A coated article
Patent Information
- Application Number
- CN202522084850.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-28
- Publication Date
- 2026-09-29
- Estimated Expiration
- 2035-09-28
AI Technical Summary
[0004]然而，现有的AR涂层(抗反射涂层，涂层厚度＜600nm)普遍存在硬度不足(＜12Gpa)或内应力过高(＞850Mpa)的问题，这些问题导致膜层易开裂，脱落，基板产品翘曲变形
[0026]本实用新型提供的镀膜制品能够兼顾优异的纳米压痕硬度以及耐磨性能，通过在基材的一侧镀特定的膜层结构(交替层叠设置的低折射率层和高折射率层)，在不改变材料硬度的情况下，使部分高折射率层的高硬材料层(通常表现压应力)表现出张应力，从而去中和其余高折射率层的高硬材料层产生的压应力，确保镀膜制品中的膜层的应力较低，有效保证了膜层结构的稳定性，从而能够有效防止膜层开裂、脱落或剥离。
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Figure CN224812472U_ABST
Abstract
Description
Technical Field
[0001] This utility model relates to the field of coating product technology, and specifically to a coating product. Background Technology
[0002] Ultra-hard and durable glass coatings have always had a large market demand and are widely used in the screens of 3C electronic products.
[0003] In applications such as camera lenses, mobile phone screen covers, and automotive and industrial touch display cover glass, hard coatings with high light transmittance and high nano-hardness are typically required.
[0004] However, existing AR coatings (anti-reflective coatings with a thickness of <600nm) generally suffer from insufficient hardness (<12Gpa) or excessive internal stress (>850Mpa). These problems lead to easy cracking and peeling of the film, and warping and deformation of the substrate product.
[0005] To address the aforementioned issues, one approach is to use a multilayer TiO2 / SiO2 / MgF2 coating. While this method can reduce reflectivity, the coating has low hardness. High-hardness materials (such as SiNx) have high internal stress, which can easily lead to product warping and deformation, especially for thinner glass substrates, where the deformation is more severe.
[0006] Secondly, by adding a wear-resistant layer between the anti-reflective coating and the substrate, the nano-indentation hardness and wear resistance of the AR coating can be improved. However, due to the absorption of the wear-resistant layer, the transmittance often fails to reach the ideal level.
[0007] Third, an ultra-thick film layer is set in the anti-reflective coating to improve the hardness of the entire coating; however, due to the thickness of the film layer, the sputtering efficiency of the entire coating is greatly extended, and at the same time, it brings extremely high stress, which will also lead to a loss of product transmittance.
[0008] Therefore, there is an urgent need to develop a new type of low-stress superhard coating product to solve the above-mentioned defects. Utility Model Content
[0009] The purpose of this invention is to provide a low-stress, ultra-hard coated product without increasing the film thickness.
[0010] To achieve the above objectives, this utility model provides a coated product, which includes a substrate and a film layer. The film layer is bonded to the substrate. The film layer includes alternating layers of low refractive index and high refractive index. The high refractive index layer is a high-hardness material layer. The high-hardness material layer includes at least one compressive stress layer and multiple tensile stress layers. The thickness of the compressive stress layer and the thickness of the multiple tensile stress layers satisfy the stress neutralization in the film layer.
[0011] Preferably, the thickness of the film is less than 550 nm, and the nanoindentation hardness of the film is above 15 GPa.
[0012] Preferably, the compressive stress of the membrane layer is n, where 0 < n < 540 MPa.
[0013] Preferably, the ratio of the total thickness of the tensile stress layer to the total thickness of the compressive stress layer is defined as m, where 1.0 < m < 1.2.
[0014] Preferably, based on the total thickness of the film, the total thickness of the high refractive index layer accounts for 56%-64%.
[0015] Preferably, the total thickness of the tensile stress layer accounts for 28%-35%.
[0016] Preferably, the total thickness of the compressive stress layer accounts for 27%-30%.
[0017] Preferably, the high refractive index layer comprises one compressive stress layer and three tensile stress layers, and the compressive stress layer is bonded to the low refractive index layer of the outermost layer of the film.
[0018] Preferably, the three tensile stress layers in the coated product, from the inside out, are defined as a first tensile stress layer, a second tensile stress layer, and a third tensile stress layer, wherein the thickness of the first tensile stress layer is less than the thickness of the second tensile stress layer and the thickness of the third tensile stress layer.
[0019] Preferably, the film layer comprises, from the inside out, a first low refractive index layer, a first tensile stress layer, a second low refractive index layer, a second tensile stress layer, a third low refractive index layer, a third tensile stress layer, a fourth low refractive index layer, a compressive stress layer, and a fifth low refractive index layer stacked sequentially.
[0020] Preferably, the material constituting the tensile stress layer includes AlN. x .
[0021] Preferably, the material constituting the compressive stress layer includes SiN. y and / or SiAlN z .
[0022] Preferably, the material constituting the low refractive index layer is selected from at least one of SiO2, MgF2, and Al2O3.
[0023] Preferably, the visible light transmittance of the coated product is >94%.
[0024] Preferably, the coated article further includes an AF layer that is bonded to the film layer.
[0025] Compared with the prior art, the present invention has at least the following advantages:
[0026] The coated product provided by this utility model can achieve both excellent nano-indentation hardness and wear resistance. By depositing a specific film structure (alternating layers of low refractive index and high refractive index) on one side of the substrate, without changing the material hardness, the high-hardness material layer of some high refractive index layers (usually exhibiting compressive stress) exhibits tensile stress, thereby neutralizing the compressive stress generated by the high-hardness material layer of the remaining high refractive index layers. This ensures that the stress of the film layer in the coated product is low, effectively guaranteeing the stability of the film structure, and thus effectively preventing the film layer from cracking, peeling, or detaching. Attached Figure Description
[0027] Figure 1 This is a schematic diagram of the structure of a preferred coated product provided by this utility model.
[0028] Explanation of reference numerals in the attached figures
[0029] 1. Substrate; 2. Film layer;
[0030] 20. Low-refractive-index layer; 201. First low-refractive-index layer;
[0031] 202. Second low-refractive-index layer; 203. Third low-refractive-index layer;
[0032] 204. Fourth low-refractive-index layer; 205. Fifth low-refractive-index layer;
[0033] 21. High refractive index layer; 211. First stress layer;
[0034] 212. Second stress layer; 213. Third stress layer;
[0035] 214. Compressive stress layer. Detailed Implementation
[0036] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0037] In this utility model, unless otherwise stated, "inner" and "outer" refer to the part that is attached to the substrate as "inner" and the part that is closer to the air as "outer".
[0038] In this utility model, AlN xThe "x" in the figure indicates that the atomic ratio of nitrogen (N) to aluminum (Al) in the film is non-stoichiometric; it may be rich in aluminum (x<1) or rich in nitrogen (x>1), and can vary within a certain range. SiN y The "y" in this context also indicates that the atomic ratio of silicon (Si) to nitrogen (N) is not stoichiometric. (SiAlN) z The “z” in the figure represents the non-stoichiometric ratio of nitrogen (N), indicating that the material is a ternary non-stoichiometric compound composed of silicon (Si), aluminum (Al) and nitrogen (N), in which the content of nitrogen atoms is not fixed but can vary within a certain range.
[0039] In this utility model, "AF coating" refers to an anti-fingerprint coating.
[0040] In this invention, the direction of "tensile stress" is opposite to the direction of "compressive stress".
[0041] It should be noted that the "visible light transmittance" in this utility model refers to the transmittance of the coated product to light at wavelengths of 400nm-700nm.
[0042] The "nanoindentation hardness" of the film layer in this invention is measured on the surface of the coated product by a Brinell indenter hardness test along an indentation depth of about 50 nm or deeper (e.g., about 100 nm or deeper, about 50 nm to about 300 nm, about 50 nm to about 400 nm, about 50 nm to about 500 nm, about 50 nm to about 600 nm, about 50 nm to about 1000 nm, or about 50 nm to about 2000 nm); the "compressive stress" of the film layer is tested according to the method specified in ASTM E673-13 (2019) standard.
[0043] As mentioned above, this utility model provides a coated product, which includes a substrate 1 and a film layer 2. The film layer is bonded to the substrate. The film layer includes alternating layers of low refractive index layer 20 and high refractive index layer 21. The high refractive index layer 21 is a high-hardness material layer. The high-hardness material layer includes at least one compressive stress layer and multiple tensile stress layers. The thickness of the compressive stress layer and the thickness of the multiple tensile stress layers satisfy the stress neutralization in the film layer 2.
[0044] It should be noted that those skilled in the art should know that "stress neutralization" in this utility model means that the compressive stress and tensile stress of the film layer 2 as a whole reach equilibrium, achieving structural stability and ensuring that the film layer 2 in the coated product does not crack, fall off, or peel off, but does not necessarily mean that the stress is completely neutralized to 0.
[0045] Furthermore, those skilled in the art should also be aware of the materials used in the high-hardness material layer of coatings, such as AlNx and SiN. ySiAlN z These high-hardness films also exhibit high compressive stress.
[0046] This invention deposits a specific film structure (alternating layers of low and high refractive index layers) on one side of a substrate. Without changing the material hardness, it causes the high-hardness material layer (which typically exhibits compressive stress) of some high-refractive-index layers to exhibit tensile stress, thereby neutralizing the compressive stress generated by the high-hardness material layer of the remaining high-refractive-index layers and effectively ensuring the stability of the film structure. Furthermore, a high-hardness film is obtained without increasing or even decreasing the film thickness.
[0047] In some embodiments, the thickness of the film layer 2 is less than 550 nm, and the nanoindentation hardness of the film layer 2 is above 15 GPa. In this preferred case, the total thickness of the film layer 2 in the coated product is controlled to be <550 nm, and the nanoindentation hardness is above 15 GPa, which is much smaller than the film thickness (>1500 nm) of the prior art at the same hardness level.
[0048] In some embodiments, the compressive stress of the film layer 2 is n, where 0 < n < 540 MPa. In this preferred case, the compressive stress of the film layer 2 in the coated product is controlled between 0 and 540 MPa, which can further meet the stability requirements of the film structure.
[0049] In some preferred embodiments, the ratio of the total thickness of the tensile stress layer to the total thickness of the compressive stress layer is defined as m, where 1.0 < m < 1.2. In this preferred case, the tensile and compressive stresses in the film layer 2 of the coated product can be better neutralized, resulting in lower stress.
[0050] In some preferred embodiments, the total thickness of the high refractive index layer 21 accounts for 56%-64% of the total thickness of the film layer 2. In this preferred case, both the visible light transmittance of the coated product and the hardness of the film layer in the coated product can be taken into account.
[0051] In some embodiments, the total thickness of the tensile stress layer accounts for 28%-35% of the total thickness of the membrane layer 2.
[0052] In some embodiments, the total thickness of the compressive stress layer accounts for 27%-30% of the total thickness of the film layer 2.
[0053] In some embodiments, both the inner and outer layers of the coated article are low-refractive-index layers.
[0054] According to a preferred embodiment, the high refractive index layer 21 includes one compressive stress layer 214 and three tensile stress layers, with the compressive stress layer 214 bonded to the outermost low refractive index layer of the film layer 2. In this preferred embodiment, the resulting coated product exhibits higher hardness, thereby providing superior scratch resistance.
[0055] In some embodiments, the material constituting the compressive stress layer includes SiN. y and / or SiAlN z .
[0056] In some embodiments, the SiN y The nanoindentation hardness is 25.9-37.9 GPa.
[0057] In some preferred embodiments, the three tensile stress layers in the coated product, from the inside out, are defined as a first tensile stress layer 211, a second tensile stress layer 212, and a third tensile stress layer 213, wherein the thickness of the first tensile stress layer 211 is less than the thickness of the second tensile stress layer 212 and the thickness of the third tensile stress layer 213.
[0058] In some embodiments, the material constituting the tensile stress layer includes AlN. x .
[0059] It should be noted that the material AlN x It can manifest as either tensile stress or compressive stress. This invention can utilize known techniques in the art to make AlN... x It exhibits tensile stress, for example, when sputtered in a PVD cavity environment with high gas content, it can exhibit good tensile stress and maintain good visible light transmittance.
[0060] In some implementations, the AlN x The nanoindentation hardness is 15-25 GPa.
[0061] In some embodiments, the material constituting the low refractive index layer 20 is selected from at least one of SiO2, MgF2, and Al2O3.
[0062] In some embodiments, the visible light transmittance of the coated article is >94%.
[0063] In order to reduce the adhesion of contaminants such as fingerprints and oil stains during the application of the coated product, and at the same time improve the surface cleanability, in one specific embodiment, the coated product further includes an AF coating that is closely attached to the film layer 2.
[0064] This invention does not have any special requirements on the type of substrate. Those skilled in the art can select it as needed. For example, the substrate is glass.
[0065] The coating layer in the coated product provided by this utility model can simultaneously meet the excellent properties of thin thickness, low reflectivity, high hardness, and good wear resistance, and is stable and not prone to cracking or falling off.
[0066] The following combination Figure 1 The present invention provides a preferred embodiment of the structure of the coated product, specifically:
[0067] The coated product includes a substrate 1 and a film layer 2. The film layer 2 comprises, from the inside out, a first low-refractive-index layer 201, a first tensile stress layer 211, a second low-refractive-index layer 202, a second tensile stress layer 212, a third low-refractive-index layer 203, a third tensile stress layer 213, a fourth low-refractive-index layer 204, a compressive stress layer 214, and a fifth low-refractive-index layer 205, stacked sequentially. The thickness of the compressive stress layer and the thickness of the multiple tensile stress layers satisfy the stress neutralization in the film layer 2. In this preferred embodiment, the film layer in the coated product can exhibit higher hardness while maintaining a relatively low thickness.
[0068] This invention does not impose any particular requirements on the preparation method of the coated product; those skilled in the art can choose according to their needs. Exemplarily, the film layer of the coated product can be formed by magnetron sputtering, and the AF coating can be formed by resistance boat evaporation. Further details are omitted here, and those skilled in the art should not construe this as a limitation of the invention.
[0069] The present invention provides the following specific embodiments by way of example.
[0070] In all the examples below, the substrate is ordinary aluminosilicate glass, with a length of 110mm, a width of 75mm, and a thickness of 0.60mm.
[0071] Example 1
[0072] like Figure 1 As shown, the coated product provided in this embodiment includes a substrate and a film layer. The film layer includes, from the inside out, a first low refractive index layer 201, a first tensile stress layer 211, a second low refractive index layer 202, a second tensile stress layer 212, a third low refractive index layer 203, a third tensile stress layer 213, a fourth low refractive index layer 204, a compressive stress layer 214, and a fifth low refractive index layer 205, which are stacked sequentially. The thickness of each layer in the coated product provided in this embodiment is shown in Table 1.
[0073] In this embodiment, the compressive stress layer SiN yThe nanoindentation hardness is 37.9 GPa.
[0074] The structures of the coated products provided in Examples 2-5 are all the same as those in Example 1; see details below. Figure 1 The difference is that the thickness of each layer in the coated products of Examples 2-5 is shown in Table 1.
[0075] Comparative Example 1
[0076] The difference between this comparative example and Example 1 is that the AlNx material that makes up each tensile stress layer in Example 1 is replaced with SiNx of the same thickness (representing compressive stress), and the nanoindentation hardness of SiNx is 25.9 GPa; all parts not listed are the same as in Example 1.
[0077] The nanoindentation hardness of the coating product in this comparative example is 12.6 GPa, the compressive stress is >850 MPa, and the visible light transmittance is approximately 92%.
[0078] Table 1
[0079]
[0080]
[0081] As can be seen from Table 1, the ratio of the total thickness of the tensile stress layer to the total thickness of the compressive stress layer in Examples 1 to 3 of this utility model is between 1.0 and 1.2, so the stress and hardness are well matched, and the visible light transmittance is also slightly higher, which can meet the preferred requirements. Examples 4 and 5 are greater than 1.2 and less than 1.0, respectively, which are reflected in the overall high stress and / or slightly lower hardness, and the visible light transmittance is also slightly lower. However, Examples 1 to 5 as a whole show that the coated product has excellent nano-indentation hardness and wear resistance, and the transmittance in the visible light region is >94%.
[0082] The coating layers of the coated products obtained in Example 1 and the coated products in Comparative Example 1 were subjected to a sandpaper rubbing test (120 grit, 50 rubs, simulating everyday life, similar to the casing of electronic products, where users may be scratched by sharp objects such as keys during use). The haze before and after rubbing was tested according to the method in ISO 13696:2022 standard, and the results are shown in Table 2:
[0083] Table 2
[0084]
[0085]
[0086] Note: "Haze A" refers to the test result under a white background, and "Haze C" refers to the test result under a black background.
[0087] As can be seen from Table 2, the coated products provided by this utility model can resist deep scratches and exhibit good hardness.
[0088] The preferred embodiments of this utility model have been described in detail above; however, this utility model is not limited thereto. Within the scope of the technical concept of this utility model, various simple modifications can be made to the technical solution of this utility model, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed by this utility model and are all within the protection scope of this utility model.
Claims
1. A coated product, characterized in that, The coated product includes a substrate (1) and a film layer (2). The film layer is bonded to the substrate. The film layer includes alternating layers of low refractive index layer (20) and high refractive index layer (21). The high refractive index layer (21) is a high-hardness material layer. The high-hardness material layer includes at least one compressive stress layer and multiple tensile stress layers. The thickness of the compressive stress layer and the thickness of the multiple tensile stress layers satisfy the stress neutralization in the film layer (2).
2. The coated product according to claim 1, characterized in that, The thickness of the film layer (2) is less than 550 nm, and the nanoindentation hardness of the film layer is above 15 GPa. And / or, the compressive stress of the membrane is n, where 0 < n < 540 MPa.
3. The coated product according to claim 1 or 2, characterized in that, The ratio of the total thickness of the tensile stress layer to the total thickness of the compressive stress layer is defined as m, where 1.0 < m < 1.
2.
4. The coated product according to claim 1 or 2, characterized in that, Based on the total thickness of the film layer (2), the total thickness of the high refractive index layer (21) accounts for 56%-64%; And / or, the total thickness of the tensile stress layer accounts for 28%-35%; And / or, the total thickness of the compressive stress layer accounts for 27%-30%.
5. The coated article according to claim 1 or 2, characterized in that, The high refractive index layer includes one layer of the compressive stress layer (214) and at least three layers of the tensile stress layer, and the compressive stress layer (214) is bonded to the low refractive index layer of the outer layer of the film layer (2).
6. The coated product according to claim 5, characterized in that, The three tensile stress layers in the coated product, from the inside out, are defined as the first tensile stress layer (211), the second tensile stress layer (212), and the third tensile stress layer (213), wherein the thickness of the first tensile stress layer is less than the thickness of the second tensile stress layer and the thickness of the third tensile stress layer.
7. The coated article according to claim 6, characterized in that, The film layer (2) comprises, from the inside out, a first low refractive index layer (201), a first tensile stress layer (211), a second low refractive index layer (202), a second tensile stress layer (212), a third low refractive index layer (203), a third tensile stress layer (213), a fourth low refractive index layer (204), a compressive stress layer (214), and a fifth low refractive index layer (205) stacked sequentially.
8. The coated article according to claim 1 or 2, characterized in that, The materials constituting the tensile stress layer include AlN x ; And / or, the material constituting the compressive stress layer includes SiN y and / or SiAlN z ; And / or, the material constituting the low refractive index layer (20) is selected from at least one of SiO2, MgF2, and Al2O3.
9. The coated article according to claim 1 or the above, characterized in that, The visible light transmittance of the coated product is >94%.
10. The coated article according to claim 1 or 2, characterized in that, The coated product also includes an AF layer that is bonded to the film layer (2).