Patent Application
20200166672
The entire disclosure of Japanese Patent Application No. 2018-219874, filed on Nov. 26, 2018, is incorporated herein by reference.
The present invention relates to an optical member and a method of producing the optical member. More specifically, the present invention relates to an optical member having excellent salt water resistance, which is free from the influence of environmental deterioration on the spectral reflectance of the lower layer and the occurrence of ghosts and flares associated therewith by improving the removability by salt water of the uppermost layer which contains SiO2 as a main component.
In order to support driving of a vehicle, a vehicle is equipped with an on-vehicle camera. More specifically, a camera for capturing the back and side of a vehicle is mounted on the vehicle body of an automobile, and the image captured by this camera is displayed at a position visible to the driver to reduce the blind spot, thereby it can contribute to safe driving.
Incidentally, the on-vehicle camera is often mounted outside the vehicle, and the lens used has a strict requirement for guaranteeing the environmental resistance. For example, in a salt spray test on a lens, when the light reflectance changes due to the dissolution of SiO2 which is a component of the anti-reflection film on the lens surface into salt water, it causes ghosts and flares.
Therefore, a low refractive index material may be used as a main component in the uppermost layer of the lens, and a protective film having a small influence may be formed on the light reflectance of the lower layer. The film thickness may be less than 20 nm because the light reflectance of the antireflective film changes if the protective film has a film thickness of 20 nm or more.
As a thin film optical element having dielectric multilayer films, a technique is disclosed in which a plurality of Al2O3 containing layers and a plurality of SiO2 containing layers are alternately laminated, and a layer containing SiO2 is further laminated as an uppermost layer (for example, refer to Patent Document 1: JP-A 2001-074931).
However, when the uppermost layer is simply a layer containing SiO2, the spectral reflectance changes due to the dissolution of the SiO2 on the surface in salt water in the salt spray test. This causes ghosts and flares.
On the other hand, from the viewpoint of durability, a film formation technique using an ion assisted deposition (hereinafter also referred to simply as “IAD”) method in addition to the vapor deposition method as a method for forming a dense uppermost layer is known (for example, refer to Patent Document 2: JP-A 2003-221663 and Patent Document 3: WO 2015/030015).
The IAD method is a method of forming a dense film by causing high kinetic energy of ions to act during film formation, or enhancing the adhesion between a film and a substrate. It may be applied as a means to improve the durability of the uppermost layer.
However, when the deposition method using the IAD method is applied to the extremely thin layer formation required for the uppermost layer, the circumferential film thickness does not become uniform in the device. In addition, when the uppermost layer material is a mixture, the materials are limited to have near vapor pressure, and it is difficult to form the uppermost layer with a desired material ratio and film thickness.
Therefore, the appearance of the following optical member is awaited. That is, while the lens top layer is mainly composed of SiO2 which is a low refractive index material, there is no change in spectral reflectance due to dissolution and peeling of the SiO2 containing layer without occurrence of ghosts and flares in the salt spray test.
One or more embodiments of the present invention provide an optical member excellent in salt water resistance and a method of manufacturing the same, which is free from the influence of environmental deterioration on the spectral reflectance of the lower layer and the occurrence of ghosts and flares associated therewith accompanying the passage of time by improving the removability by salt water of the uppermost layer which contains SiO2 as a main component.
An optical member according to one or more embodiments of the present invention is an optical member comprising a plurality of antireflection layers on a substrate, wherein an immediately lower layer of an uppermost layer is a thin film containing a low reflective index material, for example, a thin film containing any of SiO2, MgF2, and Al2O3, or a mixture made of these materials (SiO2, MgF2, and Al2O3), and the uppermost layer is a metal oxide layer mainly composed of SiO2 and containing at least a specific element.
The advantages and features provided by one or more embodiments of the invention will become more fully understood from the detailed description given hereinbelow and the appended drawings which are given by way of illustration only, and thus are not intended as a definition of the limits of the present invention.
Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the scope of the invention is not limited to the disclosed embodiments.
The optical member of one or more embodiments of the present invention is an optical member having dielectric multilayer films on a substrate, wherein an immediately lower layer of an uppermost layer is a layer containing any one of SiO2, MgF2, or Al2O3, or a mixture of any combination comprising these materials; and the uppermost layer is a metal oxide layer containing SiO2 as a main component and containing at least one element of Cr or Ti. This feature is a technical feature common or corresponding to the following embodiments.
According to one or more embodiments of the present invention, it is possible to provide an optical member excellent in salt water resistance and a method of manufacturing the same, which is free from the influence of environmental deterioration on the spectral reflectance of the lower layer and the occurrence of ghosts and flares associated therewith by improving the removability by salt water of the uppermost layer which contains SiO2 as a main component.
The expression mechanism or action mechanism of the effect of one or more embodiments of the present invention is as follows.
In the configuration of the dielectric multilayer films in which conventional Ta2O5/SiO2 containing layers are alternately laminated, in order to evaluate the salt water resistance of the SiO2 containing layer that forms the uppermost layer, a salt spray test was performed. The change in spectral reflectance when the SiO2 containing layer was dissolved and peeled was examined.
To dielectric multilayer films in which Ta2O5/SiO2 layers having an antireflection function are alternately laminated (substrate/Ta2O5 (26.4 nm)/SiO2 (24.9 nm)/Ta2O5 (26.4 nm)/SiO2 (29.4 nm)/Ta2O5 (130.1 nm)/SiO2 (87.5 nm)) (the figure in parentheses indicates the layer thickness), the SiO2 containing layer that forms the uppermost layer is subjected to the following salt spray test, and then the spectral reflection characteristics are measured. The spectral reflectance can be measured in the optical wavelength region (in the range of 350 to 800 nm), for example, with a spectrophotometer U-4100 manufactured by Hitachi High Technology Co., Ltd.
The following steps (a) to (c) are considered as 1 cycle, and 8 cycles are carried out.
(a) The following solvent at 25±2° C. is sprayed on the sample surface for 2 hours at a temperature in the spray tank of 35±2° C. (saline concentration 5%).
(b) After spraying, leave the sample at 40±2° C. and 95% RH for 22 hours.
(c) After repeating (a) and (b) four times, leave the sample at 25° C. and 55% RH for 72 hours.
Solute used: NaCl, MgCl2, CaCl2
Solute concentration: 5±1% (mass ratio)
According to
The optical member of one or more embodiments of the present invention is an optical member having a plurality of antireflection layers on a substrate, wherein a layer immediately below an uppermost layer is a layer containing either SiO2, MgF2, or Al2O3, or a mixture comprising these materials; and the uppermost layer is a metal oxide layer containing SiO2 as a main component and containing at least one element of Cr or Ti.
In particular, it has been found that the uppermost layer contains SiO2 as a main component and contains a specific amount of at least one of Cr and Ti, thereby improving the salt water solubility resistance of SiO2.
The mechanism by which the salt water resistance of the SiO2 containing layer is improved by containing any element of Cr or Ti is presumed as follows.
In the salt spray test of the SiO2 containing layer, the pH of salt water at 25° C. is about 7 (weakly alkaline), so the Si—O bond is easily broken, and the SiO2 containing layer gradually dissolves in salt water and peels off. Therefore, by adding any element of Cr or Ti in which the activity of oxides or hydroxides is higher than that of ions in the pH range to the SiO2 containing layer, the bond to salt water is stabilized and solubility will decrease.
On the other hand, the uppermost layer according to one or more embodiments of the present invention may be formed as a high-density film from the viewpoint of film formation that is thin but robust.
Film formation method from the viewpoint of productivity that the uppermost layer according to one or more embodiments of the present invention may be formed by sputtering using an ion source of an ion assisted deposition method as a sputtering source.
As described above, when the vapor deposition method using the IAD method is applied to the formation of an extremely thin layer required for the uppermost layer, the film thickness in the circumferential direction is not uniform in the apparatus. In addition, when the uppermost layer material is a mixture, the material is limited to a material having a near vapor pressure, and it is difficult to form the uppermost layer with a desired material ratio and film thickness, and the expected salt water resistance is not achieved.
In one or more embodiments of the present invention, by employing a method of forming a film on the dielectric multilayer films on the substrate by sputtering using the IAD ion source as a sputtering source, the uppermost layer can be formed at any composition ratio. In addition, a uniform and thin uppermost layer can be formed while ensuring high productivity.
Specifically, a sputtering target is disposed between the dielectric multilayer films on the substrate and the ion source, and a surface of the sputtering target opposite to a surface facing the substrate is sputtered by an ion beam. The scattering speed of the sputtered target particles to the substrate is delayed, and the film forming speed can be made slower than that of the conventional method. As a result, it is possible to form a uniform thin film with a desired material composition ratio on the substrate while being a very thin layer. For example, the uppermost layer formed in this way is an uppermost layer having excellent salt water resistance without affecting the spectral reflectance of the lower layer and free from dissolution and peeling of SiO2 by the salt spray test.
In one or more embodiments of the present invention, for example, from the viewpoint of improving salt water resistance, the content of the Cr contained in the uppermost layer may be in the range of more than 0.3 at % (i.e., atomic percent) and less than 2.3 at %, the content of the Ti contained in the uppermost layer may be in the range of more than 0.2 at % and less than 0.8 at %, and the content of the Si contained in in the uppermost layer may be in the range of more than 9 at % and less than 31 at %.
The film thickness of the uppermost layer may be 15 nm or less because it does not change the spectral reflectance of the lower layer, or it may be 10 nm or less according to one or more embodiments.
The refractive index with respect to the light wavelength of 587.56 nm of the uppermost layer may be 1.6 or less because the spectral reflectance of the lower layer is not changed. The refractive index may be in the range of 1.4 to 1.5.
A layer containing TiO2 may be provided on the lower layer side of the immediately lower layer from the viewpoint of providing the optical member according to one or more embodiments of the present invention with a photocatalytic action of self-cleaning (antifouling function).
In addition, from the viewpoint of improving the visibility of images captured as on-vehicle lenses, the optical member of one or more embodiments of the present invention may have an average spectral reflectance of 2% or less with respect to an incidence light from the normal direction in the light wavelength range of 420 to 680 nm.
In the producing method of the optical member to produce the optical member of one or more embodiments of the present invention, the uppermost layer may be formed by using an ion source of an ion assisted deposition method as a sputtering source in order to ensure high productivity.
One or more embodiments of the present invention and the constitution elements thereof, as well as configurations, will be detailed in the following. In the present description, when two figures are used to indicate a range of value before and after “to”, these figures are included in the range as a lowest limit value and an upper limit value.
An optical member of one or more embodiments of the present invention is an optical member comprising dielectric multilayer films on a substrate, wherein an immediately lower layer of an uppermost layer is a layer containing any one of SiO2, MgF2 and Al2O3, or a mixture of any combination of SiO2, MgF2 and Al2O3, and the uppermost layer is a metal oxide layer containing SiO2 as a main component and also containing at least one of Cr and Ti.
The dielectric multilayer films 100 having the antireflection function includes, for example, high refractive index layers 103 and 105 having a refractive index higher than that of the glass substrate 101 constituting the lens, and low refractive index layers 102, 104, and 106 having a refractive index lower than that of the high refractive index layer. A multilayer structure in which these high refractive index layers and low refractive index layers are alternately laminated may be provided. From the viewpoint of improving the visibility of images captured as on-vehicle lenses, the optical member of one or more embodiments of the present invention may have an average spectral reflectance of 2% or less with respect to an incidence light from the normal direction in the light wavelength range of 420 to 680 nm.
The immediately lower layer of the uppermost layer according to one or more embodiments of the present invention refers to the low refractive index layer 106 in
The uppermost layer 107 according to one or more embodiments of the present invention is a metal oxide layer containing SiO2 as a main component and containing at least one element of Cr or Ti. The refractive index with respect to the light wavelength of 587.56 nm of the uppermost layer may be 1.6 or less because the spectral reflectance of the lower layer is not changed as the light reflecting layer. The refractive index may be controlled by designing the mixing ratio of SiO2, Cr, or Ti. In addition, even when the composition ratio of the uppermost layer is changed and the refractive index exceeds 1.6, it will be possible to form an antireflection layer that can withstand salt spray while maintaining the spectral characteristics very thin.
In the optical member of one or more embodiments of the present invention indicated in
The dielectric multilayer films having an antireflection function comprises a high refractive index layer having a refractive index higher than that of the substrate, and a low refractive index layer having a refractive index lower than that of the high refractive index layer. A multilayer structure in which these high refractive index layers and low refractive index layers are alternately laminated may be provided. The number of layers is not particularly limited, but may be 12 or less from the viewpoint of the productivity of the antireflective film. The number of layers depends on the required optical performance, but by laminating approximately 3 to 8 layers, the reflectance of the entire visible region may be reduced. The upper limit number may be 12 layers or less from the viewpoint of preventing the film from peeling off due to an increase in film stress.
The refractive index to the wavelength 587.56 nm of the high refractive index layer may be in the range of 1.9 to 2.45, and the refractive index to the wavelength 587.56 nm of the low refractive index layer may be in the range of 1.3 to 1.5.
The material used for the dielectric multilayer films (high refractive index layer, low refractive index layer) according to one or more embodiments of the present invention may be, for example, oxides of Ti, Ta, Nb, Zr, Ce, La, Al, Si, and Hf, a combination of these oxides, and MgF2 are suitable. By stacking multiple layers of different dielectric materials, it is possible to add the function of reducing the reflectance over the entire visible range.
The above-described low refractive index layer is made of a material having a refractive index lower than that of the substrate. In one or more embodiments of the present invention, the low refractive index layer may be made of SiO2, or a mixture of SiO2 and Al2O3. In particular, the immediately lower layer of the uppermost layer may be a layer containing any of SiO2, MgF2, or Al2O3, or a mixture containing layer made of these materials from the viewpoint of spectral reflectance.
The above-described high refractive index layer is made of a material having a refractive index higher than that of the substrate. The materials therefor may be, for example, a mixture of an oxide of Ta and an oxide of Ti, an oxide of Ti, an oxide of Ta, a mixture of an oxide of La and an oxide of Ti. In one or more embodiments of the present invention, the material may be Ta2O5 or TiO2, or may be Ta2O5.
In the optical member of one or more embodiments of the present invention, layer containing TiO2 as a photocatalyst layer having a self-cleaning function may be provided on the lower layer side of the immediately lower layer of the uppermost layer. The self-cleaning function of TiO2 refers to an organic matter decomposition effect by the photocatalyst. In this case, when TiO2 is irradiated with ultraviolet light, OH radicals are generated after electrons are emitted, and organic substances are decomposed by the strong oxidizing power of the OH radicals. By adding the TiO2 containing layer to the optical member of one or more embodiments of the present invention, it is possible to prevent the optical system from being contaminated with organic matter attached to the optical member. In that case, the upper SiO2 containing layer may have a slightly rough film quality because OH radicals can easily move and the antifouling property of the optical member surface can be improved. This makes it possible to control the film quality by controlling the IAD conditions when forming the upper SiO2 containing layer.
The thickness of the dielectric multilayer films (the total thickness when a plurality of layers is laminated) may be in the range of 50 nm to 5 μm. When the thickness is 50 nm or more, anti-reflection optical characteristics can be exhibited, and when the thickness is 5 μm or less, it is possible to prevent surface deformation due to film stress of the multilayer films itself. As a method of forming a thin film such as the metal oxide on a substrate, there are known evaporation systems such as: vacuum evaporation, ion beam evaporation, and ion plating, and there are known sputtering systems such as: sputtering, ion beam sputtering, and magnetron sputtering. The film forming method for forming the dielectric multilayer films excluding the uppermost layer of one or more embodiments of the present invention may be a vacuum vapor deposition method using an IAD method (hereinafter also referred to as IAD vapor deposition method in one or more embodiments of the present invention).
The IAD method is a method in which high kinetic energy of ions acts during film formation to form a dense film or increase the adhesion of the film. For example, an ion beam method is a method in which a deposition material is accelerated by ionized gas molecules emitted from an ion source to form a film on a substrate surface. The IAD method is also referred to as “ion beam assist method”.
A vacuum vapor deposition apparatus 1 using the IAD method (hereinafter also referred to as an IAD vapor deposition apparatus in one or more embodiments of the present invention) includes a dome 3 in a chamber 2, and a substrate 4 is disposed along the dome 3. A vapor deposition source 5 is equipped with an electron gun for evaporating the vapor deposition substance, and the vapor deposition substance 6 from the vapor deposition source 5 scatters toward the substrate 4 and condenses and solidifies on the substrate 4. At this time, an ion beam 8 is irradiated toward the substrate from an IAD ion source 7 and the high kinetic energy of the ions is applied during the film formation to form a dense film or enhance the adhesion of the film.
Here, the substrate 4 may be glass or a resin. As a resin, a polycarbonate resin and a cycloolefin resin are mentioned.
At the bottom of the chamber 2, a plurality of deposition sources 5 may be disposed. Here, although one vapor deposition source is indicated as the vapor deposition source 5, the number of the vapor deposition sources 5 may be plural. The film forming material (vapor deposition material) of the vapor deposition source 5 is used to generate a vapor deposition substance 6 by an electron gun. The film forming material is scattered and adhered to a substrate 4 (for example, a glass plate) installed in the chamber 2. Thereby, a layer (for example, a SiO2, MgF2 or Al2O3 layer, which is a low refractive index material layer, and Ta2O5 or TiO2 layer, which is a high refractive index material layer) is formed on the substrate 4.
Further, the chamber 2 is provided with an evacuation system not illustrated, whereby the inside of the chamber 2 is evacuated. The level of vacuum in the chamber is usually in the range of 1×10−4 to 1 Pa, and may be in the range of 1×10−3 to 1×10−2 Pa according to one or more embodiments.
The dome 3 has at least one holder (not illustrated) that holds the substrate 4 and is also called a vapor deposition umbrella. The dome 3 has an arc shape in cross section, and has a rotationally symmetrical shape that passes through the center of a chord connecting both ends of the arc and rotates with an axis perpendicular to the chord as an axis of rotational symmetry. By rotating the dome 3 around the axis, for example, at a constant speed, the substrate 4 held by the dome 3 via the holder revolves around the axis at a constant speed.
The dome 3 can hold a plurality of holders side by side in a rotational radial direction (revolutional radial direction) and a rotational direction (revolutional direction). As a result, it becomes possible to simultaneously form a film on a plurality of substrates 4 held by a plurality of holders, and the manufacturing efficiency of the device may be improved.
The IAD ion source 7 is an apparatus for introducing argon or oxygen gas into the inside of the main body to ionize them, and irradiating the substrate 4 with ionized gas molecules (ion beam 8). As the ion source, a Kauffman type (filament), a hollow cathode type, an RF type, a bucket type, or a duoplasmatron type may be applied. By irradiating the substrate 4 with the above-described gas molecules from the IAD ion source 7, for example, molecules of a film forming material evaporated from a plurality of evaporation sources may be pressed onto the substrate 4. Thereby, a film with high adhesion and high density may be formed on the substrate 4. The IAD ion source 7 is disposed to face the substrate 4 at the bottom of the chamber 2, but may be disposed at a position offset from the opposing axis.
The ion beam used in the AD method is used at a low degree of vacuum and the acceleration voltage tends to be lower than the ion beam used in the ion beam sputtering method. For example, an ion beam with an acceleration voltage of 100 to 2000 V and an ion beam with a current density of 1 to 120 μA/cm2 may be used. In the film forming step, the irradiation time of the ion beam may be, for example, 1 to 800 seconds, and the number of particle irradiation of the ion beam may be, for example, 1×1013 to 5×1017/cm2. The ion beam used in the film formation process may be an ion beam of oxygen, an ion beam of argon, or an ion beam of a mixed gas of oxygen and argon. For example, the oxygen introduction amount may be set in the range of 30 to 60 sccm and the argon introduction amount may be set in the range of 0 to 10 sccm.
The monitor system (not illustrated) is a system for monitoring the characteristics of the layer formed on the substrate 4 by monitoring the layer evaporated from each deposition source 5 and attached to itself during vacuum film formation. By this monitor system, optical characteristics (for example, light transmittance, light reflectance, and optical film thickness) of a layer formed on the substrate 4 may be grasped. The monitoring system also includes a quartz crystal thickness monitor, which can also monitor the physical thickness of the layer deposited on the substrate 4. The monitor system also functions as a control unit that controls ON/OFF switching of the plurality of evaporation sources 5, and ON/OFF switching of the IAD ion source 7 according to the layer monitoring result.
The uppermost layer according to one or more embodiments of the present invention is a metal oxide layer containing SiO2 as a main component and containing at least one element of Cr or Ti. Here, the main component means that Si is contained most as an element contained in the uppermost layer.
From the viewpoint of the function as a low refractive index layer and the function of improving salt water resistance, the content of Si contained in the uppermost layer may be in the range of more than 9 at % and less than 31 at %, the content of Cr contained in the uppermost layer may be more than 0.3 at % and 2.3 at %, and the Ti content may be more than 0.2 at % and less than 0.8 at %.
For forming the uppermost layer of one or more embodiments of the present invention, an ion source used in the IAD method may be used as a sputtering source in order to ensure high productivity.
By performing such sputtering film formation, it is possible to form a mixed film containing a metal oxide such as SiO2 as a main component on a substrate at an unprecedented slow film forming rate of 10 pm/sec or less. Since the film forming rate is on the order of pm/sec, a film forming rate on the order of 1/10 to 1/100 is realized as compared with the conventional vapor deposition method and sputtering method, it is possible to produce homogeneous very thin films (e.g., film thickness in the range of 5 nm or less).
Hereinafter, the film forming method of one or more embodiments of the present invention will be described with reference to the drawings.
An ion beam sputtering film forming apparatus 50 according to one or more embodiments of the present invention includes a dome 3 in a chamber 2 similarly to the IAD vapor deposition apparatus of
The sputtering source is an IAD ion source 7, and an ion beam 8 emitted from the IAD ion source 7 is directed to a first sputtering target 52 and a second sputtering target 53. Although
The first sputtering target 52 and the second sputtering target 53 are disposed on a target holder 51 located between the substrate 4 and the IAD ion source 7. A surface of the first sputtering target 52 and the second sputtering target 53 opposite to a surface facing the substrate 4 is sputtered by the ion beam 8 from the IAD ion source 7 to generate and scatter sputtered particles 54 and 55, and a film is formed on the substrate 4.
Sputtering targets may be stacked with one or more film deposition materials, and simultaneous multi-source sputtering is possible. In
The feature of one or more embodiments of the present invention is that the sputtered particles 54 and 55 are generated by sputtering by the ion beam 8 on a surface opposite to a surface facing the substrate 4 and not on the surface directly facing the substrate. Therefore, the sputtered particles 54 and 55 scatter toward the substrate while bypassing the sputtering target to contribute to film formation, and therefore, the film forming rate may be reduced.
Therefore, in addition to the ion beam irradiation time, the control factors of the film forming rate are the size of the sputtering target (D in the figure), the distance from the IAD ion source to the sputtering target (H in the figure), the distance from the sputtering target to the substrate 4. Therefore, it is not necessary to perform adjustment such as lowering the ion beam irradiation intensity to adjust the d film forming rate as in the prior art. Compared to known vapor deposition methods and sputtering methods, a film forming rate of 10 pm/sec or less, corresponding to 1/10 to 1/100 of the film forming rate may be realized, and it is possible to produce homogeneous, extremely thin films.
The film forming rate may be 5 pm/sec or less, or may be in the range of 0.1 to 3 pm/sec.
In addition, from the viewpoint of adjusting the film forming rate, the sputtering target may change the angle facing the IAD ion source, in addition to the distance (H) from the IAD ion source. Further, forming a film by sputtering while rotating the sputtering target, or forming a film by sputtering while lifting the film may also be a method from the viewpoint of adjusting the film forming speed and the composition of the film forming material.
Regarding the multi-source sputtering, in the sputtering target according to one or more embodiments of the present invention, the sputtering surface of the target may have a metal surface and a glass surface.
The metal surface may contain at least one element of Ti, Cr, Ni and Al from the viewpoint of improving the salt water resistance as an uppermost layer.
Further, the glass surface may be mainly composed of SiO2 and may contain at least one element of Ta, Zr and Na from the viewpoint of improving the durability against alkali and acid as an uppermost layer and ensuring the environmental resistance.
Further, Ta2O5, ZrO2 or ZnO may also be used as a sputtering target by changing the components of the glass, from the viewpoint of improving the durability to the alkali and the acid.
The example of arrangement of the film forming material of the sputtering target in the case of performing multi-source sputtering is indicated below.
A first sputtering target 70 is formed in a disk shape, and second sputtering targets 71, which are film forming materials to be mixed, are arranged opposite to each other along the outer periphery of the first sputtering target. It may be arranged equally at four positions so as to be at an angle of 90°. The circle of the second sputtering target 71 indicates the position of the arrangement, and the size thereof does not indicate the size of the sputtering target.
The first sputtering target 70 is formed in a disk shape, and the second sputtering targets 71, which are film forming materials to be mixed, face each other and are arranged at four positions so as to form an angle of 90°. Further, it may be equally arranged the third sputtering targets 72 at four positions having an angle of 45° with the second sputtering targets 71.
In any case, when sputtering is performed while rotating the sputtering target, the generation of sputtered particles may be made uniform.
The first sputtering target 70 is formed in a disk shape, and the second sputtering targets 71, which are film forming materials to be mixed, face each other, and are evenly arranged at four positions so as to form an angle of 90°. The size of the first sputtering target 70 is represented by Φ1 (unit mm), and the size of the second sputtering target 71 is represented by Φ2 (unit mm).
The above-described Φ1 may be in the range of 100 to 500 mm, or may be in the range of 200 to 400 mm. The above-described Φ2 may be in the range of 10 to 100 mm, or may be in the range of 20 to 80 mm. The thickness of both may be in the range of 1 to 5 mm.
The distance from the IAD ion source 7 to the first sputtering target 70 is indicated by H1 (unit mm), and the distance to the second sputtering target 71 is indicated by H2 (unit mm).
The above-described H1 and H2 may be in the range of 50 to 200 mm, or may be in the range of 100 to 150 mm.
The above-described Φ1, Φ2, H1 and H2 may be determined as control factors of the film forming speed and the mixing ratio.
The film forming apparatus used in the uppermost layer forming method of one or more embodiments of the present invention has a means capable of arranging the sputtering target between the substrate and the ion source at a desired timing. A surface opposite to a surface facing the substrate of the sputtering target to be disposed may be sputtered by an ion beam emitted from the ion source to form a film on the substrate.
By having a means capable of arranging the sputtering target in the apparatus at a desired timing, a lower dielectric multilayer film is deposited on the substrate by the IAD method using the IAD vapor deposition apparatus indicated in
The means by which the sputtering target may be disposed at a desired timing is not particularly limited. As an example, there may be mentioned an introduction means for moving a sputtering target prepared in advance outside the apparatus along a guide rail provided inside the apparatus from a window-like entrance provided in the chamber.
A film forming apparatus 90 includes a dome 3 in a chamber 2 similarly to the vapor deposition apparatus of
A plurality of vapor deposition sources is prepared.
For example, dielectric multilayer films in which a SiO2 containing layer which is a low refractive index layer and a Ta2O5 containing layer which is a high refractive index layer are alternately laminated is formed as an under layer of the uppermost layer. The immediately lower layer of the uppermost layer is a layer containing any of SiO2, MgF2, or Al2O3, or a mixture containing layer made of these materials. Furthermore, a photocatalyst layer containing TiO2 having a self-cleaning function may be provided as a layer below it.
Then, the operation of the vapor deposition source 5 is stopped, and the sputtering target 52 (53) prepared in advance outside the apparatus is moved along the sputtering target introduction means 91 such as a guide rail provided inside the apparatus from the window-like entrance. It is placed on a target holder 51 located between the substrate 4 and the IAD ion source 7.
The ion source is an IAD ion source 7, and the ion beam 8 emitted from the IAD ion source 7 is irradiated on a surface of the first sputtering target 52 and the second sputtering target 53 opposite to a surface facing the substrate 4 to perform sputtering. The first sputtered particles 54 and the second sputtered particles 55 are scattered, and film formation is made on the dielectric multilayer films which is an undercoat film formed in advance on the substrate 4, and a laminate of dielectric multilayer films 100 and an uppermost layer 107 are formed on the substrate.
The thickness of the uppermost layer may be 15 nm or less, or may be in the range of 1 to 10 nm, or may be in the range of 1 to 5 nm, from the viewpoint of excluding the influence on the light reflectance of the lower layer.
Film forming conditions of the uppermost layer may be as follows: the level of reduced pressure in the chamber is usually in the range of 1×10−4 to 1 Pa, or may be in the range of 1×10−3 to 1×10−2 Pa, the film forming rate is in the range of 1 to 10 pm/sec, by using the RF ion source “OIS One” made by Optorun Co. Ltd., the acceleration voltage output of the ion beam is in the range of 500 to 1500 V, the acceleration current is in the range of 300 to 1500 mA, the bias current is in the range of 500 to 2000 mA, the introduction amount of oxygen is in the range of 20 to 60 sccm, and the introduction amount of argon is in the range of 0 to 15 sccm.
The optical member of one or more embodiments of the present invention may be an on-vehicle or outdoor optical lens, and in particular, a lens for an on-vehicle camera (a lens forming a lens unit).
The “on-vehicle camera” is a camera installed on the outer side of the vehicle body. It is installed in the rear part of the vehicle body and used for backward confirmation, or installed in the front part of the vehicle body and used for forward confirmation or lateral confirmation, for confirmation of the distance to the front vehicle.
Such a lens unit for an on-vehicle camera is constituted by a plurality of lenses, and more specifically, it is constituted by an object-side lens disposed on the object-side and an image-side lens group disposed on the image-side. The image-side lens unit includes a plurality of lenses and a stop provided between the lenses.
Among the plurality of lenses, the object-side lens is an exposed surface exposed to the outside air, and the optical thin film is provided on the lens having the exposed surface.
Examples of the outdoor optical member include an outdoor installation type surveillance camera, and the optical thin film is used on a lens having an exposed surface exposed to the outside air among lenses constituting the surveillance camera.
Although the embodiments of the present invention have been described and illustrated in detail, the disclosed embodiments are made for purpose of illustration and example only and not limitation. The scope of the present invention should be interpreted by terms of the appended claims.
Hereinafter, one or more embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, although the term “part” or “%” is used in examples, unless otherwise indicated, it represents “mass part” or “mass %”.
Using the film forming apparatus having both the IAD vapor deposition apparatus and the ion beam sputtering apparatus indicated in
SiO2: manufactured by Merck, Product name SiO2
Ta2O5: manufactured by Canon Optron, Inc., Product name A600
TiO2: manufactured by Fuji Titanium Co., Ltd. Product name TiO2
MgF2: manufactured by Merck, Product name MgF2
Al2O3: manufactured by Merck, Product name Al2O3
SUS304: Stainless steel
Glass Substrate
Heating temperature: 300° C.
Initial level of vacuum: 1.33×10−3 Pa
Electron Gun
Film forming material for low refractive index layer: SiO2 (manufactured by Merck, Product name SiO2) The substrate was placed in a vacuum deposition apparatus, the film forming material was loaded into the first evaporation source, a film was deposited at a deposition rate of 3 Å/sec, and a low refractive index layer with a thickness of 24.9 nm was formed on the substrate.
The low refractive index layer was formed by the IAD method, using an apparatus of RF ion source “OIS One” made by Optorun Co. Ltd. with an acceleration voltage of 1200 V, an acceleration current of 1000 mA, and a neutralization current of 1500 mA. The IAD introduction gas was set as: O2 50 sccm, Ar gas 0 sccm, and neutral gas O250 sccm.
Film forming material for high refractive index layer: Ta2O5 (manufactured by Canon Optron, Inc., Product name A600)
The substrate was placed in a vacuum deposition apparatus, the film forming material was loaded into the second evaporation source, a film was deposited at a deposition rate of 3 Å/sec, and a high refractive index layer with a thickness of 26.4 nm was formed on the low refractive index layer. The high refractive index layer was formed by the IAD method in the same way as formation of the low refractive index layer.
On the formed high refractive index layer, a low refractive index layer and a high refractive index layer were formed under the film thickness conditions described in Table I to produce a total of five dielectric multilayer films (the notation (IAD) after the film formation material indicates that the IAD method was used).
After the formation of the dielectric multilayer films, the operation of the evaporation source was stopped, the following sputtering target was introduced into the chamber, and the uppermost layer was formed by sputtering film formation using the IAD ion source as a sputtering source. The film forming material on the sputtering target was arranged as shown in
First sputtering target SUS304, H1: 125 mm, Φ1: 285 mm
Second sputtering target SiO2 (quartz glass), H2: 119 mm, Φ2: 50 mm
RF ion source “OIS One” made by Optorun Co., Ltd.
Acceleration voltage (V): 1200
Acceleration current (mA): 1000
Neutralization current (mA): 1500
Heating temperature: 300° C.
Conditions of IAD introduction gas were set as: O2 50 sccm, Ar gas 0 sccm, and neutral gas O2 50 sccm.
Level of vacuum: 1×10−2 Pa
Under the above conditions, the ion beam irradiation time from the IAD ion source was set to 165 minutes, and the surface of the sputtering target opposite to the surface facing the substrate was sputtered with the ion beam. According to the following film thickness measurement, the uppermost layer mixed with Si, Cr, Ni, and Fe having a film thickness of 15 nm was formed at a film forming rate of 1.52 pm/sec.
The composition of the uppermost layer was measured by the following X-ray photoelectron spectrometer (XPS), and had the elemental composition described in Table V.
The film thickness was measured by the following method.
(1) TiO2 and SiO2 are formed in a film thickness of ¼λ (λ=550 nm) on a white sheet glass substrate in advance, and the light reflectance is measured.
(2) A film is formed on the TiO2 and SiO2 films as described in (1) above under the conditions for forming a protective film, the light reflectance is measured, and the refractive index and the film thickness of the uppermost layer are calculated from the amount of change.
The light reflectance was measured at a light wavelength of 550 nm with a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation.
Device name: X-ray photoelectron spectroscopy (XPS)
Device type: Quantera SXM
Device manufacturer: ULVAC-PHI
Measurement conditions: X-ray source: monochromating AlKα ray 25 W-15 kV
Level of vacuum: 5.0×10−8 Pa
Depth direction analysis was performed by argon ion etching. For data processing, MultiPak manufactured by ULVAC-PHI, Inc. was used.
In the same manner as in the preparation of the optical member sample Example 1, dielectric multilayer films having the layer constitution and film thickness indicated in Tables I to III were formed, and then the uppermost layer was formed under the conditions indicated in Tables V and VI. Thus, optical member sample examples 2, 3, 4, 9, 11, 13, 14, 15, 19, 20, 23, 24 and 27 were prepared.
An example sample using MgF2 (trade name: MgF2 manufactured by Merck) as a low refractive index material was formed using an electron gun at a film forming rate of 3 mm/sec.
In optical member sample examples 13, 14, 15, 23, and 24, a photocatalyst layer using TiO2 was formed as a lower layer of the uppermost layer of the dielectric multilayer films.
In optical member sample example 27, as indicated in Table III, SiO2 and Al2O3 were mixed at a mass ratio of 97:3 as the uppermost layer of the dielectric multilayer films.
In the same manner as the preparation of the optical member sample Example 1, five-layered dielectric multilayer films were formed as described in Table I.
After the formation of the dielectric multilayer films, the operation of the evaporation source was stopped, the following sputtering target was introduced into the chamber, and the uppermost layer was formed by sputtering film formation using the IAD ion source as a sputtering source. The film forming material on the sputtering target was arranged as shown in
(Sputtering target: B material)
First sputtering target TiO2, H1: 125 mm, Φ1: 285 mm
Second sputtering target SiO2 (quartz glass), H2: 119 mm, Φ2: 50 mm
In the same manner as in the preparation of the optical member sample example 5, the uppermost layer was formed under the conditions indicated in Table VI and Table VII, and the optical member sample examples 6, 7, 8, 10, 12, 16, 17, 18 21, 22, 25 and 26 were prepared.
Optical member sample comparative examples 1 to 6 having the configuration indicated in Table IV were prepared in the same manner as in the production of optical member sample examples 1 to 27 except that the uppermost layer was not formed.
The following evaluation was carried out using the obtained optical member sample examples 1 to 27 and optical member sample comparative examples 1 to 6.
Using a spectrophotometer U-4100 manufactured by Hitachi High-Technology Co., Ltd. in the light wavelength range of 350 to 800 nm, the spectral reflectance with respect to an incidence light from the normal direction was measured.
The measurement results are indicated in
The following evaluation was performed using the obtained optical member sample.
The following steps (a) to (c) are considered as 1 cycle, and 8 cycles were carried out.
(a) The solvent at 25±2° C. is sprayed on the uppermost layer of the sample for 2 hours at a temperature in the spray tank of 35±2° C.).
(b) After spraying, leave the sample at 40±2° C. and 95% RH for 22 hours.
(c) After repeating (a) and (b) four times, leave the sample at 25° C. and 55% RH for 72 hours.
Solute used: NaCl, MgCl2, CaCl2)
Solute concentration: 5±1% (mass ratio)
The spectral reflectance of the optical member sample before and after the salt spray test was measured, and the average value of the spectral reflectance in the light wavelength range of 420 to 680 nm was evaluated. When the variation was within 0.1%, it was ranked as passing the examination (designated as ◯).
The following evaluation was performed using the obtained optical member sample.
A UV light 202 is installed on a black container box 201.
The sample is placed on a flat plate 203 with a marker surface 205 on an uppermost layer side of an optical member sample 204 set to the UV light 202 side.
Adjust the height so that the distance between the UV light 202 and the optical member sample 204 is about 35 to 40 mm.
(b) How to Paint Sample with a Pen
On the photocatalytic surface, draw a line with The Visualizer pen made of Ink Intelligent Corporation.
This is done with a manner of dropping ink in a dotted pattern rather than drawing a line.
Ink is applied in 5 points in one step×2 times.
The lamp lights up when a plug of the UV light is inserted into a socket.
Irradiate with UV light at a height of 35 to 40 mm and an integrated light amount of 10 J for 1 hour.
Check the color change after 1 hour and 2 hours.
Since the color is not stable immediately after removal of the sample, the color change at each time is evaluated after 30 minutes or more after removal. When there is a photocatalytic effect, the color change becomes transparent from blue (in this case, “photocatalytic effect” is present).
Tables I to VII below indicate the configuration, production method, and evaluation results of the optical member samples.
The following was found from Tables I to VII. Examples 1 to 27, which are optical member samples having the constitution of one or more embodiments of the present invention, were prepared by adding any element of Cr or Ti to the uppermost layer containing SiO2 as a main component as compared to Comparative Examples 1 to 6. By this constitution, Examples 1 to 27 were found to have excellent salt water resistance, no influence on spectral reflectance of the lower layer over time.
Moreover, it was found that the optical member sample which is provided with a TiO2 containing layer in the optical member as a photocatalyst layer exhibited the photocatalytic effect, and had a self-cleaning function. Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the invention should be limited only by the attached claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-219874 | Nov 2018 | JP | national |
