate carrier 130a is magnetically attached to the dome 110, the material for coating the optical coating on the glass substrate is loaded into the separation boat 126 of the optical coating carrier 124 (Means separate source container). As mentioned above, the optical coating is composed of alternating thin layers of high and low refractive index materials or alternating thin layers of high and medium refractive index materials. Exemplary high refractive index materials with a refractive index n greater than or equal to 1.7 and less than or equal to 3.0: ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , Y ₂ O ₃ , Si ₃ N _4. SrTiO ₃ , WO ₃ ; an exemplary medium refractive index material system Al ₂ O ₃ having a refractive index n greater than or equal to 1.5 and less than 1.7; and an example of a refractive index n greater than or equal to 1.3 and less than or equal to 1.6 The low refractive index materials are SiO ₂ , MgF ₂ , YF ₃ , and YbF ₃ . In some embodiments, a medium refractive index material can be used to form the low refractive index layer L. Therefore, in some embodiments, the low refractive index material may be selected from SiO ₂ , MgF ₂ , YF ₃ , YbF ₃ and Al ₂ O ₃ . In an exemplary embodiment, the optical coating material is an oxide coating, wherein the high refractive index coating lanthanide series oxide (lanthanide series oxide), such as La, Nb, Y, Gd or other lanthanide series metals, and the low refractive index coating It is SiO ₂ . In addition, the material for coating easy-to-clean (ETC) coating is loaded into at least one thermal evaporation source 128. As mentioned above, the ETC material can be, for example, fluorinated silanes, typical perfluorocarbon alkyl silanes with the chemical formula (R _F ) _X SiX _4-x , where R _f is a straight line Chain C ₆ -C ₃₀ perfluorocarbon alkyl, X=Cl or -OCH ₃ -and X=2 or 3. The fluorocarbon has a carbon chain length in the range of greater than or equal to 3 nm and less than or equal to 50 nm.

Once the coating material is loaded, the vacuum chamber 102 is sealed and evacuated to a pressure less than or equal to 10 ^-4 Torr. Then the dome 110 rotates in the vacuum chamber by rotating the vacuum shield rotating shaft 117. Then the plasma source 118 is activated to guide ions and/or plasma to the glass substrate positioned on the bottom surface of the dome 110. When the optical coating material is coated on the glass substrate, the optical coating material can be compacted. Subsequently, the optical coating and the ETC coating are sequentially applied to the glass substrate. The optical coating is first coated by vaporizing the optical material positioned in the boat 126 of the optical coating carrier 124. In particular, the electron beam source 120 is energized and emits an electron flow, and the electron flow is guided by the electron beam mirror 122 to the boat 126 of the optical coating carrier 124. When the glass substrate and the dome 110 rotate, the vaporized material is deposited on the surface of the glass substrate. The rotation of the dome 110 together with the mask 125 and the orientation of the glass substrate on the substrate carrier 130 allows the optical coating material to be evenly coated on the glass substrate carrier, so as to avoid "shadows" appearing on the coating surface of the glass substrate . As described above, the electron beam source 120 is used to sequentially deposit a thin layer of high refractive index material and a thin layer of low refractive index material or a thin layer of medium refractive index material to achieve an optical coating with desired optical characteristics. The quartz monitor 114 and the optical fiber 112 are used to monitor the thickness of the deposited material and thereby control the deposition of the optical coating, as described herein.

Once the optical coating material used for optical coating has been coated on the glass substrate to the desired thickness, the optical coating is stopped and the ETC coating is coated on the glass substrate by thermal evaporation as the dome 110 rotates. On the entire optical coating. In particular, the ETC material located in the at least one thermal evaporation source 128 is heated, thereby vaporizing the ETC material in the vacuum chamber 102. The vaporized ETC material is deposited on the glass substrate by condensation. The rotation of the dome 110 and the orientation of the glass substrate on the substrate carrier 130 help to evenly coat the ETC material on the glass substrate. The quartz monitor 114 and the optical fiber 112 are used to monitor the thickness of the deposited material and thereby control the deposition of the ETC coating, as described herein.

Figures 7A-7C are schematic representations of the grafting reaction of silane fluoride with glass or oxide optical coating (that is, the reaction between ETC coating material and glass or oxide optical coating). Figure 7C is a diagram showing that when fluorocarbon trichlorosilane is grafted with glass, silane silicon atoms can be (1) triple bonds (three Si-O bonds) to the glass substrate or substrate On the surface of the upper multilayer oxide coating, or (2) Double bond to the glass substrate and have a Si-O-Si bond adjacent to the R _F Si functional group. The ETC coating process time is very short and can be used to provide ETC coatings with a thickness greater than or equal to 3 nm and less than or equal to 50 nm, which are spread over the entire freshly coated optical coating and do not need to break the vacuum (meaning That is, there is no need to expose the optical coating to the surrounding atmosphere). In the coating process described in this article, the ETC material is vaporized from a single source. However, it should be understood that ETC materials can also be vaporized from multiple sources at the same time. For example, 2-5 separate sources of ETC material have been found to be helpful. In particular, using multiple sources containing ETC materials will form a more uniform ETC coating and increase the durability of the coating. The term "source" used in this article refers to the container or crucible from which the ETC material is thermally vaporized.

In the embodiments described herein, the SiO ₂ layer is usually coated as a cover layer of the optical coating. Before the deposition of the ETC coating, the SiO ₂ layer is usually deposited as part of the optical coating. This SiO ₂ layer provides a dense surface for the grafting and cross-linking of silicon atoms of the ETC coating, because these thin layers are deposited in a high vacuum (10 ^-4 -10 ^-6 Torr) environment without free OH groups . Free OH groups, for example, a thin layer of water on the surface of glass or AR, are disadvantageous in the deposition process of ETC materials, because OH prevents silicon atoms in ETC materials from interacting with metal oxide or silicon oxide surfaces. That is, the oxygen atoms on the optical coating surface are bonded. When the deposition device breaks the vacuum, it means that the device is opened and exposed to the atmosphere. The air in the environment containing water vapor enters and the silicon atoms of the ETC coating react with the surface of the optical coating to generate between the ETC silicon atoms and the surface oxygen atoms At least one chemical bond, and releases alcohol or acid once exposed to air. Because ETC coating materials usually contain 1-2 fluorinated groups and 2-3 reactive groups, such as CH ₃ O- groups, ETC coatings can interact with 2- The 3 oxygen atoms are bonded or cross-linked with other coating molecules, as shown in Figure 7C, to produce a strong bonding ETC coating. The surface of SiO ₂ deposited by PVD is pristine and has an active surface. For example, for PVD deposited SiO ₂ coating, it has much lower activation energy than glass with complex surface chemical composition. As shown in Figure 8, there are environmental pollutants or With a thin layer of water.

Therefore, once the ETC coating has been coated on the entire optical coating, the glass substrate that has the optical coating and ETC coating is removed from the chamber and allowed to be cured in the air. If only placed at room temperature (about 18-25 ^o C, relative humidity RH 40%) to be cured, curing will take 1-3 days. Higher temperatures can be used to accelerate curing. For example, in one embodiment, the ETC coated article may be heated to 80-100 ^o C, for about 10 minutes to about 30 minutes in a humidity greater than 50% and less than 100% of the range. Usually the relative humidity is in the range of 50-85%.

Once the ETC coating is cured, the coating surface is wiped with a soft brush or isopropyl alcohol to remove any ETC materials that have not yet been bonded to the optical coating.

The methods and devices described herein can be used to produce coated glass products, such as coated glass substrates, which have both optical coatings (such as AR coatings or coatings with similar optical functions) and ETC coatings positioned on the entire optical coatings. Using the methods and devices described in this article, coated glass products usually have no shadows on the entire optical coating surface of the glass products. In some embodiments, the optical coating coated on the glass article may have a plurality of periods, and each period includes a high refractive index material H layer having a refractive index n greater than or equal to 1.7 and less than or equal to 3.0 and a layer having a refractive index greater than or equal to 1.3. And the low refractive index material L layer with refractive index n less than or equal to 1.6. The high refractive index material layer may be the first layer per period and the low refractive index material L layer may be the second layer per period. Alternatively, the low refractive index material layer may be the first layer per period and the high refractive index material H layer may be the second layer per period. In some embodiments, the number of coating cycles in the optical coating can be greater than or equal to 2 and less than or equal to 1,000. The optical coating may further include a covering layer of SiO ₂ . The cover layer can be coated on one or more periods and can have a thickness in the range of greater than or equal to 20 nm and less than or equal to 200 nm. In the embodiments described herein, the optical coating film may have a thickness in the range of greater than or equal to 100 nm and less than or equal to 2000 nm. However, larger thicknesses are also possible, depending on the intended use of the coated product. For example, in some embodiments, the thickness of the optical coating may be in the range of 100 nm to 2000 nm. In some other embodiments, the optical coating thickness may be in the range of 400 nm to 1200 nm or even in the range of 400 nm to 1500 nm.

The thickness of each layer of the thin layer of high refractive index material and the thin layer of low refractive index material may range from greater than or equal to 5 nm and less than or equal to 200 nm. The thickness of each layer of the thin layer of high refractive index material and the thin layer of low refractive index material may range from greater than or equal to 5 nm and less than or equal to 100 nm. As will be described further herein, coated glass articles exhibit improved scratch resistance to the specific coating method or technique used herein. The degradation of the coating film applied to the glass product can be evaluated by the water contact angle of the glass coating film after the scratch test. The implementation of the scratch test is to use 0000# grade steel wool to scrape the coating surface of the glass substrate under a positive load of 10 kg. The size of the scraping area is 10 mm×10 mm. The wiping frequency is 60 Hz and the wiping distance of steel wool is 50 mm. The scratch test is performed under the relative humidity RH<40%. In the examples described herein, the glass article has a water contact angle of at least 75 ^° after 6,000 scratch cycles. In certain embodiments, the glass article has a water contact angle of at least 105 ^° after 6,000 scratch cycles. In still other embodiments, the glass article having a water contact angle greater than 90 ^o times after 10,600 cycles scratched.

The scratch resistance and degradation resistance of glass products can also be evaluated by the length of the scratch on the glass product after the scratch test. In the examples described herein, the coated glass article has a surface scratch length of less than 2 mm after 8000 scratch cycles.

In addition, the scratch resistance and degradation resistance of glass products can also be evaluated by the changes in reflectivity and/or transmittance of the glass products after the scratch test, which will be described in more detail herein. In some embodiments, the% reflectance of the glass article after at least 8,000 scratch/scratch cycles is substantially the same as the% reflectance of the unscratched/unscratched glass article. In some embodiments, the% transmission of the glass article after at least 8,000 scratch/scratch cycles is substantially the same as the% transmission of the unscratched/unscratched glass article.

The deposition methods described in this article can be used to produce shadow-removing optical coatings. This means that the optical coating is uniformly deposited on the entire coating surface of the glass substrate. In the embodiment of the coated glass substrate described herein, the variation of the optical coating thickness from the first edge of the optical coating of the glass substrate to the second edge of the optical coating is less than 4%. For example, in some embodiments, the thickness variation of the optical coating from the first edge of the optical coating on the glass substrate to the second edge of the optical coating is less than or equal to 3%. In some other embodiments, the thickness variation of the optical coating from the first edge of the optical coating of the glass substrate to the second edge of the optical coating is less than or equal to 2%. In still other embodiments, the thickness variation of the optical coating from the first edge of the optical coating on the glass substrate to the second edge of the optical coating is less than or equal to 1%.

The coating device 500, substrate carrier 130 and/or method described herein can be used to form other coatings on glass substrates or other substrates (such as plastic substrates). Such other coatings may include optical decorative coatings or protective coatings, which may include, but are not limited to, non-absorptive materials and absorptive materials. Exemplary decorative coatings can be formed of transparent dielectric or absorbing materials. Such materials include metals (such as Cr, Ag, Au, W, Ti and the like), semiconductors (such as Si, AlN, TCO materials such as ITO and SnO _x , Ge and the like) and absorptive materials (SiN _x , SiO _x N _y , TiN, AlSiO _x , CrO _x and the like).

Ion-assisted electron beam deposition provides unique advantages for coating small and medium glass substrates, such as those with a face size ranging from approximately 40 mm×60 mm to approximately 180 mm×320 mm, depending on the cavity The size of the room. The ion-assisted coating process provides a freshly deposited optical coating on the glass surface. The glass surface has low surface activation energy for subsequent ETC coating coating, because there are no surface contaminants that may affect the performance and reliability of ETC coating ( Water or other environment). After the optical coating is completed, directly coating the ETC coating system can improve the cross-linking between the difluorocarbon functional groups, improve the abrasion resistance, and improve the contact angle performance after thousands of scratch cycles applied to the coating (higher oleophobic and hydrophobic Contact angle). In addition, ion-assisted electron beam coating greatly reduces the coating cycle time to increase the utilization rate and output rate of the coating machine. Furthermore, there is no need for heat treatment or ultraviolet curing after the deposition of the ETC coating, because the lower activation energy of the optical coating surface makes the process compatible with the ETC process after heating is not allowed. Using the ion-assisted electron beam PVD process described in this article, ETC materials can be coated on selected areas to avoid contamination to other locations on the substrate. Example 1 :

第2表

範例 2 ： Four layers of SiO ₂ /Nb ₂ O ₅ /SiO ₂ /Nb ₂ O ₅ /substrate AR optical coating are deposited on 60 pieces of Gorilla ^TM glass (available from Corning on the market), each piece size (length, width) , Thickness) is about 115 mm L×60 mm W×0.7 mm T. The coating is deposited using the method described in this article. The AR coating has a thickness of approximately 600 nm. After the AR coating is deposited, the ETC coating is coated on top of the AR coating by thermal evaporation using perfluoroalkyl trichlorosilanes. The perfluoroalkyl trichlorosilanes have a range of 5 nm to 20 nm The inner carbon chain length (Daikin’s Optool ^TM fluorine coating is used as an exemplary type). The deposition of AR and ETC coatings is performed in a single chamber coating device as shown in Figure 1A. After the AR coating is deposited, the AR coating source material is turned off and the ETC material is thermally evaporated and deposited on the AR coated glass. The coating process includes part loading/unloading in 73 minutes. Next, after the ETC coating is cured, the surface is wiped using the various scratch cycles shown in Table 1 to determine the water contact angle. The scratch test was conducted with #0 steel wool under a load of 1 kg. The data in Table 1 indicate that the sample has very good anti-wear and hydrophobic properties. The coating sequence and the thickness of each layer of 6 layers of Nb ₂ O ₅ /SiO ₂ coated on the glass substrate are shown in Table 2. Table 1: Water contact angle scratch test results

Table 2

Example 2 :

In this example, the same fluorine coating used in Example 1 is coated on the GRIN lens as an optical connector, as shown in FIG. 9, which is used on the optical fiber 206 for laptop computers. The symbol 200 and the arrow point to the selected area of the GRIN lens 208 for placing the ETC coating on top of the 850 nm AR coating to provide particle resistance and abrasion resistance. Symbol 202 indicates the connection of the optical fiber to a laptop or tablet device, and symbol 204 indicates that the coated optical fiber is used to connect to a laptop or media dock.

Figure 10 is a 6-layer AR coating with a 8-10nm thermal deposition ETC coating on the substrate/(Nb ₂ O ₅ /SiO ₂ )3. The ETC/6L-AR coating is compared to the spray coating ETC coating. Scratch test data of glass samples. The glass is 0.7 mm thick and is commercially available Corning's No. 2319 glass, which is chemically tempered (ion exchange) glass. The scratch test is carried out under the following conditions: 0000# steel wool, 10 kg load on 10 mm×10 mm area, 60 Hz, 50 mm wiping distance, RH<40%. The water contact angle greater than 75 ^° is the criterion for judging the failure of the coating. It has been found that glass with AR coating but no ETC coating is scratched after only 10-12 wipe cycles. Figure 10 shows that the two glass samples were tested with a water contact angle of 120 ^o , and after 6000 scratch cycles, only the glass sample with ETC coating had a water contact angle of 80 ^o , but as described in this article The glass sample, ETC/6 layer-AR coating, has a water contact angle of at least 105 ^o . After 10,000 cycles scratches, water -AR coated article of ETC / 6-based layer in contact angle greater than 90 ^o. This test clearly indicates that glass products with ETC coating deposited on top of AR coating have a greater degree of scratch resistance than glass products with only ETC coating applied to glass.

Figure 11 is (1) a glass product with 6 layers of PVD IAD-DB AR coating and a layer of 8-10 nm thermal deposition ETC coating on top of the AR coating (indicated by the symbol 220 and the diamond data mark). ) Commercially available glass products with PVD-AR coating deposited by the first commercial coater device and ETC deposited by commercial processes such as immersion or spraying in the second chamber (indicated by the symbol 222 and the square data mark ) Comparison of scratch durability. The two coatings were deposited on the same chemical blend (ion exchange), 0.7 mm thick Corning No. 2319 glass. The glass product 220 is coated according to the method described herein. Commercially available glass products are coated by commercial coating suppliers. The scratch durability test is carried out at 40% relative humidity. At the point indicated by the arrow 224, after 800 cycles, only shallow scratches with a length of less than 2 mm appeared. On the contrary, at the point indicated by the arrow 226, only after 200 cycles, a deep scratch with a length greater than 5 mm appears. The test results indicate that the scratch durability of the AR coated-ETC glass coated in this article is at least 10 times greater than that of the commercially available products.

Figure 17B is a graph depicting the water contact angle compared to the scratch cycle, which shows the improvement obtained by using the coating device configured as depicted in Figure 17A. The water contact angle results can be compared with the water contact angle results in Figures 10 and 11. The data in Figure 17B shows that after 10,000 scratch cycles, all the substrates shown in Figure 17B have a water contact angle greater than 110 ^° , and substantially all substrates have a water contact angle of 112 ^° or greater . In contrast, the data in Figures 10 and 11 show that after 10,000 scratch cycles, the water contact angle is less than 100 ^° . Furthermore, the data in Figure 17B shows that for the substrate after 12,000 scratch cycles, the water contact angle of the substrate is greater than 106 ^° .

Figure 12 is a graph of% reflectivity versus wavelength, where reflectivity means the percentage of light reflected from the surface of coated glass products coated with AR coating and ETC coating as described in this article. New (unscratched or unscratched) products are used in each scratch test. Scratching/scraping is performed under the following conditions: 0000# steel wool, 10 kg load in the area of 10 mm×10 mm, 60 Hz, 50 mm wiping distance, RH<40%. The reflectance was measured after 6K, 7K, 8K and 9K wipes. The graph shows that the new product has substantially the same reflectivity as the product after being wiped up to 8K times. After 8K wipes, the reflectivity increased. This increase in reflectivity is believed to be the result of slight scratches on the glass surface caused by a large amount of scratching. The letter "A" in the figure means "after wiping" and the letter "B" means "before wiping" (no wiping). The letter "K" means "kilo" or "thousand".

Figure 13 shows the relationship between% transmittance and wavelength. The test was performed on coated glass products coated with AR coating and ETC coating as described herein. New (unscratched or unscratched) products are used in each scratch test. The penetration test uses the same products as the reflection test. The graph points out that the new product has substantially similar penetration rate with the product after being wiped for up to 8K times, and the penetration rate is in the range of 95-96%. After 8K wipes, the transmittance dropped to about 92% across the entire wavelength range. This reduction in penetration is believed to be the result of slight scratches on the glass surface caused by a large amount of scratching. The letter "A" in the figure means "after wiping" and the letter "B" means "before wiping" (no wiping). The letter "K" means "kilo" or "thousand".

The data in Figures 12 and 13 indicate that the optical coating on glass products not only has excellent water contact angle retention as shown in Figures 10 and 11, but also has a high degree of durability.

Figure 14 is a graph of reflectivity% versus wavelength, which shows the effect of AR coating layer/number of cycles on reflectivity, compared to glass without AR coating. Curve 240 represents uncoated ion exchange glass, Corning's number 2319. Curve 244 represents a ₂ -layer or 1-period coating composed of a pair of SiO ₂ /Nb ₂ O ₃ thin layers. Curves 246 and 248 are 4-layer (2-period) and 6-layer (3-period) coatings composed of SiO ₂ /Nb ₂ O ₃ thin layer pairs. Curve 242 is a 1-layer Nb ₂ O ₃ coating. The data pointed out that increasing the number of AR coating stacks (layers/period) will expand the effectiveness of the AR coating spectral range and will also reduce the reflectivity%. Example 3 :

Figure 18 is a computer simulation graph of reflectance (y-axis) as a function of wavelength (x-axis), which is for glass substrates coated with 6 layers of AR coating (Nb ₂ O ₅ /SiO ₂ ) and ETC. The AR coating is simulated with a thickness variation of 2%. As a result, the obtained reflectance profile simulates the reflectance of 6-layer AR coating (Nb ₂ O ₅ /SiO ₂ ) and ETC coating, where the ETC coating has a thickness variation of 2%. Figure 19 graphically depicts reflectance (y-axis) as a function of wavelength (x-axis), which is for the 6-layer AR coating (Nb ₂ O ₅ /SiO ₂ ) and Multiple real samples with 1 layer of ETC coating and coating. As depicted in Figure 19, the reflectance profile of the real sample is similar to the reflectance profile of the simulated sample, thus showing that the sample coated with the method has an optical coating, which is on the entire coated substrate (meaning from the optical The thickness variation of the optical coating from the first edge to the second edge of the coating is less than 3%.

The AR/ETC coating described in this article can be used in many commercial products. For example, the resulting coating can make televisions, mobile phones, electronic tablets, and book readers and other devices readable in sunlight. AR/ETC coatings are also useful in the following products: anti-reflective beam splitters, mirrors, mirrors and laser products; optical fibers and components used in telecommunications; used in biological and medical applications and used in antimicrobial surfaces Optical coating.

It is obvious to those skilled in the art that various modifications and changes can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Therefore, the purpose of the description covering the modifications and variations of the various embodiments described herein is to provide such modifications and variations within the scope of the appended patent claims and their equivalents.

100‧‧‧Coating device 102‧‧‧Vacuum chamber 110‧‧‧Rotating Dome 110a‧‧‧block 112‧‧‧Fiber 114‧‧‧Quartz monitor 116‧‧‧glass plate 116a‧‧‧Opening 116b‧‧‧surface 117‧‧‧Rotation axis 118‧‧‧Plasma source 118a‧‧‧Ion source 119‧‧‧Vacuum Sealed Bearing 120‧‧‧Electron beam source 120a‧‧‧First electron beam source 120b‧‧‧Second electron beam source 121‧‧‧Neutralizer 122‧‧‧Electron beam mirror 124‧‧‧Optical Coating Carrier 125‧‧‧Mask, first mask 125a‧‧‧bracket 126‧‧‧boat 127‧‧‧Mask 128‧‧‧Thermal evaporation source 129‧‧‧Second Mask 130‧‧‧Substrate Carrier 130a‧‧‧Surface, adjustable substrate carrier 130b‧‧‧Substrate carrier 131‧‧‧Substrate carrier base 131a‧‧‧Retention surface 131b‧‧‧Bottom 132‧‧‧Spring System 133‧‧‧Spring 134‧‧‧Components, magnets 136‧‧‧Latch 137‧‧‧Orbit 138a‧‧‧Spring-loaded adjustable latch, retractable latch 138aa‧‧‧Shell 138b‧‧‧ Bolt, fixed bolt 138h‧‧‧Head 139‧‧‧Mobile latch 140‧‧‧Substrate/Product 140a‧‧‧Top surface 140b‧‧‧Bottom 141‧‧‧Substrate retention area, forming edge 142‧‧‧Around 143‧‧‧Adhesive material 144‧‧‧Polymer film 150‧‧‧Side stop 150a‧‧‧Side stop 160‧‧‧Frame 161‧‧‧Lip/Edge 162‧‧‧spoke 164‧‧‧Open 168‧‧‧Side edge 171‧‧‧Rotation axis 172‧‧‧Outer edge 173‧‧‧Protruding from the periphery 175‧‧‧Actuator 180‧‧‧First position 181‧‧‧Second position 206‧‧‧Fiber 208‧‧‧GRIN lens 220‧‧‧Glassware 224‧‧‧Arrow 240‧‧‧Curve 242‧‧‧Curve 244‧‧‧Curve 246‧‧‧Curve 248‧‧‧Curve 300‧‧‧Dome Vehicle 302‧‧‧Open 304‧‧‧lens 306‧‧‧Shoulder 400‧‧‧point source 402‧‧‧Vertical normal vector 404‧‧‧Normal 410‧‧‧Contour 500‧‧‧Coating device

FIG. 1A is a schematic diagram of the coating device 100 according to one or more embodiments described in this document;

Figure 1B schematically depicts an enlarged view of the glass plate 116 and illustrates the opening 116a for receiving the quartz monitor;

Figure 1C schematically depicts an enlarged view of a glass plate and optical fiber with a quartz monitor housed in the opening, both of which are used to measure and control the deposition of optical coating materials attached to the glass substrate of the substrate carrier;

Figure 2 shows a top view of the dome portion of the coating device shown in Figure 1A, showing a plurality of substrate carriers magnetically attached to the dome;

Figure 3A schematically depicts an oblique top view of the dome block of the coating device in Figure 1A with a plurality of substrate carriers magnetically attached to the dome;

Figure 3B schematically depicts the frame supporting the dome block 110a; the frame 160 has an outer lip/edge 161 as shown in Figure 3A, and an opening on the rotating shaft 117 (not shown) to be attached to The inner edge (unnumbered) at 164 and wide enough to accommodate the plurality of spokes 162 on the side edge of the dome block at 168 as shown in the figure;

FIG. 4A schematically depicts a non-magnetic substrate carrier 130 having a plurality of elements 134 for magnetically attaching the carrier to the dome 110 and for holding the glass substrate/product 140 during the coating process;

Fig. 4B is a side view of Fig. 4A, showing the glass placed on the pin 136 extending from the substrate carrier surface 130a into the substrate carrier base 131 at a distance from the substrate 140 and extending from the surface 130a of the substrate carrier 130 A plurality of magnets 134 passing through the substrate for a certain distance beyond the base 130b, and a side stop 150 extending from the base of the carrier 130 to a distance from the top surface 140a of the glass product 140;

FIG. 4C is a bottom view of the substrate carrier base 131, which depicts the magnet 134 positioned outside the periphery 142 of the substrate stagnation area 141;

Figure 5 schematically depicts one of the plug pins 138a and 138b and the shaped edge 141. The glass substrate 140 is held against the plug by the force of the spring-loaded adjustable plug 138a against the glass substrate. The shaped edge 141 is in contact with the plug. , In this example, the chamfered edge;

Figure 6 shows the substrate carrier 130 attached to the dome 110 so that the retractable pin 138a is positioned perpendicular to the rotation direction, which means that the pin 138b is closer to the opening of the top T of the dome 110. Also shown in Figure 6;

Figure 7A-Figure 7C are schematic representations of the fluorinated silane grafting reaction with glass or oxide AR coating;

Figure 8 shows the AR optical coating layer under the ECT coating to provide a barrier layer that isolates the chemical composition and contamination of the glass surface, and further provides a lower activation energy address for fluorinated silane to maximize Coating density and chemical bonding of AR optical coating with crosslinking on the coating surface to maximize abrasion reliability (persistence);

Figure 9 shows the use of AR-ETC coated GRIN lens 208 with optical fiber 206 and some of its uses;

Figure 10 shows the scratches of glass products with 1 layer of PVD 8-10nm ETC on top of 6 layers of ARC (Nb ₂ O ₅ /SiO ₂ ) coating and glass products with only spray coated ETC coating (spray coated ETC coating) Test data comparison;

Figure 11 is a comparison of scratch reliability: glass products with 6 layers of PVD IAD-DB AR coating and 1 layer of 8-10 nm thermal deposition ETC coating on top of AR coating are compared with those with the first conventional coating machine (coater) PVD AR coating deposited in the glass product and ETC deposited in the second conventional coating machine;

Figure 12 is a graph showing the relationship between% reflectance and wavelength of glass products coated with AR coating and ETC coating after 6K, 7K, 8K and 9K wipes;

Figure 13 is a graph showing the relationship between% transmittance and wavelength of glass products coated with AR coating and ETC coating after 6K, 7K, 8K and 9K wipes;

Figure 14 is a graph of reflectance% vs. wavelength and shows the effect of AR coating layer/period reflectance vs. glass without AR coating;

Fig. 15 shows an adjustable magnetic carrier 130a, which is substantially similar to the carrier 130 shown in Fig. 4A and can be used for a single carrier with different size substrates;

FIG. 16A shows a conventional dome carrier 300, which has a plurality of openings 302 for placing the coated lens;

FIG. 16B shows the lens 304 sliding down from the shoulder 306 of the carrier 300 in the opening 302. The lens 304 is located at a position where the carrier 300 will break when the carrier 300 cools;

Figure 17A is a diagram of an embodiment of the coating device. The coating device has a mask covering a selected area of the dome to improve the uniformity of the optical coating;

Figure 17B shows the water contact angle (Water Contact Angle) compared to the Abrasion Cycle (Abrasion Cycle) graph, which shows the improvement obtained by using the mask shown in Figure 17A;

Figure 18 is a simulated graph of reflectance (y-axis) as a function of wavelength (x-axis), which is for a glass substrate coated with 6 layers of AR coating (Nb ₂ O ₅ /SiO ₂ ) and 1 layer of ETC coating , ETC coating is AR coating with 2% thickness variation;

Figure 19 graphically depicts the reflectance (y-axis) as a function of wavelength, which is for multiple real samples coated with 6 layers of AR coating (Nb ₂ O ₅ /SiO ₂ ) and 1 layer of ETC coating;

FIG. 20A schematically depicts the retention surface 131a of the substrate carrier with a layer of adhesive material 143 deposited thereon;

Figure 20B schematically depicts a cross-sectional view of the substrate carrier. The polymer film 144 and the adhesive material 143 are positioned on the substrate carrier base;

Figure 21A is a vertical cross-sectional view schematically depicting an embodiment of the coating device;

Figure 21B schematically depicts a horizontal cross-sectional view of the coating device of Figure 21A; and

Figure 22 graphically depicts the variation of the coating thickness as a function of the relative positioning of the coating source and the substrate to be coated.

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100‧‧‧Coating device

102‧‧‧Vacuum chamber

110‧‧‧Rotating Dome

112‧‧‧Fiber

114‧‧‧Quartz monitor

116‧‧‧glass plate

117‧‧‧Rotation axis

118‧‧‧Plasma source

119‧‧‧Vacuum Sealed Bearing

120‧‧‧Electron beam source

121‧‧‧Neutralizer

122‧‧‧Electron beam mirror

124‧‧‧Optical Coating Carrier

125‧‧‧Mask, first mask

125a‧‧‧bracket

126‧‧‧boat

128‧‧‧Thermal evaporation source

130‧‧‧Substrate Carrier

160‧‧‧Frame

171‧‧‧Rotation axis

Claims (12)

A glass product, comprising: a glass substrate; an optical coating applied on the top of the glass substrate, the optical coating comprising at least three periods consisting of a layer of high refractive index material H and a layer of low refractive index material L, the layer The high refractive index material H has a refractive index n greater than or equal to 1.7 and less than or equal to 3.0, and the layer of low refractive index material L has a refractive index n greater than or equal to 1.3 and less than or equal to 1.6, the layer has a high refractive index Material H is a first layer per period, and the layer of low refractive index material L is a second layer per period; and the optical coating includes an SiO ₂ coating layer; an easy-to-clean coating is applied to the SiO ₂ coating layer And after 10,000 scratch cycles, the glass product formed by the glass substrate, the optical coating including the SiO ₂ coating and the easy-to-clean coating exhibits a water contact angle greater than 90°. The glass product according to claim 1, wherein a number of coating cycles is in a range greater than or equal to 3 and less than or equal to 1000. The glass product according to claim 1, wherein the optical coating film has a thickness in a range from greater than or equal to 100 nm to less than or equal to 2000 nm. The glass product according to claim 1, wherein a number of coating cycles is in a range greater than or equal to 3 and less than or equal to 20, and a thickness of each layer of the high refractive index material H and the low refractive index material L is In a range greater than or equal to 5 nm and less than or equal to 200 nm. The glass product according to claim 1, wherein the layer of high refractive index material H is selected from the group consisting of ZrO ₂ , HfO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , Y ₂ O ₃ , Si ₃ N ₄ , SrTiO ₃ and WO ₃ . The glass product according to claim 1, wherein the layer of low refractive index material L is selected from the group consisting of SiO ₂ , MgF ₂ , YF ₃ , YbF ₃ and Al ₂ O ₃ . The glass article according to claim 1, wherein the glass article has a water contact angle of at least 75° after 6000 scratch cycles. The glass article of claim 1, wherein a% reflectance of the glass article after at least 8000 scratch/scratch cycles is substantially the same as the% reflectance of an unscratched/unscratched glass article rate. The glass article according to claim 1, wherein after at least 8000 scratching/wiping cycles, a% transmission rate of the glass article is substantially the same as the% of an unscratched/unscratched glass article wear Transmittance. The glass product according to claim 1, wherein a change in a thickness of the optical coating film of the glass product from a first edge of the optical coating film to a second edge of the optical coating film is less than or equal to 3%. The glass product according to claim 1, wherein a change in a thickness of the optical coating film of the product from a first edge of the optical coating film to a second edge of the optical coating film is less than or equal to 2%. The glass product according to claim 1, wherein a change in a thickness of the optical coating film of the glass product from a first edge of the optical coating film to a second edge of the optical coating film is less than or equal to 1%.

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