CN107102383B - Infrared-transmitting film, optical film, antireflection film, optical member, optical system, and imaging device - Google Patents
Infrared-transmitting film, optical film, antireflection film, optical member, optical system, and imaging device Download PDFInfo
- Publication number
- CN107102383B CN107102383B CN201611094455.XA CN201611094455A CN107102383B CN 107102383 B CN107102383 B CN 107102383B CN 201611094455 A CN201611094455 A CN 201611094455A CN 107102383 B CN107102383 B CN 107102383B
- Authority
- CN
- China
- Prior art keywords
- film
- infrared
- oxide
- optical
- transmitting film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
The invention provides an infrared transmitting film provided in an optical member used in a far infrared wavelength region, the infrared transmitting film being a novel infrared transmitting film which is easy to form and has high water resistance. The invention also provides an optical film, an antireflection film, an optical member, an optical system, and an imaging device, each of which is provided with the infrared-transmitting film. The infrared transmitting film of the present invention is characterized by containing zinc oxide as a main component and a metal oxide having an attenuation coefficient of 0.4 or less over the entire wavelength range of 8 to 14 μm as an additive.
Description
Technical Field
The present invention relates to an infrared transmitting film, an optical film, an antireflection film, an optical member, an optical system, and an imaging device, and more particularly, to an infrared transmitting film, an optical film, an antireflection film, an optical member, an optical system, and an imaging device, which are suitable for an optical system using far infrared rays.
Background
Conventionally, optical systems using infrared rays have been used for various purposes such as monitoring imaging devices, in-vehicle imaging devices, and thermal distribution analysis. As these optical systems, there are generally known a mid-infrared optical system using light in the mid-infrared wavelength region (2.5 to 4 μm) and a far-infrared optical system using light in the far-infrared wavelength region (8 to 14 μm). For example, a far infrared optical system is mainly used in a monitoring image pickup device, an in-vehicle image pickup device, and the like. Optical components such as infrared transmission lenses constituting these optical systems have a lower transmittance of incident light than optical components constituting visible light optical systems. Therefore, it is important to provide an antireflection film on the incident surface of the optical member to increase the amount of transmitted light of the incident light and to prevent the shortage of light due to surface reflection.
As an antireflection film of an optical member used in a far infrared optical system, for example, patent document 1 (japanese patent application laid-open No. 2007-298661) discloses a method in which a Ge film, a ZnS film, a YF film, and a Ge film are laminated in this order from the substrate side on an Si substrate3An antireflection film having a 5-layer structure. And areFurther, patent document 2 (Japanese patent application laid-open No. 2011-221048) discloses a chalcogenide glass substrate on which BiO is laminated in this order from the substrate side2Film, YF3An antireflection film having a 2-layer structure. As described in these patent documents, an antireflection film has a multilayer structure formed by laminating a plurality of infrared-transmitting films, and it is easy to realize a low reflectance over the entire wavelength range for light in a large wavelength range. Conventionally, as a layer constituting material of an antireflection film used in a far infrared wavelength region, the following materials including those disclosed in patent documents 1 and 2 are known.
High refractive index material: ge. Si
Low refractive index material: YF3、YbF3、NaF、NdF3、LaF3、CaF2、SrF2
Intermediate refractive index material: ZnS, ZnSe, PbTe, Y2O3、CeO2、HfO2
When an antireflection film is provided on the surface of an optical member, a vacuum deposition method is generally used in which a raw material is heated and deposited by electron beam heating or resistance heating. However, in view of the future expansion of demand for infrared optical systems, a film formation method for producing an antireflection film by a method suitable for mass production with high production efficiency is currently required.
For example, magnetron sputtering is an example of a film deposition method that has higher production efficiency than vacuum deposition. However, when the low refractive index material, i.e., the fluoride, is used as a raw material, fluorine in the target material is lost in the sputtering step. Therefore, it is difficult to obtain a film having a stoichiometric composition, and an infrared-transmitting film transparent to light in the wavelength range of use cannot be obtained. The same applies to the intermediate refractive index materials ZnS, ZnSe, and PbTe, and it is difficult to produce a film of a stoichiometric composition by a magnetron sputtering method using these materials.
On the other hand, the high refractive index materials Ge and Si can be formed by magnetron sputtering. As described above, for light in a large wavelength region, an optical film having a multilayer structure is required to achieve a low reflectance over the entire wavelength region.
Here, since the refractive index of the fluoride is too low for Ge or Si, a good antireflection performance cannot be obtained even when a fluoride film is laminated on a Ge film or a Si film. As described above, it is difficult to produce a fluoride film having a desired composition by the magnetron sputtering method.
In view of these problems, a configuration may be considered in which a Ge film or a Si film is alternately laminated with a film formed of an intermediate refractive index material. However, as described above, ZnS, ZnSe, and PbTe are difficult to be formed into films by magnetron sputtering, and these materials are toxic, and thus their handling is difficult. On the other hand, with respect to Y2O3、CeO2、HfO2However, the film is translucent to light in the far infrared region (8 to 14 μm), and a film transparent to far infrared rays cannot be obtained.
Further, many of the monitoring imaging devices, the in-vehicle imaging devices, and the like are installed outdoors for use. Since the optical film is provided on the surface of these optical members, it is required to have high water resistance in addition to adhesion to the film surface.
Disclosure of Invention
Problems to be solved by the invention
In view of the above problems, an object of the present invention is to provide a novel infrared transmitting film, an optical film, an antireflection film, an optical member, an optical system, and an imaging device, which are easy to form and have high water resistance.
Means for solving the problems
In order to achieve the object of the present invention, an infrared transmitting film of the present invention is characterized by containing zinc oxide as a main component and a metal oxide having an attenuation coefficient of 0.4 or less over the entire wavelength range of 8 to 14 μm as an additive.
The optical film, the antireflection film, the optical member, and the optical system of the present invention are each characterized by being provided with the infrared-transmitting film of the present invention.
The imaging device of the present invention is characterized by comprising an optical system including an optical surface on which the infrared-transmitting film of the present invention is provided.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an infrared transmitting film provided in an optical member used in a far infrared wavelength region, the infrared transmitting film being a novel infrared transmitting film which is easy to form and has high water resistance. The invention also provides an optical film, an antireflection film, an optical member, an optical system, and an imaging device, each of which is provided with the infrared-transmitting film.
Detailed Description
Embodiments of the infrared transmitting film, the optical film, the antireflection film, the optical member, the optical system, and the imaging device according to the present invention will be described below.
1. Infrared ray transmission film
First, an embodiment of the infrared-transmitting film of the present invention will be described. The infrared transmitting film of the present invention is characterized by containing zinc oxide as a main component and a metal oxide having an attenuation coefficient of 0.4 or less over the entire wavelength range of 8 to 14 μm as an additive. The infrared ray transmitting film is an optical film that transmits infrared rays.
1-1, zinc oxide
Zinc oxide has an attenuation coefficient of less than 0.05 over the entire wavelength range of 8 to 14 μm, that is, over the entire far infrared wavelength range, and is a material having high transparency to far infrared rays (light having a wavelength of 8 to 14 μm).
The refractive index of zinc oxide for far infrared rays is in the range of 1.5 to 2.5, and zinc oxide is a medium refractive index material in the far infrared wavelength region. Therefore, the infrared ray transmitting film is also suitable as a constituent material of the antireflection film. For example, by alternately laminating the infrared ray transmitting film and a Ge film, a Si film, or the like having a high refractive index in the far infrared wavelength region, an antireflection film having a good antireflection performance over the entire far infrared wavelength region can be obtained.
However, zinc oxide is a material that is easily crystallized. The zinc oxide film formed by physical vapor deposition such as vacuum vapor deposition or sputtering has a polycrystalline structure. Therefore, the grain boundaries are liable to contain water or the like, and the zinc oxide film has low water resistance and is difficult to satisfy durability which is actually required. In view of these problems, the present inventors have found that water resistance can be improved by using a film containing zinc oxide as a main component and a specified metal oxide as an additive. According to the present invention, high water resistance can be achieved. Hereinafter, a specific metal oxide used as an additive in the present invention will be described.
1-2, metal oxide
1) Coefficient of attenuation
The metal oxide is required to have an attenuation coefficient of 0.4 or less over the entire far infrared wavelength range. When the attenuation coefficient in the far infrared wavelength region exceeds 0.4, the transparency to far infrared rays is lowered. That is, the transmittance of far infrared rays of the infrared ray transmitting film is lowered, and it is difficult to use the infrared ray transmitting film as an optical film.
As the metal oxide having an attenuation coefficient of 0.4 or less over the entire far infrared wavelength region, for example, zirconium oxide (ZrO)2) Chromium oxide (Cr)2O3) Hafnium oxide (HfO)2) Bismuth oxide (Bi)2O3) Yttrium oxide (Y)2O3) Copper oxide (CuO), magnesium oxide (MgO), and the like. When these metal oxides are used as additives, the zinc oxide film can maintain its transmittance for far infrared rays and can have improved water resistance.
Here, from the viewpoint of promoting the transparency of the infrared ray transmitting film in the use wavelength region to become higher, the attenuation coefficient of the metal oxide used as an additive is preferably less than 0.4, more preferably less than 0.2, and further preferably less than 0.1 over the entire use wavelength region. An appropriate metal oxide can be selected from the above-listed metal oxides and the like according to the wavelength region in which the infrared-transmitting film is used. Further, the attenuation coefficients of the respective metal oxides listed above are shown below. Hereinafter, k (8 μm) represents an attenuation coefficient (k) at a wavelength of 8 μm, and k (14 μm) represents an attenuation coefficient at a wavelength of 14 μm. The attenuation coefficient of zinc oxide is also shown below.
Zinc oxide: k (8 μm) is 0.004, k (14 μm) is 0.03
Zirconium oxide: k (8 μm) is 0.06, k (14 μm) is 0.35
Chromium oxide: k (8 μm) is 0.007, k (14 μm) is 0.37
Hafnium oxide: k (8 μm) is 0.006 and k (14 μm) is 0.4
Bismuth oxide: k (8 μm) is 0.002, k (14 μm) is 0.025
Yttrium oxide: k (8 μm) is 0.00027, k (14 μm) is 0.078
Copper oxide: k (8 μm) is 0.0001, k (14 μm) is 0.04
Magnesium oxide: k (8 μm) is 0.00025, k (14 μm) is 0.014
As described above, the attenuation coefficients of bismuth oxide, yttrium oxide, copper oxide, and magnesium oxide are small as compared with those of zirconium oxide, chromium oxide, and hafnium oxide, and are less than 0.1 over the entire far infrared wavelength region. Therefore, from the viewpoint of maintaining high transparency over the entire far infrared wavelength range, it is more preferable to use one or more additives selected from the group consisting of bismuth oxide, yttrium oxide, copper oxide, and magnesium oxide. In this case, one of these metal oxides may be used as an additive, or one or more of these metal oxides may be mixed and used.
Further, from the viewpoint of improving the water resistance of the zinc oxide film, tantalum oxide (Ta) may be used2O5) Metal oxides having an attenuation coefficient outside the above range are used as additives. The damping coefficient of tantalum oxide is shown below. However, as described below, tantalum oxide has a large attenuation coefficient, and when it is contained as an additive in a zinc oxide film, the transmittance of the zinc oxide film with respect to far infrared rays is lowered, and it is difficult to use it as an optical film.
Tantalum oxide: k (8 μm) is 0.028, k (14 μm) is 0.75
2) Refractive index
The refractive index of the metal oxide with respect to light in the far infrared wavelength region is preferably 0.8 to 2.5. By using a metal oxide having a refractive index equal to that of zinc oxide as an additive, the refractive index of the obtained infrared ray transmitting film can be made equal to that of zinc oxide. In addition, the refractive index of each of the metal oxides listed above in the far infrared wavelength region is in the range of 0.8 to 2.5. Here, from the viewpoint of not causing a large change in the refractive index of zinc oxide, it is preferable to use a metal oxide having a refractive index equivalent to that of zinc oxide. From this viewpoint, a metal oxide having a refractive index of 1.0 to 2.5 is more preferably used as the additive, and a metal oxide having a refractive index of 1.5 to 2.5 is more preferably used as the additive.
3) Content (wt.)
Next, the content of the metal oxide as an additive in the infrared ray transmitting film will be described. The content of the metal oxide in the infrared ray transmitting film is preferably 0.1 mass% or more and less than 50 mass%. The content mentioned here means the total amount of metal oxide contained as an additive in the infrared ray transmitting film. That is, when a plurality of metal oxides are used as additives, the total amount thereof is referred to. In the infrared-transmitting film, zinc oxide is the main component. That is, the infrared ray transmitting film contains 50 mass% or more of zinc oxide. The infrared ray transmitting film is composed of zinc oxide and a metal oxide as an additive, except for inevitable impurities.
By containing the metal oxide as an additive in the above range with respect to zinc oxide having high transparency to light in the far infrared wavelength region, the transparency to far infrared rays of the infrared ray transmitting film can be maintained at a high level, and the water resistance can be improved. At the same time, acid resistance, mechanical strength, and the like can be improved.
Here, the attenuation coefficient of the metal oxides listed above is equal to or greater than that of zinc oxide. Therefore, the content of the metal oxide having a higher attenuation coefficient than zinc oxide is more preferably 0.1 to 15 mass%, even more preferably 0.1 to 10 mass%, and most preferably 0.1 to 5 mass%, from the viewpoint of obtaining an infrared ray transmitting film having higher transparency to light in the far infrared region.
4) Crystal structure
In the infrared transmitting film of the present invention, the metal oxide is preferably segregated in the grain boundary of zinc oxide. The metal oxide segregated in the grain boundaries of zinc oxide makes it difficult for the grain boundaries to contain water, and the infrared-transmitting film has good water resistance. When the metal oxide is segregated in the grain boundary, crystal growth is inhibited and the crystal grains become fine. Therefore, the residual stress in the film is small, which is one of the factors that the water resistance is improved. Further, the film has a fine crystal structure, and thus the mechanical strength of the film is also high. Further, acid resistance and the like are also improved.
That is, in order to improve the water resistance of the zinc oxide film, the metal oxide as an additive is preferably in an amount sufficient to fill the grain boundaries of the zinc oxide film. From this viewpoint, the content of the metal oxide having an attenuation coefficient equivalent to that of zinc oxide in the infrared-transmitting film is more preferably 0.1 mass% or more and 15 mass% or less, still more preferably 0.1 mass% or more and 10 mass% or less, and most preferably 0.1 mass% or more and 5 mass% or less. For example, bismuth oxide has a smaller attenuation coefficient than zinc oxide and has high transparency to far infrared rays, but bismuth oxide itself has poor water resistance. However, by containing bismuth oxide in the more preferable range described above, the water resistance of the zinc oxide film can be improved more.
5) Film forming method
In the production of the infrared transmitting film of the present invention, for example, zinc oxide is used as a main component, sintered ceramics to which the metal oxide is added is used as a starting material, and the film can be formed by various dry film forming methods such as a vacuum deposition method and a sputtering method. In these methods, a sintered product of a mixed oxide can be used as a starting material.
Among various dry film-forming methods, the magnetron sputtering method is particularly simple and convenient, and the production efficiency is high compared with the vacuum evaporation method. Therefore, when the infrared ray transmitting film is produced for optical parts to be mass-produced, it is preferable to use a magnetron sputtering method. At this time, as the discharge form, a direct current, a high frequency discharge, or an alternating current discharge may be employed.
When the infrared ray transmitting film is produced by the magnetron sputtering method, a metal alloy target in which a metal constituting the metal oxide is added to metallic zinc in a predetermined amount may be used as a starting material. The infrared transmitting film of the present invention containing zinc oxide as a main component and the metal oxide can be obtained by forming a film using the metal alloy target in an oxygen-protected atmosphere.
When a zinc oxide film is produced by these physical vapor deposition methods, the metal oxide is not formed as a composite oxide with zinc oxide, but is segregated in the grain boundary of zinc oxide. That is, an infrared transmitting film having a polycrystalline structure of zinc oxide in which the metal oxide is segregated in grain boundaries can be obtained.
The infrared transmitting film of the present invention is not limited to a dry film formation method, and various wet film formation methods such as a chemical vapor deposition method and a sol-gel method may be used. Among various film-forming methods, an appropriate film-forming method can be selected depending on the use of the infrared-transmitting film, the material of the substrate, and the like.
1-3, base Material
The infrared ray transmitting film of the present invention may be provided on the surface of an optical member or the like, for example. In this case, the material of the base material of the optical member or the like is not particularly limited.
The infrared transmission film of the present invention has good adhesion to germanium (Ge), silicon (Si), zinc selenide (ZnSe), and zinc sulfide (ZnS) which are transparent to light in the far infrared wavelength region. The infrared transmitting film of the present invention has good adhesion to various chalcogenide glasses containing germanium (ge), arsenic (As), selenium (Se), sulfur (S), antimony (Sb), Ga (Ga), and the like As components. Therefore, when various infrared optical members such as an optical lens for infrared rays formed of these materials are used as a base material, the infrared transmitting film of the present invention can be directly provided on the surface of the infrared optical member, and good adhesion can be obtained.
2. Optical film
Next, the optical film of the present invention will be described. In the present invention, the optical film refers to an optical filter such as an antireflection film, a boundary filter, or a band-pass filter. The optical film of the present invention may be a single layer film composed of one optical film or a multilayer film in which two or more optical films are laminated. In each case, the optical film of the present invention includes the infrared-transmitting film of the present invention. That is, the optical film may be a single layer film composed of the infrared ray transmitting film of the present invention, or may be a multilayer film having at least one infrared ray transmitting film.
The infrared transmitting film of the present invention contains zinc oxide as a main component, which is an intermediate refractive index material, and has a refractive index equivalent to that of zinc oxide. The infrared transmitting film also has good adhesion to a high refractive index material or a low refractive index material described below.
High refractive index material: ge. Si
Low refractive index material: YF3、YbF3、NaF、NdF3、LaF3、CaF2、SrF2
Therefore, an optical film having an arbitrary layer structure can be obtained in which the infrared ray transmitting film is used as an intermediate refractive index layer, and further, a high refractive index layer and/or a low refractive index layer made of the above-mentioned material are appropriately laminated.
3. Anti-reflection film
Next, an embodiment of the antireflection film of the present invention will be described. The antireflection film of the present invention is one of the optical films described above, and is characterized by comprising the infrared-transmitting film of the present invention. The antireflection film of the present invention may be a single layer film composed of one layer of the infrared-transmitting film, but is more preferably a multilayer film laminated with the high refractive index layer and/or the low refractive index layer. In the case of forming an antireflection film having a multilayer structure, interface reflection light generated at each interface makes it easy to realize low reflectance in a large wavelength region by utilizing the interference action of light.
4. Optical component
The optical member of the present invention is characterized by comprising the infrared-transmitting film of the present invention. Examples of the optical member include various optical members constituting an imaging optical system, a projection optical system, and the like of an imaging device or a projection device. More specifically, lenses, prisms (dichroic prism, color combining prism, etc.), Polarizing Beam Splitters (PBS), cut-off filters (for long wavelength, for short wavelength, etc.), and the like can be cited. In particular, an infrared lens constituting a far infrared imaging optical system using light in a far infrared wavelength region is preferable.
5. Optical system/image pickup apparatus
The optical system of the present invention is characterized by comprising the infrared-transmitting film of the present invention. The optical system is preferably an imaging optical system, and particularly preferably a far infrared imaging optical system using light in a far infrared wavelength region. For example, an optical system of a monitoring imaging device or an in-vehicle imaging device is preferable. The imaging device of the present invention is characterized by comprising an optical system including an optical surface on which the infrared-transmitting film is provided, and is preferably a monitoring imaging device, an in-vehicle imaging device, or the like comprising the far-infrared imaging optical system.
The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
Example 1
In example 1, zinc oxide films containing bismuth oxide as an additive were formed on both surfaces of a substrate by a magnetron sputtering method. The following specifically describes the film formation step.
First, a target material as a film forming raw material is disposed in a magnetron sputtering apparatus so as to face a substrate. As a film-forming raw material, a sintered target of zinc oxide was used. At this time, small tablets of bismuth oxide were uniformly arranged on the target. As the substrate, chalcogenide glass (IRG 206, manufactured by north Huohua optical information materials Co., Ltd.) was used.
Next, the inside of the entire apparatus is evacuated. Subsequently, the pressure in the apparatus reached 3X 10-4At Pa, 20SCCM of argon (standard ml/min, 1 atmosphere (25 ℃)) was injected, and 5SCCM of oxygen was injected. The exhaust speed was adjusted so that the pressure in the apparatus at this time became 0.3 Pa.
Subsequently, a high frequency (about 500W) of 13.56MHz was applied to the surface of the target, and a zinc oxide film containing bismuth oxide as an additive was formed on the surface of the substrate while the substrate was rotated in front of the target. By this method, zinc oxide films containing 4 mass% of bismuth oxide were formed on both surfaces of the substrate.
Example 2
A zinc oxide film containing bismuth oxide as an additive was produced in the same manner as in example 1, except that the content of bismuth oxide was adjusted to 0.7 mass% in example 2.
Example 3
A zinc oxide film containing bismuth oxide as an additive was produced in the same manner as in example 1, except that the content of bismuth oxide was adjusted to 14.7 mass% in example 3.
Example 4
A zinc oxide film containing bismuth oxide as an additive was produced in the same manner as in example 1, except that the content of bismuth oxide was adjusted to 44.7 mass% in example 4.
Example 5
In example 5, a zinc oxide film containing yttrium oxide as an additive was produced in the same manner as in example 1, except that bismuth oxide was replaced with yttrium oxide in an amount of 2.0 mass%.
Example 6
A zinc oxide film containing yttrium oxide as an additive was produced in the same manner as in example 1, except that in example 6, bismuth oxide was replaced with yttrium oxide in an amount of 32.0 mass%.
Example 7
In example 7, a zinc oxide film containing copper oxide as an additive was produced in the same manner as in example 1, except that the bismuth oxide was replaced with copper oxide in an amount of 3.1 mass%.
Example 8
A zinc oxide film containing magnesium oxide as an additive was produced in the same manner as in example 1, except that in example 8, magnesium oxide was used in place of bismuth oxide in an amount of 1.8 mass%.
Example 9
In example 9, an antireflection film was produced in which a Ge film and a bismuth oxide-containing zinc oxide film were laminated in this order from the substrate side. In the case of producing a Ge film, germanium was used as a target material, and in the case of producing a zinc oxide film containing bismuth oxide, a sintered target material of zinc oxide containing 2 mass% of bismuth oxide was used, and each film was produced in the same manner as in example 1.
Example 10
In example 10, a Ge film, a zinc oxide film containing bismuth oxide, a Ge film, and a zinc oxide film containing bismuth oxide were laminated in this order from the substrate side. At this time, each film was produced in the same manner as in example 9, except that the content of bismuth oxide was adjusted to 5 mass%.
Comparative example 1
A zinc oxide film was produced in the same manner as in example 1, except that only the sintered target of zinc oxide was used as the starting material in comparative example 1. That is, in comparative example 1, a zinc oxide film containing no metal oxide as an additive was produced.
Comparative example 2
In comparative example 2, a bismuth oxide film containing zinc oxide and containing bismuth oxide as a main component was produced in the same manner as in example 1, except that the content of bismuth oxide was adjusted to 70 mass%.
Comparative example 3
In comparative example 3, a bismuth oxide film was formed in the same manner as in example 1, except that a sintered target of bismuth oxide was used as a starting material.
Comparative example 4
In comparative example 4, an yttrium oxide film was obtained in the same manner as in example 1, except that a sintered target of yttrium oxide was used as a starting material.
Comparative example 5
In comparative example 5, a tantalum oxide film was obtained in the same manner as in example 1, except that a sintered target of tantalum oxide was used as a starting material.
Comparative example 6
In comparative example 6, an antireflection film in which a Ge film and a bismuth oxide film were laminated in this order from the substrate side was obtained in the same manner as in example 9, except that the bismuth oxide film prepared in the same manner as in comparative example 2 was used instead of the zinc oxide film containing bismuth oxide.
Evaluation of
The film thickness, composition, and average transmittance for far infrared rays of each film produced in examples 1 to 10 and comparative examples 1 to 6 were measured, and the water resistance was evaluated by a water resistance test.
Film thickness: the film thickness of each film was measured by a stylus profilometer. The results are shown in tables 1 and 2. The film thicknesses shown in tables 1 and 2 are actual film thicknesses of the respective films, and are not so-called optical film thicknesses.
Consists of the following components: the composition of each film was analyzed by ICP (inductively coupled plasma emission spectrometry). The results are shown in tables 1 and 2.
Average transmittance: the average transmittances of the samples obtained in the examples and comparative examples in the wavelength range of 8 μm to 12 μm and in the wavelength range of 8 μm to 14 μm were measured by FT-IR Spectrum 100 optical of Perkinelmer. Each sample was provided with a film (hereinafter, the same) designated on both surfaces of the substrate. The results are shown in tables 1 and 2.
The results are shown in tables 1 and 2, and the results of the water resistance test are shown by "○" and "x" in tables 1 and 2, where "○" indicates that the adhesion between the substrate and the film is good even after 24 hours have elapsed since the sample was immersed in pure water, and that no film peeling or the like has occurred at all, and "x" indicates that the adhesion between the substrate and the film has been observed to be lifted from the substrate or the adhesion between the substrate and the film has been reduced such as film peeling or the like during 24 hours elapsed since the sample was immersed in pure water.
As shown in table 1, the samples of examples 1 to 10 all showed good results in the water resistance test, and the film did not peel off from the substrate at all even after 24 hours from the immersion of each sample in pure water. On the other hand, the sample of comparative example 1 had a zinc oxide film containing no additive. As shown in table 2, in the sample of comparative example 1, floating of the film was observed after immersing the sample in pure water for 2 hours, and the film was completely peeled off from the substrate after 24 hours. From this, it was confirmed that the water resistance of the zinc oxide film can be remarkably improved by forming the zinc oxide film containing the specified metal oxide as an additive in a range of less than 50 mass%. The sample of comparative example 2 contains bismuth oxide as a main component. The sample of comparative example 3 was provided with a bismuth oxide film, and the sample of comparative example 4 was provided with a yttrium oxide film. The film of comparative example 2 containing bismuth oxide as a main component had good water resistance, but the bismuth oxide film of comparative example 3 and the yttrium oxide film of comparative example 4 had poor water resistance. However, as shown in examples 5 to 6, it was confirmed that when yttrium oxide was added to the zinc oxide film as an additive, the water resistance was good. The sample of comparative example 5 was a tantalum oxide film and had good water resistance. Although not shown in the table, it was confirmed that the zinc oxide film containing tantalum oxide in an amount of less than 5 mass% has good water resistance, and that the zinc oxide film containing tantalum oxide as an additive has improved water resistance.
As shown in table 1, the samples of examples 1 to 10 had an average transmittance of 90% or more in the wavelength range of 8 to 12 μm, and exhibited high transparency to light in these wavelength ranges. Therefore, the infrared ray transmitting films of the present invention produced in examples 1 to 10 are suitable for use as optical films.
On the other hand, as shown in Table 2, the sample of comparative example 1 had an average transmittance of 90% or more in the wavelength range of 8 μm to 12 μm, and had optical characteristics suitable for use as an optical film. However, as described above, the durability required in practice cannot be satisfied due to the poor water resistance. The samples of comparative examples 2 to 6 each had an average transmittance of less than 90% in the wavelength range of 8 μm to 12 μm, and had low transparency to far infrared rays, and thus were difficult to use as optical films.
Industrial applicability
According to the present invention, a novel infrared transmitting film which is easy to form and has durability such as water resistance that satisfies practical requirements, and an optical film, an antireflection film, an optical member, an optical system, and an imaging device provided with the infrared transmitting film can be provided.
Claims (11)
1. An infrared-transmitting film is characterized by containing zinc oxide as a main component and a metal oxide having an attenuation coefficient of 0.4 or less over the entire wavelength range of 8 to 14 μm as an additive.
2. The infrared transmitting film according to claim 1, wherein the metal oxide has a refractive index of 0.8 to 2.5 in a wavelength region of 8 to 14 μm.
3. The infrared transmitting film according to claim 1, wherein the metal oxide is segregated at grain boundaries of the zinc oxide.
4. The infrared ray transmitting film according to claim 1, wherein the metal oxide is one or more selected from the group consisting of bismuth oxide, yttrium oxide, copper oxide, and magnesium oxide.
5. The infrared ray transmitting film according to claim 1, wherein a content of the metal oxide in the infrared ray transmitting film is 0.1% by mass or more and less than 50% by mass.
6. The infrared ray transmitting film according to claim 1, wherein a content of the metal oxide in the infrared ray transmitting film is 0.1 mass% or more and 5 mass% or less.
7. An optical film comprising the infrared-transmitting film according to any one of claims 1 to 6.
8. An antireflection film comprising the infrared-transmitting film according to any one of claims 1 to 6.
9. An optical member comprising the infrared-transmitting film according to any one of claims 1 to 6 on an optical surface.
10. An optical system comprising the infrared-transmitting film according to any one of claims 1 to 6 on an optical surface.
11. An imaging apparatus comprising an optical system including an optical surface on which the infrared-transmitting film according to any one of claims 1 to 6 is provided.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016030980 | 2016-02-22 | ||
| JP2016-030980 | 2016-02-22 | ||
| JP2016-203525 | 2016-10-17 | ||
| JP2016203525A JP2017151408A (en) | 2016-02-22 | 2016-10-17 | Infrared transmission film, optical film, antireflection film, optical component, optical system and imaging device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107102383A CN107102383A (en) | 2017-08-29 |
| CN107102383B true CN107102383B (en) | 2020-04-10 |
Family
ID=59676512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611094455.XA Active CN107102383B (en) | 2016-02-22 | 2016-12-02 | Infrared-transmitting film, optical film, antireflection film, optical member, optical system, and imaging device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107102383B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112859208B (en) * | 2021-02-20 | 2022-05-17 | 无锡奥夫特光学技术有限公司 | Infrared window anti-reflection protective film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101231352A (en) * | 2007-06-11 | 2008-07-30 | 北京有色金属研究总院 | HfON/BP antireflecting protective film for infrared optical window and manufacture method thereof |
| CN101280414A (en) * | 2008-01-07 | 2008-10-08 | 桂林电子科技大学 | ZnO: Bi photoemissive thin film and preparation thereof |
| JP2009086533A (en) * | 2007-10-02 | 2009-04-23 | Sumitomo Electric Hardmetal Corp | Infrared multilayered film, infrared antireflection film, and infrared laser reflecting mirror |
| CN101620280A (en) * | 2009-06-30 | 2010-01-06 | 中国航空工业集团公司洛阳电光设备研究所 | Film system of infrared double-waveband antireflection film system and plating method thereof |
| CN102584011A (en) * | 2012-03-02 | 2012-07-18 | 中国建筑材料科学研究总院 | Aluminate glass, preparation thereof and application thereof |
| CN102998723A (en) * | 2012-11-29 | 2013-03-27 | 法国圣戈班玻璃公司 | Antireflection optical assembly and manufacturing method thereof |
-
2016
- 2016-12-02 CN CN201611094455.XA patent/CN107102383B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101231352A (en) * | 2007-06-11 | 2008-07-30 | 北京有色金属研究总院 | HfON/BP antireflecting protective film for infrared optical window and manufacture method thereof |
| JP2009086533A (en) * | 2007-10-02 | 2009-04-23 | Sumitomo Electric Hardmetal Corp | Infrared multilayered film, infrared antireflection film, and infrared laser reflecting mirror |
| CN101280414A (en) * | 2008-01-07 | 2008-10-08 | 桂林电子科技大学 | ZnO: Bi photoemissive thin film and preparation thereof |
| CN101620280A (en) * | 2009-06-30 | 2010-01-06 | 中国航空工业集团公司洛阳电光设备研究所 | Film system of infrared double-waveband antireflection film system and plating method thereof |
| CN102584011A (en) * | 2012-03-02 | 2012-07-18 | 中国建筑材料科学研究总院 | Aluminate glass, preparation thereof and application thereof |
| CN102998723A (en) * | 2012-11-29 | 2013-03-27 | 法国圣戈班玻璃公司 | Antireflection optical assembly and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107102383A (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6682188B2 (en) | Hard antireflective film and its manufacture and use | |
| US8535807B2 (en) | Anti-reflection film and infrared optical element | |
| KR102313266B1 (en) | Scratch-resistant coatings, substrates having scratch-resistant coatings and methods for producing same | |
| JP6817020B2 (en) | Infrared transmissive film, optical film, antireflection film, optical components, optical system and imaging device | |
| US11643357B2 (en) | Chalcogenide glass material | |
| WO2020105719A1 (en) | Chalcogenide glass lens | |
| JP6368941B2 (en) | Method for producing glass member with optical multilayer film | |
| US11747520B2 (en) | Optical thin film having metal layer containing silver and high standard electrode potential metal | |
| US10641927B2 (en) | Optical thin film, optical element, optical system, and method for producing optical thin film | |
| US9575216B2 (en) | Infrared-transmitting film, method for producing infrared-transmitting film, infrared optical component, and infrared device | |
| AU2019205016B2 (en) | Optical component with scratch resistant anti-reflection coating and method for producing same | |
| CN107102383B (en) | Infrared-transmitting film, optical film, antireflection film, optical member, optical system, and imaging device | |
| US11643361B2 (en) | Method of increasing strength of glass substrate for optical filter and tempered-glass optical filter made thereby | |
| JP6702039B2 (en) | Thin film manufacturing method, thin film forming material, optical thin film, and optical member | |
| JP2004334012A (en) | Antireflection film and optical filter | |
| WO2023008123A1 (en) | Film-equipped base material and manufacturing method for same | |
| JP4447393B2 (en) | Glass member with optical multilayer film, and optical element using the glass member | |
| JP7216471B2 (en) | Plastic lens for in-vehicle lens and manufacturing method thereof | |
| JP2017032852A (en) | Anti-reflection film and optical component | |
| JP3197272B2 (en) | Optical element | |
| JPH03218821A (en) | Heat ray reflective glass | |
| JPH05129277A (en) | Multilayer reflection preventive film | |
| WO2023153242A1 (en) | Far-infrared transmission member, far-infrared sensor, automotive sensor, smartphone-mounted sensor, and sensor for wearable terminal | |
| WO2019208366A1 (en) | Optical thin film, optical element, optical system, and optical thin film production method | |
| JPH04136901A (en) | Optical parts made of silicon for infrared transmission |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |