CN116699735A - Semi-reflective semi-transparent automobile inner rearview mirror and preparation method thereof - Google Patents
Semi-reflective semi-transparent automobile inner rearview mirror and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims description 34
- 239000003086 colorant Substances 0.000 claims description 9
- 229910003697 SiBN Inorganic materials 0.000 claims description 8
- 230000002708 enhancing effect Effects 0.000 claims description 7
- 229910007717 ZnSnO Inorganic materials 0.000 claims description 6
- 230000003667 anti-reflective effect Effects 0.000 claims description 6
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- 230000004075 alteration Effects 0.000 abstract description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 22
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
- B60R1/02—Rear-view mirror arrangements
- B60R1/08—Rear-view mirror arrangements involving special optical features, e.g. avoiding blind spots, e.g. convex mirrors; Side-by-side associations of rear-view and other mirrors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Multimedia (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
The invention relates to the technical field of automobile parts, in particular to a semi-reflective semi-transparent automobile inner rearview mirror and a preparation method thereof. The semi-reflective semi-transparent automobile inner rearview mirror comprises a glass substrate, at least one antireflection layer and at least one antireflection layer which are respectively formed on opposite surfaces of the glass substrate, and a third medium refractive index layer and a third high refractive index layer which are sequentially laminated and formed on the surfaces of the antireflection layers; the reflection increasing layer comprises a medium refractive index layer, a high refractive index layer and a low refractive index layer which are sequentially laminated; the refractive index of the middle refractive index layer and the third middle refractive index layer is 1.60-2.30; the refractive index of the high refractive index layer and the third high refractive index layer is 2.30-2.72; the refractive index of the low refractive index layer is 1.46-1.80. The semi-reflective semi-transparent automobile inner rearview mirror lens provided by the invention has no double image and no chromatic aberration of the displayed/reflected image.
Description
Technical Field
The invention relates to the technical field of automobile parts, in particular to a semi-reflective semi-transparent automobile inner rearview mirror and a preparation method thereof.
Background
The automobile indoor rearview mirror in the cab is mainly used for a driver to observe and know the condition of the tail of an automobile and observe the condition of passengers behind the driver in the automobile. The structure and the structure of the indoor rearview mirror are repeatedly improved, the electronic display screen is embedded in the indoor rearview mirror from a simple plane mirror, and the technical structure of integrating an optical lens connected with a camera assembled at the tail of an automobile and a wireless video by using a lead is developed, for example, chinese patent CN2782478Y discloses an automobile indoor rearview mirror, when the electronic receiving screen is in an opened state, the electronic image area of the plane mirror of the indoor rearview mirror fully guarantees that a driver observes the tail state of the automobile, and meanwhile, the left plane mirror image area and the right plane mirror image area separated by the centered electronic receiving screen also meet the functional requirement that the driver clearly observes the state of passengers in the automobile behind the automobile; chinese patent CN1087449724a discloses a multifunctional rearview mirror, which improves visibility in environments with poor light such as glare, darkness, rainy days, etc. by adopting an LCD anti-glare screen; chinese patent CN200960887Y discloses a display for a rear-view mirror of a vehicle, which can be used as a rear-view mirror in a vehicle and can be used as a display screen of a vehicle-mounted image system.
However, the existing automobile interior rearview mirrors generally have the problem of image blurring caused by mirror image ghost, and also have the problems of color distortion (bluish) of a reflected image, reddish image of a display area (reddish transparent color) and the like, so that both the reflected image and the displayed image are unreal, and potential safety hazards exist.
Disclosure of Invention
In order to overcome the defects in the prior art, the technical problems to be solved by the invention are as follows: provides a semi-reflective semi-transparent automobile inner rearview mirror lens with no double image and no chromatic aberration of a display/reflection image and a preparation method of the semi-reflective semi-transparent automobile inner rearview mirror lens.
In order to solve the technical problems, the invention provides a semi-reflective semi-transparent automobile inner rearview mirror lens, which comprises a glass substrate, at least one antireflection layer and at least one antireflection layer which are respectively formed on opposite surfaces of the glass substrate, and a third medium refractive index layer and a third high refractive index layer which are sequentially laminated and formed on the surfaces of the antireflection layers;
the reflection increasing layer comprises a medium refractive index layer, a high refractive index layer and a low refractive index layer which are sequentially laminated;
the refractive index of the middle refractive index layer and the third middle refractive index layer is 1.60-2.30;
the refractive index of the high refractive index layer and the third high refractive index layer is 2.30-2.72;
the refractive index of the low refractive index layer is 1.46-1.80.
The method for manufacturing the semi-reflective semi-transparent inner rearview mirror comprises the steps of forming at least one antireflection layer on one side of a glass substrate, forming at least one antireflection layer on the other side of the glass substrate, and sequentially laminating a third medium refractive index layer and a third high refractive index layer on the surface of the antireflection layer.
The invention has the beneficial effects that: by combining an antireflection film system and a semi-reflection and semi-transparent film system and using a HiPIMS (high power pulse magnetron sputtering) power supply to deposit high refractive index TiO with a refractive index of 2.50-2.72 2 The film layer and the reasonable film system design are utilized, so that the reflectivity of the rearview mirror in the automobile is improved, the rearview image of the rearview mirror in a large visual field range of 0-120 degrees and the image displayed by the electronic display screen are clear and have no double image, the color is natural and cannot be deceived, and the driving safety of the automobile is effectively improved.
Drawings
FIG. 1 is a schematic view of a conventional mirror plate for an automobile interior mirror with a semi-reflective and semi-permeable membrane according to the present invention;
FIG. 2 is a light path diagram of an automotive interior mirror lens having a semi-reflective semi-transmissive film and an anti-reflective film according to an embodiment of the present invention;
FIG. 3 shows the invention in an embodiment of the deposition of TiO from HiPIMS power and MF power 2 The morphology photo of the film and the composition of relevant components form an analysis table;
FIG. 4 is a schematic view showing a structure of an automobile inner rear view mirror lens according to the present invention in an embodiment;
FIG. 5 is a schematic view showing another structure of an automobile interior mirror lens according to the present invention in an embodiment;
FIG. 6 shows the deposition of high refractive index TiO using HiPIMS power in various examples and comparative examples of the present invention in a specific embodiment 2 (n is more than 2.50) the magnetron sputtering process parameters of the film layer.
Description of the reference numerals:
in fig. 1 and 2: 11. a light source; 22 31, 42, refracting light; 21 32, reflecting light; 4. a semi-reflective semi-permeable membrane; 5. a glass substrate; 6. an antireflection film;
in fig. 4: 1. a glass substrate; 2. a first reflection enhancing layer; 3. a second reflection enhancing layer; 4. a third high refractive index layer; 5. a first anti-reflection layer; 6. a second anti-reflection layer;
in fig. 5: 11. a glass substrate; 21. a first medium refractive index layer; 22. a first high refractive index layer; 23. a first low refractive index layer; 31. a second medium refractive index layer; 32. a second high refractive index layer; 33. a second low refractive index layer; 41. a third medium refractive index layer; 42. a third high refractive index layer; 51. a fourth high refractive index layer; 53. a fourth high refractive index layer; 61. a fifth high refractive index layer; 63. and a fifth low refractive index layer.
Detailed Description
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments in conjunction with the accompanying drawings.
In order to solve the defects of the existing intelligent rearview mirrors in the market in the prior art, a semi-reflective and semi-transparent film is plated on the back surface (the side surface deviating from the incident light) of a glass substrate, and the structure of the semi-reflective and semi-transparent film is shown in fig. 1. The semi-reflective and semi-permeable membrane 4 is located inside the mirror, i.e. between the display screen and the glass substrate 5. When a human eye views the rear view through the rearview mirror, a certain included angle (transverse/longitudinal included angle) is formed between the human eye and the rearview mirror, and the rear light source 11 (100%) is incident to the glass interface from the air, so that reflected light rays 21 and refracted light rays 22 are generated, and only about 4% of the reflected light rays 21 enter the human eye. Since the film layer (semi-reflective and semi-permeable film 4) is excessively thin in overall thickness, reflection and refraction of the refracted light rays 22 in the semi-reflective and semi-permeable film 4 can be temporarily ignored. At this time, the refracted ray 22 also generates reflected ray 32 and refracted ray 31 from the glass/film, air interface, and the reflected ray 32 is about 46% because the film is designed to have semi-reflective and semi-transmissive properties, and thus the refracted ray 31 is about 50%. The reflected light 32 reflects off the glass substrate 5, again creating reflected light (shown in phantom, but not considered due to the small amount) and refracted light 42 (about 42%) at the glass/air interface, where the refracted light 42 enters the human eye. Therefore, since the sub-image (4%) formed by the reflected light ray 21 and the main image (about 46%) formed by the refracted light ray 42 are simultaneously entered into the eyes, both the brightness is relatively large, thereby causing image blurring in the human eye. Meanwhile, the brightness ratio of the two increases with the increase of the observation angle. Similarly, the image displayed on the rear view mirror rear display screen also becomes blurred in the human eye.
On the basis of the prior art, the structure of the antireflection film is shown in fig. 2. As can be seen from the figure, the antireflection film 6 can significantly reduce the luminance of the sub-image and enhance the luminance of the main image, and thus the luminance ratio of the sub-image (0.5%) formed by the reflected light ray 21 and the main image (about 49.5%) formed by the refracted light ray 42 is reduced, thereby achieving the effect of augmented reality and avoiding the occurrence of ghost images. The specific data are shown in table 1.
TABLE 1
As can be seen from table 1, the anti-reflective film can effectively reduce the reflectivity of the secondary image while the brightness of the primary image is improved, so that the brightness ratio of the secondary image to the primary image can be reduced by plating the anti-reflective film on the outer surface of the glass substrate, thereby avoiding the occurrence of the ghost phenomenon.
When the automobile inner rear-view mirror lens is practically applied, the brightness of the existing display can be adjusted, so that the semi-reflective and semi-transparent film (namely at least one reflection increasing layer, a third medium refractive index layer and a third medium refractive index layer are arranged in the film systemA combination of high refractive index layers) so that a brighter field of view can be obtained in the interior rear view mirror and clearer information on the rear of the vehicle can be obtained. By proper choice of the high refractive index layer material in a semi-reflective semi-permeable membrane system is key to achieving its high reflectivity, see for example comparative example 1 and example 1 below. Wherein ZrO is used in comparative example 1 x (n=2.24) as its high refractive index layer material, its visible light reflectance was only 50.8%, whereas example 1 was carried out by using TiO 2 (n=2.64) as its high refractive index material, its visible light reflectance is increased to 71.6%, thus TiO is obtained 2 (n=2.64) the rear view mirror image and the in-vehicle scene of the automobile interior rear view mirror prepared as the high refractive index material will be brighter and clearer.
However, it is difficult to prepare a film layer with high refractive index and high quality by using the existing magnetron sputtering technology, such as using an MF power supply. TiO as the material 2 In other words, tiO 2 The material has three crystal structures including brookite type TiO 2 Rutile TiO 2 Anatase TiO 2 . Among them, brookite type synthesis is more difficult. The rutile form has a higher stability, and has a higher refractive index, relative density, and dielectric constant than anatase. Anatase is a metastable phase, and as the heating temperature increases, tiO 2 The phases of the film undergo a microstructural transformation of the amorphous-anatase phase-anatase and rutile mixed phase-rutile phase. According to the description of the prior related literature, tiO 2 The heating temperature for completely converting the film into the rutile state needs to reach more than 1000 ℃. However, tiO is deposited from conventional MF sources 2 After the film layer is heated and annealed (600-790 ℃), the film layer is difficult to be completely converted into a rutile structure due to the insufficient heating temperature, and the refractive index n of the annealed film layer is generally limited to be less than or equal to 2.50, so that the film layer with the refractive index larger than 2.50 is difficult to prepare. Meanwhile, conventional MF power supply magnetron sputtering deposited TiO 2 The film layer has less ions and lower ionization rate. Although vacuum cathodic arc deposition can produce very high particle ionization rates, it can produce large particles of metal/metal compounds that cause excessive coating impurities and increased cooling requirements when the cathode is overheatedTherefore, the coating is difficult to be applied to the automobile glass coating industry. The HiPIMS power supply has higher pulse peak power and lower pulse duty ratio, and has no extra requirement on cathode cooling when ensuring high ionization rate, so the HiPIMS power supply is suitable for the use of the automobile glass coating industry. Relevant comparative parameters of HiPIMS (high power pulsed magnetron sputtering) power supply and MF power supply are shown in table 2.
TABLE 2
| MF | HiPIMS | |
| Working power (non-average power) | ＜120kW | 100kW～2MW |
| Power density of | 10W/cm 2 Stage | 1～3KW/cm 2 Stage |
| Current density | 10mA/cm 2 Stage | 1～5A/cm 2 Stage |
| Duty cycle | 100％ | 1％～15％ |
| Operating voltage | 0～800V | 0～2000V |
| Operating current | 0～200A | 0～1000A |
| Ionization rate | 30％～40％ | Up to > 80% |
| Film layer attachment force | Weak and weak | Strong strength |
Meanwhile, it has been demonstrated in preliminary experiments that TiO is deposited using HiPIMS power supply 2 The film layer had a rutile structure and the results are shown in table 3 and fig. 3.
TABLE 3 Table 3
Therefore, the TiO with the refractive index n of 2.50-2.72 after the heating annealing can be obtained by adjusting the power supply parameters of the HiPIMS 2 And (3) a film layer. And benefit from TiO x High ionization rate of the film layer, and TiO during the heating annealing process of the antireflection film system x The film layer can be more transformed towards the rutile structure.
In a process for preparing TiO having a refractive index n of 2.50 to 2.72 x In the embodiment of the single film layer, the process parameters are shown in table 4.
TABLE 4 Table 4
| Sequence number | Project | Parameters (parameters) |
| 1 | Power supply | HiPIMS power supply |
| 2 | Target material | TiO x A target material, wherein x is more than or equal to 1.8 and less than or equal to 1.9 |
| 3 | Process gas | Ar、O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein O is 2 The inlet amount is 0-30 sccm |
| 4 | Pulse peak power | 100kW～2000kW |
| 5 | Pulse current | 300A～1000A |
| 6 | Pulse voltage | 300V～2000V |
| 7 | Duty cycle | 1％～15％ |
| 8 | Pulse width | 0～150μs |
How to avoid the color cast of the reflection color of the rearview mirror lens on the premise of existence of the high refractive index layer is one of the problems to be solved by the film system design of the invention. According to the invention, the intermediate refractive index layer is introduced in front of the high refractive index layer, so that the angle reflection color of the rearview mirror lens is adjusted, the reflection color of the rearview mirror lens at 0-60 degrees is ensured to be neutral, and the visual field image reflected by the rearview mirror at 0-60 degrees is not color cast. In an alternative embodiment, the medium refractive index layer is introduced between the high refractive index layer and the glass substrate, between the high refractive index layer and the low refractive index layer, and between the third high refractive index layer and the anti-reflection layer in the reflection enhancing layer. See, for example, comparative example 2, comparative example 3 and example 6 below. In comparative example 2, tiO was used 2 (n=2.70) as a high refractive index layer material, the reflectivity of the rearview mirror lens can be effectively improved to 80.1%, the reflection color of the rearview mirror lens is neutral to the 0-30 DEG angle, but when visible light is incident at the angle of 45 DEG and 60 DEG, the Lab value of the reflection color of the rearview mirror to the visible light is-5.3, -6.7, the whole reflection color is greenish, namely, a rear view image reflected by the rearview mirror at the angle of 45 DEG to 60 DEG is provided with a green filter, and the view is severely distorted. Comparative example 3 uses ZnSnO 3 (n=2.09) as its high refractive index layer material, the mirror reflectance was only 41.2%, and the value of a in the color Lab value of the mirror reflecting visible light was-9.4, -13.1 when the visible light was incident at 45 ° and 60 °, the overall color was greenish, i.e., the rear view field in the mirror was severely distorted as in comparative example 2. In example 6, however, by using TiO 2 (n=2.61) as the material of the high refractive index layer, the reflectivity of the rearview mirror is improved to 70.9%, meanwhile, the value a in Lab values of 45 DEG and 60 DEG of visible light reflection colors of the rearview mirror is changed by introducing the medium refractive index layer in front of the high refractive index layer, the reflection colors of the rearview mirror lens are neutral to the visible light reflection colors of 0 DEG to 60 DEG, the visual field is true and undistorted, and the safety of automobile driving is further improved.
Another object of the film system design in the present invention is to avoid mutual interference between the antireflection film system (i.e., the antireflection layer) and the transflective film system (i.e., the combination of at least one antireflection layer, the third medium refractive index layer, and the third high refractive index layer) to achieve the transflective effect and the reflected image reality enhancement effect. Meanwhile, the thickness of the semi-reflective and semi-permeable membrane system is designed to eliminate the side color change when the two membrane systems are combined. See, for example, comparative example 4 and example 8 below. In comparative example 4, tiO was used 2 As its high refractive index layer material, and a medium refractive index layer is introduced before the high refractive index layer, but because of unreasonable film system design, i.e. the thickness of the first high refractive index layer, the first low refractive index layer and the third high refractive index layer all exceed reasonable film system ranges, the visible light reflectivity of the rearview mirror is only 52.7%, and when visible light is incident at 30 °, 45 ° and 60 °, the a value and b value of the Lab value of the reflection color of the rearview mirror for visible light are respectively (4.1, -5.5), (6.1, -8.3), (4.4, -7.8), the overall reflection color is reddish purple, i.e. the rearview mirror has a red-violet filter in the rear view of 30 ° to 60 °, resulting in serious distortion of the view. In the embodiment 8, through reasonable film system design, the front reflectivity can reach 67.5%, and when visible light is incident at an angle of 0-60 degrees, the value a and the value b in the Lab value of the visible light reflection color of the rearview mirror are in a neutral range, so that the real rear view of the rearview mirror can be effectively ensured, and the rear view is not distorted.
Specifically, in one embodiment, the half-reflecting half-transmitting automobile inner rear view mirror lens comprises a glass substrate, at least one antireflection layer and at least one antireflection layer respectively formed on opposite surfaces of the glass substrate, and a third medium refractive index layer and a third high refractive index layer formed on the surfaces of the antireflection layers in a laminated manner; the reflection increasing layer comprises a medium refractive index layer, a high refractive index layer and a low refractive index layer which are sequentially laminated; the refractive index of the middle refractive index layer and the third middle refractive index layer is 1.60-2.30; the refractive index of the high refractive index layer and the third high refractive index layer is 2.30-2.72; the refractive index of the low refractive index layer is 1.46-1.80.
Wherein, the glass substrate is a glass substrate for a conventional rearview mirror, such as ultra-white glass, and the thickness of the glass substrate can be selected according to actual needs, such as 0.7-3.5 mm. Illustratively, the glass substrate has a thickness of 0.7mm, 2.1mm, 3.5mm.
In one embodiment, the anti-reflection layer includes at least one high refractive index layer in which the refractive index of the high refractive index layer is 1.90 to 2.72 and at least one low refractive index layer in which the refractive index of the low refractive index layer is 1.46 to 1.60.
In an alternative embodiment, as shown in fig. 4 and 5, a first antireflection layer and a second antireflection layer are sequentially stacked on one side surface of the glass substrate, where the first antireflection layer includes a fourth high refractive index layer and a fourth low refractive index layer that are sequentially stacked, and the second antireflection layer includes a fifth high refractive index layer and a fifth low refractive index layer that are sequentially stacked.
In an alternative embodiment, as shown in fig. 4 and 5, a first reflection enhancing layer, a second reflection enhancing layer, a third medium refractive index layer and a third high refractive index layer are sequentially laminated on the other side surface of the glass substrate; the first reflection increasing layer comprises a first medium refractive index layer, a first high refractive index layer and a first low refractive index layer which are sequentially stacked; the second reflection increasing layer comprises a second medium refractive index layer, a second high refractive index layer and a second low refractive index layer which are sequentially stacked.
In one embodiment, the material of the fourth and fifth high refractive index layers is selected from SiN x 、SiAlN x 、SiBN x 、SiTiN x 、SiZrN x 、ZnAlO x 、ZnO x 、ZnSnO x 、NbO x 、ZrO x TiO deposited using MF power supply 2 Film or TiO deposited using HiPIMS power supply 2 At least one of (a) and (b); wherein x is more than 1 and less than 3.
In one embodiment, the material of the fourth low refractive index layer and the fifth low refractive index layer is selected from SiO x 、SiBO x 、SiTiO x 、SiAlO x 、SiZrO x At least one of (a) and (b); wherein x is more than 1 and less than 3.
In one embodiment, the fourth high refractive index layer has a thickness of 5 to 30nm, the fourth low refractive index layer has a thickness of 30 to 55nm, the fifth high refractive index layer has a thickness of 15 to 45nm, and the fifth low refractive index layer has a thickness of 85 to 120nm.
In one embodiment, the material of the first medium refractive index layer, the second medium refractive index layer, and the third medium refractive index layer is SiN x 、SiAlN x 、SiBN x 、SiTiN x 、SiZrN x 、ZnAlO x 、ZnO x 、ZnSnO x 、ZrO x 、SiN x O y 、SiBN x O y 、SiTiN x O y 、SiAlN x O y 、SiZrN x O y At least one of (a) and (b); wherein x is more than 1 and less than or equal to 3, and y is more than 1 and less than 3.
In one embodiment, the material of the first high refractive index layer, the second high refractive index layer and the third high refractive index layer is selected from NbO x TiO deposited using MF power supply 2 Film or TiO deposited using HiPIMS power supply 2 At least one of the film layers; wherein x is more than 1 and less than or equal to 3.
In one embodiment, the material of the first low refractive index layer and the second low refractive index layer is selected from SiO x 、SiBO x 、SiTiO x 、SiAlO x 、SiZrO x 、SiN x O y 、SiBN x O y 、SiTiN x O y 、SiAlN x O y 、SiZrN x O y At least one of (a) and (b); wherein x is more than 1 and less than or equal to 3, and y is more than 1 and less than 3.
In one embodiment, the first medium refractive index layer 21 has a thickness of 5 to 100nm; the thickness of the first high refractive index layer 22 is 50-125 nm; the thickness of the first low refractive index layer 23 is 60-155 nm; the thickness of the second medium refractive index layer 31 is 5-100 nm; the thickness of the second high refractive index layer 32 is 20-75 nm; the thickness of the second low refractive index layer 33 is 65-110 nm; the thickness of the third medium refractive index layer 41 is 5-100 nm; the thickness of the third high refractive index layer 42 is 15 to 65nm.
For convenience of writing, tiO is used herein 2 The film refers to the film formed by MF or HiPIMS power supply, but for TiO formed by HiPIMS power supply 2 The material of the film layer is understood to be TiO x Wherein X is more than or equal to 1.8 and less than or equal to 2.
In one embodiment, the value of a in the Lab value of the visible light reflection color of the semi-reflective semi-transmissive automobile interior mirror lens pair incident at an angle of 8 ° satisfies: -1.ltoreq.a.ltoreq.1; b is more than or equal to-1 and less than or equal to-1; the visible light reflectance R satisfies: r is more than or equal to 60 and less than or equal to 80.
In one embodiment, the value of a in the Lab value of the visible light reflection color of the semi-reflective semi-transmissive automobile interior mirror lens pair incident at an angle of 30 ° satisfies: -1.ltoreq.a.ltoreq.1; b is more than or equal to-3 and less than or equal to 0.
In one embodiment, the value of a in the Lab value of the visible light reflection color of the half-reflection half-transmission automobile inner rearview mirror lens pair incident at the angle of 45 ° is as follows: -3.ltoreq.a.ltoreq.0; b is more than or equal to-5 and less than or equal to 0.
In one embodiment, the value of a in the Lab value of the visible light reflection color of the semi-reflective semi-transmissive automobile interior mirror lens pair incident at an angle of 60 ° satisfies: -a is more than or equal to 4.5 and less than or equal to 0; b is more than or equal to-4.5 and less than or equal to 0.
In one embodiment, the half-reflective half-transmissive automobile interior mirror lens satisfies the following a value in the Lab value of the visible light transmission color incident at an angle of 8 °: -1.ltoreq.a.ltoreq.1; the visible light transmittance T satisfies: t is more than or equal to 20 and less than or equal to 40.
The preparation method of the semi-reflective semi-transparent automobile inner rearview mirror lens further comprises the steps of forming at least one antireflection layer on one side surface of a glass substrate, forming at least one antireflection layer on the other side surface of the glass substrate, and sequentially laminating a third medium refractive index layer and a third high refractive index layer on the surface of the antireflection layer.
In an alternative embodiment, the method further comprises the step of heating and annealing the coated raw sheet after coating. The annealing can be performed by any existing high-temperature annealing process of glass, such as tempering, semi-tempering and the like. On the premise of not specifically describing, the embodiment and the comparative example of the invention adopt a semi-hardening technology, and the specific parameters are as follows: heating process (with the temperature of the heated air as a set standard): preheating temperature is 570 ℃, and preheating time is 240s; heating temperature is 690 ℃, and heating time is 240s; and (3) annealing: annealing temperature 300 ℃ and annealing time 240s.
Preparation example (see FIG. 5 for an example of example 1)
A preparation method of a semi-reflective semi-transparent automobile inner rearview mirror lens comprises the following steps:
s1, washing and drying float ultrawhite plate glass with the thickness of 3.5mm, and then entering a magnetron sputtering coating line to coat an antireflection film layer;
s2, magnetron sputtering a fourth high refractive index layer 51: si (Si) 3 N 4
Target number: 1 double-rotating cathode; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: n (N) 2 ＝600：540；
Sputtering air pressure is 3.3E-3mbar; the thickness of the coating is 16.5nm;
s3, magnetron sputtering a fourth low-emissivity layer 53: siO (SiO) 2
Target number: 2 double rotary cathodes; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: o (O) 2 ＝700：350；
Sputtering air pressure is 3.5E-3mbar; the thickness of the coating is 44.7nm;
s4, magnetron sputtering a fifth high refractive index layer 61: si (Si) 3 N 4
Target number: 1 double-rotating cathode; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: n (N) 2 ＝600：540；
Sputtering air pressure is 3.3E-3mbar; the thickness of the coating film is 27.4nm;
s5, magnetron sputtering fifth low-refractionEmissivity layer 63: siO (SiO) 2
Target number: 4 double rotary cathodes; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: o (O) 2 ＝700：350；
Sputtering air pressure is 3.4E-3mbar; the thickness of the coating is 106.7nm;
s6, after film coating is completed, optical testing and quality inspection are carried out on the antireflection film layer, and the optical testing is completed and is transmitted to a powder spraying machine for powder spraying and film collecting;
s7, after being fully packed, the film is transported to a film coating line film placing position and is rotated by using a crane, and after washing and drying, the film enters a magnetron sputtering film coating line to plate a semi-reflective semi-transparent film layer;
s8, magnetron sputtering a first medium refractive index layer 21: siO (SiO) x N y
Target number: 2 double rotary cathodes; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: n (N) 2 ：O 2 ＝700：100：300；
Sputtering air pressure is 3.6E-3mbar; the thickness of the coating is 30.4nm;
s9, magnetron sputtering a first high refractive index layer 22: tiO (titanium dioxide) 2
Target number: 4 double rotary cathodes; and (3) a target power supply: hiPIMS (high power pulsed magnetron sputtering power supply);
the target is configured as ceramic TiO x (x=1.8); process gas: ar: o (O) 2 ＝1000：10；
Pulse peak power: 891.5kW; pulse width: 23 μs;
pulse current: 858-899A; pulse voltage: 935-978V;
sputtering air pressure is 2.34E-3mbar; the thickness of the coating film is 90.3nm;
s10, magnetron sputtering a first low-emissivity layer 23: siO (SiO) 2
Target number: 4 double rotary cathodes; and (3) a target power supply: MF (intermediate frequency power supply);
the target is configured as SiAl (Si: al=92:8 wt%); process gas: ar: o (O) 2 ＝700：350；
Sputtering air pressure is 3.4E-3mbar; the thickness of the coating film is 87.5m;
s11, magnetron sputtering the second medium refractive index layer 31: siO (SiO) x N y
Target number: 1 double-rotating cathode; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: n (N) 2 ：O 2 ＝700：100：300；
Sputtering air pressure is 3.6E-3mbar; the thickness of the coating film is 17.5nm;
s12, magnetron sputtering the second high refractive index layer 32: tiO (titanium dioxide) 2
Target number: 3 double rotary cathodes; and (3) a target power supply: hiPIMS (high power pulsed magnetron sputtering power supply);
the target is configured as ceramic TiO x (x=1.8); process gas: ar: o (O) 2 ＝1000：10；
Pulse peak power: 894.3kW; pulse width: 23 μs;
pulse current: 861-904A; pulse voltage: 931-975V;
sputtering air pressure is 2.34E-3mbar; the thickness of the coating film is 49nm;
s13, magnetron sputtering the second low refractive index layer 33: siO (SiO) 2
Target number: 4 double rotary cathodes; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: o (O) 2 ＝700：350；
Sputtering air pressure is 3.4E-3mbar; the thickness of the coating film is 89.2nm;
s14, magnetron sputtering the third intermediate refractive index layer 41: siO (SiO) x N y
Target number: 1 double-rotating cathode; and (3) a target power supply: MF (intermediate frequency power supply);
the target was configured as SiAl (Si: al=92:8 wt%); process gas: ar: n (N) 2 ：O 2 ＝700：100：300；
Sputtering air pressure is 3.6E-3mbar; the thickness of the coating film is 15.5nm;
s15, magnetron sputtering a third high refractive index layer 42: tiO (titanium dioxide) 2
Target number: 2 double rotary cathodes; and (3) a target power supply: hiPIMS (high power pulsed magnetron sputtering power supply);
the target is configured as ceramic TiO x (x=1.8); process gas: ar: o (O) 2 ＝1000：10；
Pulse peak power: 889.4kW; pulse width: 23 μs;
pulse current: 865-909A; pulse voltage: 928-969V;
sputtering air pressure is 2.34E-3mbar; the thickness of the coating is 25.4nm;
s16, after film coating is completed, carrying out optical test and quality inspection on the whole film layer, and conveying the optical test to a powder spraying machine for powder spraying and film collecting, and conveying to a cutting procedure after one package is fully collected;
s17, cutting the film-plated raw sheet into rectangular small sheets by using a glass cutting machine, cutting glass into the size of a rearview mirror drawing by using a CNC (computer numerical control) processing center, edging, cleaning the film-plated raw sheet by using pure water and a hairbrush to clean dirt on the surface of the film-plated raw sheet, and drying to provide clean condition guarantee for the next glass semi-steel so as to avoid the problems of spotting, distortion and the like of a mirror surface;
and S18, heating and annealing the cleaned film-coated raw sheet in a tempering furnace.
S19, detecting the dimensional stability and the coating effect (the lens with defects such as scratches, pits, distortion, edge burst and the like on the surface are eliminated) of the lens, and finally, checking to obtain the finished automobile inner rear view mirror lens.
Examples 1 to 10 and comparative examples 1 to 4
The automobile interior mirror lenses were prepared according to the following tables 5, 7 to 9, 11, 13 and fig. 6 (including film materials and corresponding thickness data and refractive index data, and preparation parameters of high refractive index layers, film sequence numbers see fig. 5), in combination with the foregoing preparation examples, and the results are shown in tables 6, 10 and 12, respectively.
Wherein, table 5 is thickness data corresponding to the film material, and table 7 is refractive index data corresponding to the film material; table 8 is refractive index data corresponding to the film material, and table 9 is thickness data corresponding to the film material; table 11 is thickness data corresponding to the film material, and table 13 is refractive index data corresponding to the film material.
TiO having refractive indices n=2.70, n=2.64, and n=2.61 in tables 7, 8, 11, and 13 2 The film layers are all obtained by magnetron sputtering of HiPIMS power supply, and TiO in the antireflection layers in the rest examples and comparative examples 2 (n=2.50) film layers are all obtained by MF power supply magnetron sputtering. Deposition of high refractive index TiO using HiPIMS power supply 2 The magnetron sputtering process parameters of the (n > 2.50) film layer are shown in FIG. 6.
In the following, the optical data were measured using an Agilent Cary 7000 angle colorimeter, and the color characterization system used the CIELab color system.
Unless otherwise specified, ultra-white glass was used as the glass substrate in each of examples and comparative examples.
The thickness data of each layer in examples and comparative examples were given in nm without specific labeling.
TABLE 5
TABLE 6
TABLE 7
As shown in tables 5 to 7 above, in comparative example 1, although the rear view image and the in-vehicle electronic image of the automobile were made ghost-free by using the antireflection film layer, zrO was used x (n=2.24) as a material of the high refractive index layer, the visible light reflectance thereof was only 50.8%, and the rear view and the in-vehicle scene image were not bright enough.
Examples 1 to 5, in which an antireflection film layer was used to make a rear view image and an in-vehicle electronic image of an automobile ghost-free, tiO was used separately 2 (n＝2.64)、TiO 2 (n＝2.70)、TiO 2 (n＝2.70)、TiO 2 (n=2.70) and TiO 2 (n=2.70) as their high refractive index layer materials, that is, by increasing the refractive index of the high refractive index materials, the reflectivities are respectively increased to 71.6%, 74.6%, 76%, 67.9% and 61.6%, so that the mirror image of the rear view of the vehicle and the scene in the vehicle will be brighter and clearer.
TABLE 8
TABLE 9
Table 10
As can be seen from the data in tables 8 to 10 above, comparative example 2 uses TiO 2 (n=2.70) as its high refractive index layer material, to make the reflectivity of the rear view mirror reachWhen 80.1% of the reflection color of the rear-view mirror lens is neutral to the angle of 0-30 degrees, but when the visible light is incident at the angles of 45 degrees and 60 degrees, the value a in the Lab value of the reflection color of the rear-view mirror lens to the visible light is-5.3, -6.7, the whole reflection color is greenish, namely, the rear view image of the rear-view mirror reflected at the angle of 45-60 degrees is provided with a green filter, and the view is distorted.
Comparative example 3 uses ZnSnO 3 (n=2.09) as the material of the high refractive index layer, the reflectivity of the rearview mirror only reaches 41.2%, when the visible light is incident at an angle of 45 degrees and 60 degrees, the value a of Lab values of the reflection color of the visible light of the rearview mirror is-9.4 and-13.1, the whole reflection color is greenish, namely, a rear view image reflected by the rearview mirror at an angle of 45 degrees to 60 degrees is provided with a green filter, and the view is distorted.
Examples 6 and 7 use TiO respectively 2 (n=2.61) and TiO 2 (n=2.50) as the high refractive index layer materials, the reflectivity of the rearview mirror reaches 70.9 and 63.5 respectively, and meanwhile, the value a of the rearview mirror in the Lab value of 45-60 degrees for visible light reflection color is changed by adding the medium refractive index layer in front of the high refractive index layer, so that the rearview mirror lens is neutral for 0-60 degrees for the angle reflection color, and the view behind the rearview mirror is real and does not lose color, thereby improving the safety of automobile driving.
TABLE 11
Table 12
TABLE 13
As can be seen from the data in tables 11 to 13 above, comparative example 4 uses TiO 2 (n=2.50) as its high refractive index layer material, and adds the middle refractive index layer before the high refractive index layer, but because the film system design is unreasonable, the film thickness of the first high refractive index layer 22, the first low refractive index layer 23, the third high refractive index layer 42 is beyond the reasonable film system range, so that the visible light reflectivity is only 52.7%, when the visible light is incident at 30 DEG, 45 DEG and 60 DEG, the value a and the value b in the Lab value of the visible light reflection color of the rearview mirror are (4.1, -5.5), (6.1, -8.3), (4.4, -7.8), and the whole reflection color is reddish purple, namely the rearview mirror wears a red-violet filter at the rear view of 30 DEG-60 DEG, and the view distortion.
Examples 8 to 10 have a reasonable film system design, the front reflectivity reaches 67.5%, 71% and 60.8%, and when visible light is incident at an angle of 0-60 degrees, the values a and b in Lab values of visible light reflection colors of the rearview mirror are neutral, so that the rear view field of the rearview mirror is real and does not lose color.
In summary, the invention combines the antireflection film system and the semi-reflection and semi-transmission film system to be applied to the automobile inner rear-view mirror, and simultaneously uses the HiPIMS technology to deposit TiO with the refractive index of 2.50-2.72 2 The film layer is designed by a reasonable film system, so that the effects of high reflectivity of the inner rearview mirror, augmented reality in a large visual field range of 0-120 degrees, clear and natural display of rear visual field and electronic images are achieved.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent changes made by the specification and drawings of the present invention, or direct or indirect application in the relevant art, are included in the scope of the present invention.
Claims (17)
1. The semi-reflective semi-transparent automobile inner rearview mirror lens is characterized by comprising a glass substrate, at least one antireflection layer and at least one antireflection layer which are respectively formed on opposite surfaces of the glass substrate, and a third medium refractive index layer and a third high refractive index layer which are sequentially laminated and formed on the surfaces of the antireflection layers;
the reflection increasing layer comprises a medium refractive index layer, a high refractive index layer and a low refractive index layer which are sequentially laminated;
the refractive index of the middle refractive index layer and the third middle refractive index layer is 1.60-2.30;
the refractive index of the high refractive index layer and the third high refractive index layer is 2.30-2.72;
the refractive index of the low refractive index layer is 1.46-1.80.
2. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 1, wherein the anti-reflective layer comprises at least one high refractive index layer and at least one low refractive index layer, wherein the refractive index of the high refractive index layer in the anti-reflective layer is 1.90 to 2.72 and the refractive index of the low refractive index layer in the anti-reflective layer is 1.46 to 1.60.
3. The lens according to claim 2, wherein a first antireflection layer and a second antireflection layer are sequentially laminated on one side surface of the glass substrate, the first antireflection layer includes a fourth high refractive index layer and a fourth low refractive index layer sequentially laminated, and the second antireflection layer includes a fifth high refractive index layer and a fifth low refractive index layer sequentially laminated.
4. The lens according to claim 1, wherein a first reflection enhancing layer, a second reflection enhancing layer, a third medium refractive index layer and a third high refractive index layer are sequentially laminated on the other side surface of the glass substrate;
the first reflection increasing layer comprises a first medium refractive index layer, a first high refractive index layer and a first low refractive index layer which are sequentially stacked;
the second reflection increasing layer comprises a second medium refractive index layer, a second high refractive index layer and a second low refractive index layer which are sequentially stacked.
5. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 3, wherein the fourth and fifth high refractive index layers are made of SiN x 、SiAlN x 、SiBN x 、SiTiN x 、SiZrN x 、ZnAlO x 、ZnO x 、ZnSnO x 、NbO x 、ZrO x TiO deposited using MF power supply 2 Film or TiO deposited using HiPIMS power supply 2 At least one of (a) and (b);
wherein x is more than 1 and less than 3.
6. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 3, wherein the fourth and fifth low refractive index layers are made of a material selected from the group consisting of SiO x 、SiBO x 、SiTiO x 、SiAlO x 、SiZrO x At least one of (a) and (b);
wherein x is more than 1 and less than 3.
7. The lens according to any one of claims 3, 5 or 6, wherein the fourth high refractive index layer has a thickness of 5 to 30nm, the fourth low refractive index layer has a thickness of 30 to 55nm, the fifth high refractive index layer has a thickness of 15 to 45nm, and the fifth low refractive index layer has a thickness of 85 to 120nm.
8. The lens as claimed in claim 4, wherein the material of the first medium refractive index layer, the second medium refractive index layer, and the third medium refractive index layer is SiN x 、SiAlN x 、SiBN x 、SiTiN x 、SiZrN x 、ZnAlO x 、ZnO x 、ZnSnO x 、ZrO x 、SiN x O y 、SiBN x O y 、SiTiN x O y 、SiAlN x O y 、SiZrN x O y At least one of (a) and (b);
wherein x is more than 1 and less than or equal to 3, and y is more than 1 and less than 3.
9. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 4, wherein the materials of the first, second and third high refractive index layers are selected from NbO x TiO deposited using MF power supply 2 Film or TiO deposited using HiPIMS power supply 2 At least one of the film layers;
wherein x is more than 1 and less than or equal to 3.
10. The lens as claimed in claim 4, wherein the material of the first low refractive index layer and the second low refractive index layer is selected from the group consisting of SiO x 、SiBO x 、SiTiO x 、SiAlO x 、SiZrO x 、SiN x O y 、SiBN x O y 、SiTiN x O y 、SiAlN x O y 、SiZrN x O y At least one of (a) and (b);
wherein x is more than 1 and less than or equal to 3, and y is more than 1 and less than 3.
11. The semi-reflective semi-transmissive automobile interior mirror lens according to any one of claims 4, 8 to 10, wherein the thickness of the first medium refractive index layer 21 is 5 to 100nm; the thickness of the first high refractive index layer 22 is 50-125 nm; the thickness of the first low refractive index layer 23 is 60-155 nm; the thickness of the second medium refractive index layer 31 is 5-100 nm; the thickness of the second high refractive index layer 32 is 20-75 nm; the thickness of the second low refractive index layer 33 is 65-110 nm; the thickness of the third medium refractive index layer 41 is 5-100 nm; the thickness of the third high refractive index layer 42 is 15 to 65nm.
12. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 1, wherein a value of a in Lab values of visible light reflection colors incident at an angle of 8 ° of the semi-reflective semi-transmissive automobile interior mirror lens satisfies: -1.ltoreq.a.ltoreq.1; b is more than or equal to-1 and less than or equal to-1; the visible light reflectance R satisfies: r is more than or equal to 60 and less than or equal to 80.
13. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 1, wherein a value of a in Lab values of visible light reflection colors incident at an angle of 30 ° of the semi-reflective semi-transmissive automobile interior mirror lens satisfies: -1.ltoreq.a.ltoreq.1; b is more than or equal to-3 and less than or equal to 0.
14. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 1, wherein a value of a in Lab values of visible light reflection colors incident at an angle of 45 ° of the semi-reflective semi-transmissive automobile interior mirror lens satisfies: -3.ltoreq.a.ltoreq.0; b is more than or equal to-5 and less than or equal to 0.
15. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 1, wherein a value among Lab values of visible light reflection colors incident at an angle of 60 ° of the semi-reflective semi-transmissive automobile interior mirror lens satisfies: -a is more than or equal to 4.5 and less than or equal to 0; b is more than or equal to-4.5 and less than or equal to 0.
16. The semi-reflective semi-transmissive automobile interior mirror lens according to claim 1, wherein a value of a in Lab values of visible light transmission colors incident at an angle of 8 ° of the semi-reflective semi-transmissive automobile interior mirror lens satisfies: -1.ltoreq.a.ltoreq.1; the visible light transmittance T satisfies: t is more than or equal to 20 and less than or equal to 40.
17. A method for producing a half-reflecting half-transmitting mirror sheet for an automobile according to any one of claims 1 to 16, comprising a step of forming at least one antireflection layer on one side of a glass substrate, a step of forming at least one antireflection layer on the other side of the glass substrate, and a step of sequentially laminating a third medium refractive index layer and a third high refractive index layer on the surface of the antireflection layer.
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