CN107102383A - Infrared transmitting film, optical film, antireflection film, optical component, optical system and camera device - Google Patents
Infrared transmitting film, optical film, antireflection film, optical component, optical system and camera device Download PDFInfo
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- CN107102383A CN107102383A CN201611094455.XA CN201611094455A CN107102383A CN 107102383 A CN107102383 A CN 107102383A CN 201611094455 A CN201611094455 A CN 201611094455A CN 107102383 A CN107102383 A CN 107102383A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
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Abstract
The present invention provides the infrared transmitting film set in the optical component that far infrared wavelength region is used, and the infrared transmitting film is the new infrared transmitting film for being film-made easily and having high water resistance.The present invention also provides optical film, antireflection film, optical component, optical system and the camera device for possessing above-mentioned infrared transmitting film.The infrared transmitting film of the present invention is characterised by, using zinc oxide as principal component, and the metal oxide that the attenuation coefficient for containing less than 14 μm of the whole wavelength region more than 8 μm is less than 0.4 is as additive.
Description
Technical field
It is special the present invention relates to infrared transmitting film, optical film, antireflection film, optical component, optical system and camera device
It is not to relate to the use of infrared transmitting film, optical film, antireflection film, optical component, light that the optical system of far infrared is applicable
System and camera device.
Background technology
At present, profit is employed with the various uses such as camera device, vehicle-mounted camera device or heat distribution parsing in monitoring
Use ultrared optical system.It is commonly known to have use middle infrared wavelength region (2.5 μm~4 μm) as these optical systems
The mid-infrared light system of light, uses the far infrared optical system of far infrared wavelength region (8 μm~14 μm) light.Example
Such as, mainly far infrared optical system is employed in monitoring camera device, vehicle-mounted camera device etc..Constitute these optics
The optical components such as the infrared transmitting camera lens of system are compared with constituting the optical component of visible light optical system, the transmission of incident light
Rate is low.Therefore, antireflection film is set in the plane of incidence of optical component, increases the transmission light quantity of incident light, prevent because surface is anti-
Deficiency in light quantity etc. is just particularly important caused by penetrating.
As the antireflection film of the optical component used in far infrared optical system, for example, (the Japan of patent document 1
Patent Application Kokai 2007-298661 publications) in disclose one kind on Si substrates from substrate-side laminated successively Ge films,
ZnS films, Ge films, ZnS films, YF3The antireflection film of 5 Rotating fields of film.Also, (the Japanese Patent Application Laid-Open of patent document 2
2011-221048 publications) in disclose one kind laminated successively BiO from substrate-side on chalcogenide glass substrate2Film,
YF3The antireflection film of 2 Rotating fields of film.As described in these patent documents, antireflection film passes through laminated multiple infrared transmitting films
To form sandwich construction, for the light of big wavelength region, antiradar reflectivity is integrally easily achieved in wavelength region.At present, make
For the layer constituent material of the antireflection film used in far infrared wavelength region, it is known to public including patent document 1 and patent document 2
Following material including the material opened.
High-index material：Ge、Si
Low-index material：YF3、YbF3、NaF、NdF3、LaF3、CaF2、SrF2
Middle refractive index material：ZnS、ZnSe、PbTe、Y2O3、CeO2、HfO2
When on the surface of optical component, antireflection film is set, generally heated using by electron beam heating or resistance heating
And the vacuum vapour deposition of raw material is deposited.However, it is contemplated that from now on for infrared optical system demand expansion, at present for
Using the high method of the production efficiency suitable for largely producing requirement is proposed to manufacture the film-forming method of antireflection film.
For example, as the high film-forming method of the production efficiency compared with vacuum vapour deposition, magnetron sputtering method can be enumerated.But will
Above-mentioned low-index material, when fluoride being used as into raw material, the fluorine element in target material can have been damaged in sputtering process
Lose.So as to, it is difficult to obtain the film of stoichiometric composition, it is impossible to obtain saturating for the transparent infrared ray of the light using wavelength region
Penetrate film.When above-mentioned middle refractive index material ZnS, ZnSe, PbTe are also same, it is difficult to these materials by magnetic control
Sputtering method manufactures the film of stoichiometric composition.
On the other hand, for above-mentioned high-index material Ge, Si, it can be film-made by magnetron sputtering method.As described above,
For the light of big wavelength region, want to be accomplished by the optical film of sandwich construction when whole wavelength region realizes antiradar reflectivity.
Here, relative to Ge or Si, the refractive index of fluoride is too low, thus the laminated fluoride films on Ge films or Si films
When can not also obtain good antireflection property.Also, as described above, it is difficult to which desired composition is manufactured by magnetron sputtering method
Fluoride films.
In view of these problems, or it can contemplate Ge films or Si films and the film alternately laminated formed by middle refractive index material
Constitute.But as described above, ZnS, ZnSe, PbTe are difficult to be film-made by magnetron sputtering method, and these materials have toxicity, thus
Its operating difficulties.On the other hand, with regard to Y2O3、CeO2、HfO2For, it can be film-made by magnetron sputtering method, and without toxicity,
But the light for far infrared region (8 μm~14 μm) is translucent, it is impossible to be made for the transparent film of far infrared.
Furthermore, monitoring camera device or vehicle-mounted camera device etc. is provided in outdoor application.Optical film is arranged on
The surface of these optical components, thus in addition to the adaptation for being film-made face, in addition it is also necessary to high water resistance.
The content of the invention
Problems to be solved by the invention
In view of the foregoing, it is an object to provide the new infrared ray for being film-made easily and there is high water resistance
Transmission film, optical film, antireflection film, optical component, optical system and camera device.
The method solved the problems, such as
In order to realize the purpose of the present invention, infrared transmitting film of the invention is characterised by, using zinc oxide as it is main into
Point, and the metal oxide that the attenuation coefficient for contain less than 14 μm of the whole wavelength region more than 8 μm is less than 0.4 is as adding
Plus thing.
Also, the optical film of the present invention, antireflection film, optical component, optical system are characterised by possessing above-mentioned respectively
The infrared transmitting film of the present invention.
Furthermore, camera device of the invention is characterised by possessing optical system, includes and is provided with the optical system
State the optical surface of the infrared transmitting film of the present invention.
The effect of invention
According to the present invention it is possible to provide the infrared transmitting set in the optical component that far infrared wavelength region is used
Film, the infrared transmitting film is the new infrared transmitting film for being film-made easily and having high water resistance.The present invention is also provided
Possess optical film, antireflection film, optical component, optical system and the camera device of above-mentioned infrared transmitting film.
Embodiment
Hereinafter, infrared transmitting film, optical film, antireflection film, optical component, optical system and the shooting of the present invention is illustrated
The embodiment of device.
1st, infrared transmitting film
First, the embodiment of the infrared transmitting film of the present invention is illustrated.The feature of the infrared transmitting film of the present invention exists
In, using zinc oxide as principal component, and containing more than 8 μm less than 14 μm of whole wavelength region attenuation coefficient be 0.4 with
Under metal oxide be used as additive.In addition, the infrared transmitting film refers to transmit ultrared optical thin film.
1-1, zinc oxide
Zinc oxide less than 14 μm of whole wavelength region, attenuation coefficient of i.e. whole far infrared wavelength region more than 8 μm
It is for far infrared (light of less than more than 8 μm 14 μm wavelength) the high material of transparency less than 0.05.
Also, zinc oxide for far infrared refractive index more than 1.5 less than 2.5 scope, zinc oxide is far infrared
The middle refraction materials of wavelength region.Therefore, the infrared transmitting film is also suitable as the constituent material for antireflection film.Example
Such as, by by alternately laminateds such as the infrared transmitting film and the Ge films or Si films in far infrared wavelength region with high refractive index
Deng the antireflection film that there is good antireflection property in whole far infrared wavelength region can be obtained.
However, zinc oxide is the material for being easy to crystallization.The oxygen being film-made by physical vapor depositions such as vacuum vapour deposition, sputtering methods
Changing zinc film has polycrystalline structure.Therefore, crystal boundary is easy to containing immersion etc., and the water resistance of Zinc oxide film is low, it is difficult to meet actual need
The durability asked.In view of these problems, the present inventor, as principal component, and contains the metal oxygen specified by using using zinc oxide
Compound is as the film of additive, and discovery can improve water resistance.According to the present invention it is possible to realize high water resistance.Hereinafter, explanation
The metal oxide specified of additive is used as in the present invention.
1-2, metal oxide
1) attenuation coefficient
For the metal oxide, it is desirable to whole far infrared wavelength region attenuation coefficient be less than 0.4.Remote red
When the attenuation coefficient of outer wavelength region is more than 0.4, the transparency for far infrared declines.That is, the infrared transmitting film is remote
Ultrared transmissivity declines, so as to be difficult to the infrared transmitting film being used as optical film.
The metal oxide for being less than 0.4 as the attenuation coefficient in whole far infrared wavelength region, for example, can enumerate
Zirconium oxide (ZrO2), chromium oxide (Cr2O3), hafnium oxide (HfO2), bismuth oxide (Bi2O3), yittrium oxide (Y2O3), cupric oxide (CuO) and
Magnesia (MgO) etc..When these metal oxides are used as into additive, can maintain Zinc oxide film for far infrared
Transmissivity, it is possible to improve the water resistance of Zinc oxide film.
Here, for promoting the transparency in the infrared transmitting film using wavelength region to become higher viewpoint, use
Attenuation coefficient as the metal oxide of additive is preferably entirely being less than 0.4, more preferably less than 0.2 using wavelength region,
Even more preferably below 0.1.According to the use wavelength region of the infrared transmitting film, in above-mentioned metal oxide enumerated etc.
Suitable, suitable metal oxide can be selected.In addition, shown below the decay system of the above-mentioned each metal oxide enumerated
Number.Hereinafter, the attenuation coefficient (k) that (8 μm) of k is represented when wavelength is 8 μm, the attenuation coefficient that (14 μm) of k is represented when wavelength is 14 μm.
Also, the attenuation coefficient of zinc oxide is also shown for below.
Zinc oxide：K (8 μm)=0.004, k (14 μm)=0.03
Zirconium oxide：K (8 μm)=0.06, k (14 μm)=0.35
Chromium oxide：K (8 μm)=0.007, k (14 μm)=0.37
Hafnium oxide：K (8 μm)=0.006, k (14 μm)=0.4
Bismuth oxide：K (8 μm)=0.002, k (14 μm)=0.025
Yittrium oxide：K (8 μm)=0.00027, k (14 μm)=0.078
Cupric oxide：K (8 μm)=0.0001, k (14 μm)=0.04
Magnesia：K (8 μm)=0.00025, k (14 μm)=0.014
As described above, compared with zirconium oxide, chromium oxide and hafnium oxide, bismuth oxide, yittrium oxide, cupric oxide and magnesia decline
Subtract coefficient small, be less than 0.1 in whole far infrared wavelength region.Therefore, it can remain high in whole far infrared wavelength region
Transparency viewpoint, as additive, more preferably using selected from being made up of bismuth oxide, yittrium oxide, cupric oxide and magnesia
One or more of group.At this point it is possible to which one kind in these metal oxides is used as into additive, one kind can also be mixed
Use above.
In addition, for the viewpoint for the water resistance for improving Zinc oxide film, can also be by tantalum oxide (Ta2O5) etc. attenuation coefficient exist
Metal oxide beyond above range is used as additive.Hereinafter, the attenuation coefficient of tantalum oxide is shown.But it is as described below,
The attenuation coefficient of tantalum oxide is big, when containing the tantalum oxide as additive in Zinc oxide film, for the zinc oxide of far infrared
The transmissivity of film can decline, it is difficult to be used as optical film.
Tantalum oxide：K (8 μm)=0.028, k (14 μm)=0.75
2) refractive index
Also, the metal oxide for the light in far infrared wavelength region refractive index preferably more than 0.8 2.5 with
Under.By the way that additive will be used as with the metal oxide with the equal refractive index of the refractive index of zinc oxide, obtained by can making
The refractive index of infrared transmitting film be changed into and zinc oxide identical refractive index.In addition, the above-mentioned each metal oxide enumerated exists
The refractive index of far infrared wavelength region is more than 0.8 in less than 2.5 scope.Here, for not making the refraction of zinc oxide
There is the viewpoint of big change in rate, it is preferred to use with the metal oxide with the equal refractive index of the refractive index of zinc oxide.It is based on
The viewpoint, is more preferably used as additive by refractive index for less than more than 1.0 2.5 metal oxide, further preferably will folding
Penetrate the metal oxide that rate is less than more than 1.5 2.5 and be used as additive.
3) content
Secondly, the content of the metal oxide as the additive in the infrared transmitting film is illustrated.The infrared transmitting
The content of the metal oxide in film is preferably 0.1 mass % less than 50 mass %.Wherein, referred to herein as content
Refer to the total amount of metal oxide contained in the infrared transmitting film as additive.That is, using the oxidation of multiple metals
When thing is as additive, refer to its total amount.Also, in the infrared transmitting film, principal component is zinc oxide.That is, this is infrared
Line transmission film contains zinc oxide more than 50 mass %.Also, except inevitable impurity, the infrared transmitting film is by aoxidizing
Zinc and the metal oxide composition as additive.
For the high zinc oxide of the light-transparency for far infrared wavelength region, by containing the metal in above range
Oxide is used as additive, the transparency for far infrared of the infrared transmitting film can be maintained into high level, and
Water resistance can be improved.At the same time, acid resistance, mechanical strength etc. can also be improved.
Here, compared with zinc oxide, the attenuation coefficient of metal oxide listed above is in equal or big numerical value.Cause
This, for the attenuation coefficient metal oxide bigger than zinc oxide, has higher for the light obtained for far infrared region
Transparency infrared transmitting film viewpoint, the content of the metal oxide is more preferably more than 0.1 mass % 15 mass %
Hereinafter, more preferably below the mass % of more than 0.1 mass % 10, most preferably below the mass % of more than 0.1 mass % 5.
4) crystal structure
As the infrared transmitting film of the present invention, preferably there is above-mentioned metal oxide in the cyrystal boundary segregation of zinc oxide.Due to
In the metal oxide of the cyrystal boundary segregation of zinc oxide, crystal boundary becomes to be difficult to containing water, and the water resistance of the infrared transmitting film becomes
Well.Also, when cyrystal boundary segregation has above-mentioned metal oxide, crystal growth is hindered, crystal grain becomes fine.Therefore, in film
Residual stress is small, and this is also one of key element that water resistance is improved.Also, due to fine crystal structure, the film
Mechanical strength is also uprised.Furthermore, acid resistance etc. is also improved.
It is preferably to fill as the metal oxide of additive when i.e., to improve the water resistance of Zinc oxide film as purpose
Fill out the amount of the crystal boundary degree of zinc oxide.Based on the viewpoint, for attenuation coefficient and the equal metal oxide of zinc oxide, at this
Content in infrared transmitting film is more preferably more than 0.1 mass % below 15 mass %, more preferably 0.1 mass % with
Upper below 10 mass %, most preferably below the mass % of more than 0.1 mass % 5.For example, the attenuation coefficient of bismuth oxide compares zinc oxide
It is small, though it is the high material of the transparency for far infrared, the poor water resistance of bismuth oxide itself.However, by more than more
Contain bismuth oxide for preferred scope, can preferably improve the water resistance of Zinc oxide film.
5) film-forming method
When manufacturing the infrared transmitting film of the present invention, for example, zinc oxide can be used as into principal component, it will with the addition of above-mentioned
Sintering ceramics of metal oxide etc. are used as initiation material, by the various dry types such as vacuum vapour deposition, sputtering method be film-made methods come
Film.In these methods, the sinter of mixed oxide can be used as initiation material.
In various dry type film methods, magnetron sputtering method is particularly easy, and production efficiency is high compared with vacuum vapour deposition.Therefore,
When manufacturing the infrared transmitting film for the optical component largely produced, it is preferred to use magnetron sputtering method.Now, as electric discharge shape
Formula, can use DC current, high-frequency discharge or alternating current discharge.
When manufacturing infrared transmitting film using magnetron sputtering method, it can also be constituted be with the addition of in metallic zinc with specified amount
The metal alloy targets of the metal of above-mentioned metal oxide are used as initiation material.The metal alloy targets are used, in oxygen environmental protection
In be filmed, can obtain using zinc oxide as principal component, and containing above-mentioned metal oxide infrared ray of the invention it is saturating
Penetrate film.
When manufacturing Zinc oxide film using these physical vapor depositions, above-mentioned metal oxide does not form combined oxidation with zinc oxide
Thing, but it is segregated in the crystal boundary of zinc oxide.I.e., it is possible to which obtained in cyrystal boundary segregation above-mentioned metal oxide has zinc oxide
The infrared transmitting film of polycrystalline structure.
In addition, for the infrared transmitting film of the present invention, it is not limited to which dry type is film-made method, it would however also be possible to employ chemical gas
The various film by wet method films such as phase growth method, sol-gal process., can be according to the infrared transmitting in various film-forming methods
The selection such as the purposes of film or the material of base material is suitable, be suitably film-made method.
1-3, base material
As the infrared transmitting film of the present invention, for example, the surface of optical component etc. can be arranged on.Now, for light
There is no particular limitation for the material of the base material of department of the Chinese Academy of Sciences's part etc..
The infrared transmitting film of the present invention and the transparent germanium of the light for far infrared wavelength region (Ge), silicon (Si), selenium
Changing zinc (ZnSe), zinc sulphide (ZnS) has good adaptation.Also, the present invention infrared transmitting film with germanium, arsenic
(As), selenium (Se), sulphur (S), antimony (Sb), Ga (gallium) etc. have good adaptation as the various chalcogenide glass of composition.
Therefore, can be with when the infrared ray being made up of these materials being used as into base material with the various infrared optical parts such as optical lens
The infrared transmitting film of the present invention is directly set on the surface of infrared optical part, good adaptation can be obtained.
2nd, optical film
Secondly, the optical film of the present invention is illustrated.In the present invention, optical film refers to antireflection film, boundary filter, band logical filter
Optical filters such as ripple device etc..The optical film of the present invention can be the monofilm or two being made up of one layer of optical thin film
The laminated multilayer film of more than layer optical thin film.Under various situations, optical film of the invention is provided with above-mentioned of the invention
Infrared transmitting film.That is, the optical film can be the monofilm that constitutes of infrared transmitting film or at least by the present invention
Multilayer film with one layer of infrared transmitting film.
As the present invention infrared transmitting film, using middle refractive index material oxidation zinc as principal component, with oxidation
The equal refractive index of zinc.Also, the infrared transmitting film and following high-index materials or the adaptation of low-index material
Also it is good.
High-index material：Ge、Si
Low-index material：YF3、YbF3、NaF、NdF3、LaF3、CaF2、SrF2
Therefore, it can to obtain that the infrared transmitting film is used as into intermediate-index layer, so suitably with by above-mentioned material
Expect the optical film of the laminated any Rotating fields of the high refractive index layer and/or low-index layer that constitute.
3rd, antireflection film
Secondly, the embodiment of the antireflection film of the present invention is illustrated.The antireflection film of the present invention is the one of above-mentioned optical film
Kind, it is characterized in that possessing the infrared transmitting film of the present invention.The antireflection film of the present invention can be saturating by one layer of above-mentioned infrared ray
Penetrate the monofilm of film composition, but the multilayer film laminated more preferably with above-mentioned high refractive index layer and/or low-index layer.Formed
During the antireflection film of sandwich construction, by the interface reflected light produced at each interface, it is easy to using the dry Wataru effects of light big
Wavelength region realizes low reflectivity.
4th, optical component
The optical component of the present invention is characterized in the infrared transmitting film for possessing the present invention.It is used as optical component, Ke Yilie
Enumerate the various optical components of the imaging optical system or projection optical system of composition camera device or projection arrangement etc..More specifically
Ground is said, can enumerate lens, prism (colour splitting prism, color-combination prism etc.), polarization beam splitter (PBS), cut-off filter (long
Wavelength is used, short wavelength uses etc.) etc..It is particularly preferred to the far infrared camera shot light to constitute the light using far infrared wavelength region
The infrared ray lens of system.
5th, optical system/camera device
The optical system of the present invention is characterized in the infrared transmitting film for possessing the present invention.As the optical system, preferably
For imaging optical system, it is particularly preferred to use the far infrared camera shot optical system of the light of far infrared wavelength region.Example
Such as, preferably monitor with camera device, the optical system of vehicle-mounted camera device.Also, the feature of the camera device of the present invention
It is to possess optical system, comprising the optical surface for being provided with the infrared transmitting film in the optical system, preferably possesses these remote
Monitoring camera device, vehicle-mounted camera device of infrared pick-up optical system etc..
Hereinafter, in conjunction with the embodiments and comparative example illustrates the present invention.But the invention is not limited in following implementation
Example.
Embodiment 1
In embodiment 1, using magnetron sputtering method, made respectively on the two sides of base material and contained bismuth oxide as additive
Zinc oxide film.Hereinafter, the step of illustrating film.
First, the target as film raw material is configured in magnetic control sputtering device in opposite directions with base material.As film raw material,
Employ the sinter target of zinc oxide.Now, the tablet small pieces of bismuth oxide are equably arranged on the target.It is used as base
Material, employs chalcogenide glass (Hubei New Huaguang Information Materials Co., Ltd. IRG206).
Secondly, it will be evacuated inside whole device.Then, the pressure in device reaches 3 × 10-4During Pa, argon is injected
After gas 20SCCM (standard milliliters/minute, 1 atmospheric pressure (25 DEG C)), oxygen 5SCCM is filled with.Exhaust velocity is adjusted, is made now
Device in pressure be changed into 0.3Pa.
Then, 13.56MHz high frequency (about 500W) is applied in target material surface, make that base material rotates before target is same
When, the Zinc oxide film for containing bismuth oxide as additive has been made on the surface of base material.By this method, on the two sides of base material
The Zinc oxide film containing 4 mass % bismuth oxides has been made respectively.
Embodiment 2
In embodiment 2, in addition to the content of bismuth oxide is adjusted into 0.7 mass %, make same as Example 1ly
Contain bismuth oxide as the Zinc oxide film of additive.
Embodiment 3
In embodiment 3, in addition to the content of bismuth oxide is adjusted into 14.7 mass %, make same as Example 1ly
Contain bismuth oxide as the Zinc oxide film of additive.
Embodiment 4
In embodiment 4, in addition to the content of bismuth oxide is adjusted into 44.7 mass %, make same as Example 1ly
Contain bismuth oxide as the Zinc oxide film of additive.
Embodiment 5
In embodiment 5, in addition to substituting bismuth oxide with content for 2.0 mass % yittrium oxide, same as Example 1ly
The Zinc oxide film for containing yittrium oxide as additive is made.
Embodiment 6
It is same as Example 1 in addition to substituting bismuth oxide with content for 32.0 mass % yittrium oxide in embodiment 6
Ground has made the Zinc oxide film for containing yittrium oxide as additive.
Embodiment 7
In embodiment 7, in addition to substituting bismuth oxide with content for 3.1 mass % cupric oxide, same as Example 1ly
The Zinc oxide film for containing cupric oxide as additive is made.
Embodiment 8
In embodiment 8, in addition to substituting bismuth oxide with content for 1.8 mass % magnesia, same as Example 1ly
The Zinc oxide film for containing magnesia as additive is made.
Embodiment 9
In embodiment 9, laminated successively Ge films, the antireflection of the Zinc oxide film containing bismuth oxide from substrate-side have been made
Film.When making Ge films, with germanium as target, when making the Zinc oxide film containing bismuth oxide, the content of bismuth oxide is used for 2 matter
The sinter target of % zinc oxide is measured, so as to make each film same as Example 1ly.
Embodiment 10
In embodiment 10, from substrate-side laminated successively Ge films, the Zinc oxide film containing bismuth oxide, Ge films, containing aerobic
Change the Zinc oxide film of bismuth.Now, in addition to the content of bismuth oxide is adjusted into 5 mass %, make same as Example 9ly
Each film.
Comparative example 1
It is same as Example 1 in addition to only with the sinter target of zinc oxide as initiation material in comparative example 1
Ground has made Zinc oxide film.That is, the Zinc oxide film for not containing the metal oxide as additive has been made in comparative example 1.
Comparative example 2
In comparative example 2, in addition to the content of bismuth oxide is adjusted into 70 mass %, make same as Example 1ly
Contain the bismuth oxide film that zinc oxide and principal component are bismuth oxide.
Comparative example 3
In comparative example 3, in addition to the sintering target of bismuth oxide as initiation material, it is film-made same as Example 1ly
After obtained bismuth oxide film.
Comparative example 4
In comparative example 4, in addition to the sintering target of yittrium oxide as initiation material, it is film-made same as Example 1ly
After obtained yittrium oxide film.
Comparative example 5
In comparative example 5, in addition to the sintering target of tantalum oxide as initiation material, it is film-made same as Example 1ly
After obtained tantalum-oxide film.
Comparative example 6
In comparative example 6, except containing bismuth oxide with using the bismuth oxide film replacement made with the identical method of comparative example 2
Beyond Zinc oxide film, laminated successively Ge films, the antireflection of bismuth oxide film from substrate-side have been obtained same as Example 9ly
Film.
Evaluate
Thickness, the group of each film made in 1~embodiment of embodiment 10,1~comparative example of comparative example 6 are determined respectively
Into, for the average transmittance of far infrared, and by water resistant test have rated water resistance.
Thickness：The thickness of each film is determined with contact pin type contourgraph.As a result it is shown in table 1 and table 2.In addition, table 1 and table 2
In the thickness that shows be each film actual thickness, be not so-called blooming.
Composition：The composition of each film is analyzed with ICP (inductively coupled plasma luminescence spectrometer method).As a result be shown in table 1 and
In table 2.
Average transmittance：Determined with the FT-IR Spectrum 100Optica of PerkinElmer company systems in each reality
Sample that example and comparative example obtain is applied in 8 μm~12 μm of wave-length coverage and the average transmittance in 8 μm~14 μm of wave-length coverage.This
Outside, each sample possesses the film (following, identical) each specified on the two sides of substrate.As a result it is shown in table 1 and table 2.
Water resistant test：Impregnated of the sample obtained in each embodiment and comparative example in pure water.Then, often 1 hour is spent to see
Examine the phenomenon for film stripping whether occur.Then, act the time point that have passed through 24 hours in pure water and finish sample is immersed in
Observation.As a result it is shown in table 1 and table 2.In table 1 and table 2, the result of water resistant test is represented with "○", "×".Here, "○"
Represent base material and film it is closely sealed sample is immersed in pure water rise have passed through 24 hours after be also good, do not occur film completely
Peel off etc..Also, "×" represent sample is immersed in pure water rise have passed through 24 hours untill during observed film from
Float on base material or base material and the film such as film is peeled off adaptation situation about declining.
As shown in table 1, for the sample of 1~embodiment of embodiment 10, the result of water resistant test is good, by each sample
It is immersed in rise have passed through in pure water and does not also occur the situation that film is peeled off from substrate after 24 hours completely.On the other hand, compare
The sample of example 1 possesses the Zinc oxide film for not containing any additive.As shown in table 2, for the sample of comparative example 1, this is tried
Sample impregnates in pure water observed floating for film after 2 hours, the shape that film is completely exfoliated from substrate was presented after 24 hours
State.It is possible thereby to confirm, the metal oxide specified is contained with the scope less than 50 mass % it is used as additive by being formed
Zinc oxide film, the water resistance of Zinc oxide film can be significantly improved.In addition, the sample of comparative example 2 be using bismuth oxide as it is main into
Point.Also, the sample of comparative example 3 possesses bismuth oxide film, the sample of comparative example 4 possesses yittrium oxide film.Comparative example 2 with bismuth oxide
Be as the water resistance of the film of principal component it is good, but comparative example 3 bismuth oxide film and comparative example 4 yittrium oxide film water resistance not
It is good.But as shown in 5~embodiment of embodiment 6, confirm when containing yittrium oxide in Zinc oxide film as additive, water resistance
Become good result.Also, the sample of comparative example 5 is tantalum-oxide film, and water resistance is good.It is not shown, but also confirms in table
The water resistance for having arrived the Zinc oxide film containing the tantalum oxide less than 5 mass % is good, can when containing tantalum oxide as additive
With the result for the water resistance for improving Zinc oxide film.
Also, as shown in table 1, the average transmittance of the sample of 1~embodiment of embodiment 10 in 8 μm~12 μm of wave-length coverage
For more than 90%, high transparency is shown for the light of these wave-length coverages.Therefore, made in 1~embodiment of embodiment 10
The infrared transmitting film of the invention of work is suitable for use as optical film.
On the other hand, as shown in table 2, the sample of comparative example 1 is 90% in the average transmittance of 8 μm~12 μm of wave-length coverage
More than, with the optical characteristics being suitable for use as optical film.But as noted previously, as poor water resistance, it is impossible to meet actual demand
Durability.Also, the sample of 2~comparative example of comparative example 6 is below in the average transmittance of 8 μm~12 μm of wave-length coverage
90%, the transparency for far infrared is low, it is difficult to be used as optical film.
Industrial applicibility
According to the present invention it is possible to provide the new of the durability that film easily and with water resistance etc. meets actual demand
Infrared transmitting film, and possess optical film, antireflection film, optical component, optical system and the shooting of the infrared transmitting film
Device.
Claims (11)
1. a kind of infrared transmitting film, it is characterised in that using zinc oxide as principal component, and containing less than 14 μm more than 8 μm
The attenuation coefficient of whole wavelength region be used as additive for less than 0.4 metal oxide.
2. infrared transmitting film as claimed in claim 1, wherein, the metal oxide is for less than more than 8 μm 14 μm
The refractive index of light in wavelength region is less than more than 0.8 2.5.
3. infrared transmitting film as claimed in claim 1, wherein, there is the metal oxygen in the cyrystal boundary segregation of the zinc oxide
Thing.
4. infrared transmitting film as claimed in claim 1, wherein, the metal oxide be selected from by bismuth oxide, yittrium oxide,
One or more of group of cupric oxide and magnesia composition.
5. infrared transmitting film as claimed in claim 1, wherein, the metal oxide in the infrared transmitting film contains
Amount is in 0.1 mass % less than 50 mass %.
6. infrared transmitting film as claimed in claim 1, wherein, the metal oxide in the infrared transmitting film contains
Amount is in below the mass % of more than 0.1 mass % 5.
7. a kind of optical film, it is characterised in that possess the infrared transmitting film described in any one in claim 1~6.
8. a kind of antireflection film, it is characterised in that possess the infrared transmitting film described in any one in claim 1~6.
9. a kind of optical component, it is characterised in that the infrared ray in optical surface possesses claim 1~6 described in any one
Transmission film.
10. a kind of optical system, it is characterised in that the infrared ray in optical surface possesses claim 1~6 described in any one
Transmission film.
11. in a kind of camera device, it is characterised in that possess optical system, the optical system comprising be provided with claim 1~
The optical surface of infrared transmitting film in 6 described in any one.
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| JP2016-030980 | 2016-02-22 | ||
| JP2016030980 | 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 |
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| CN107102383A true CN107102383A (en) | 2017-08-29 |
| CN107102383B CN107102383B (en) | 2020-04-10 |
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| 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 |
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Cited By (1)
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| CN112859208A (en) * | 2021-02-20 | 2021-05-28 | 无锡奥夫特光学技术有限公司 | Infrared window anti-reflection protective film |
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