CN101435888B - Optical multilayer filter, method of manufacturing the same, and electronic apparatus - Google Patents
Optical multilayer filter, method of manufacturing the same, and electronic apparatus Download PDFInfo
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- CN101435888B CN101435888B CN 200810176318 CN200810176318A CN101435888B CN 101435888 B CN101435888 B CN 101435888B CN 200810176318 CN200810176318 CN 200810176318 CN 200810176318 A CN200810176318 A CN 200810176318A CN 101435888 B CN101435888 B CN 101435888B
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Abstract
The invention provides an optical multilayer filter and manufacturing method thereof. The optical multilayer filter can reduce adhesion of dust and remove the adhered dust easily. In the inorganic thin film 2, on surface of the glass substrate, a TiO2 layer and an SiO2 layer are laminated in sequence, the upmost layer being composed of SiO2 layers (2L30); the optical multilayer filter 10 has an inorganic thin film 2 composed of a plurality of layers on a substrate including a fluorinated organic silicon compound film 5 formed on a surface of the inorganic thin film 2. Density of the SiO2 that forms the upmost layer is 1.9g/cm<3> to 2.1g/cm<3>. The upmost layer SiO2 layer of the inorganic thin film 2 is set as a first layer, an TiO2 layer with density 4.1g/cm<3> to 4.8g/cm<3> is formed selectively on a second layer (2H30) and a fourth layer (2H29) at a lower layer of the first layer SiO2 layer and an SiO2 layer with density 1.9g/cm<3> to 2.1g/cm<3> is formed selectively the third layer (2L29). The SiO2 layer and the TiO2 layer are formed with film by vacuum vaporization method.
Description
Technical field
The present invention relates to the manufacture method of optical multilayer film filter, optical multilayer film filter and be assembled with the electronic apparatus of optical multilayer film filter.
Background technology
As the optical multilayer film filter, known have semi-permeable mirror, cutoff filter, a low-pass filter etc., and these optical multilayer film filters are used for electronic apparatus more.This optical multilayer film filter is made of substrate and the inorganic thin film that is formed on this substrate by evaporation etc.
Inorganic thin film has by titania (TiO
2) wait the high refractive index film of formation and by silicon dioxide (SiO
2) wait the mutual lamination of low refractive index film of formation and the membrane structure of the multilayer that obtains.Generally, be formed with the silicon dioxide film with diaphragm function on the top layer of this inorganic thin film, so its surface does not have electric conductivity, be easy to static electrification.Therefore, the surface of optical multilayer film filter is easy to adsorb dust, and this dust brings harmful effect for sometimes the optical characteristics of the e-machine of having assembled the optical multilayer film filter.
As the technology of static on the such surface of reply when substrate is formed with inorganic thin film, known have an example (referring to patent documentation 1) that ITO nesa coatings such as (tin indium oxide, Indium Tin Oxide) for example is set at the outside surface of dustproof glass.This nesa coating can not damage the transparency of glass, and has electric conductivity, thereby can effectively remove the static that the surface of nesa coating has.
Patent documentation 1: TOHKEMY 2004-233501 communique
Summary of the invention
But for the optical multilayer film filter of the optical property of the film of emphasizing to constitute multi-layer film surface, if nesa coating as patent documentation 1 is put down in writing is set on the surface, then the optical characteristics of optical multilayer film filter self changes.
In addition, in the said structure, by suppressing the static on surface, thereby can reduce adhering to of dust that static causes, but because the surface energy on the top layer of nesa coating is big, so in case adhered to dust, accompanying dust is difficult to break away from and goes.Therefore, above-mentioned structure is inadequate as the structure of adhering to and easily removing accompanying dust that reduces dust.
The present invention finishes in order to solve the above-mentioned problem of at least a portion, can realize the present invention with following form or application examples.
[application examples 1]
Should the related optical multilayer film filter of use-case be the optical multilayer film filter that has the inorganic thin film that is constituted by plural layer at substrate, it is characterized in that, above-mentioned inorganic thin film is made of low-density forming portion and high density forming portion, be formed with fluorine-containing organo-silicon compound film on the surface of above-mentioned inorganic thin film, in the above-mentioned low-density forming portion, the top layer of above-mentioned inorganic thin film or comprise that the plural layer on this top layer is formed by low-density titanium dioxide layer and/or low-density silicon dioxide layer, above-specified high density forming portion lamination between above-mentioned low-density forming portion and aforesaid substrate is highdensity silicon dioxide layer with respect to above-mentioned low-density silicon dioxide and is that highdensity titanium dioxide layer forms with respect to above-mentioned low-density titanium dioxide layer that the total film thickness of above-mentioned low-density forming portion is in the 280nm.
According to this formation, the top layer of inorganic thin film or comprise that the plural layer on this top layer is the low-density forming portion that is formed by low-density titanium dioxide layer and/or low-density silicon dioxide layer, make thus inorganic thin film top layer or comprise the insulativity reduction (electric conductivity increases) of the plural layer on this top layer.Therefore, the electric charge that is present in the surface because of static etc. can or comprise in the plural layer on this top layer mobile on top layer.By with this electric charge ground connection (ground wire), thereby make electric charge be difficult to accumulate in the most surperficial of optical multilayer film filter, adhering to of dust due to the static etc. is difficult to carry out.And then, be in the 280nm by the total film thickness that makes the low-density forming portion, thereby obtain the dustproof effect in surface that low-density layer brings.
On the other hand, be formed with fluorine-containing organo-silicon compound film on the surface on the top layer of inorganic thin film, reduce surface energy thus, suppress adhering to of dust, and in case adhered to dust, also can easily remove.In addition, formed fluorine-containing organo-silicon compound film be film (＜10nm), compare with inorganics, density is also lower, thereby electric charge is penetrated into lower floor easily, and to dichroism also not influence.
And the density on the top layer of inorganic thin film is low, thereby the surface area on top layer increases (being equivalent to concavo-convex increase on the microcosmic), and the bond area of fluorine-containing organo-silicon compound film increases.Therefore, the adaptation of fluorine-containing organo-silicon compound film improves, and permanance improves.In the past, wave length shift etc. takes place in inorganic thin film easily that be made of low-density layer, but, in the above-mentioned formation, except low-density forms layer, also be formed with high density and form layer, form and have both the inorganic thin film that is derived from highdensity high optical quality, so realized the necessary low wave length shift of optical multilayer film filter and low turbidity superperformance and dust tightness such as (HAZE) simultaneously.
[application examples 2]
The optical multilayer film filter of above-mentioned application examples preferably has following formation: the density of above-mentioned low-density silicon dioxide layer is 1.9～2.1g/cm
3, the density of above-mentioned low-density titanium dioxide layer is 4.1～4.8g/cm
3, the top layer of above-mentioned inorganic thin film is formed by above-mentioned low-density silicon dioxide layer, selects in any number of plies of the number of plies of above-mentioned low-density forming portion from 2 layers to 4 layers.
Constitute according to this, the density of above-mentioned low-density silicon dioxide layer is 1.9～2.1g/cm
3, the density of above-mentioned low-density titanium dioxide layer is 4.1～4.8g/cm
3In the above-mentioned low-density forming portion, when the layer that will constitute above-mentioned top layer is made as the 1st layer, by forming low-density titanium dioxide layer or low-density silicon dioxide layer to the 4th layer-selective ground at the 2nd layer, as mentioned above, having obtained dust etc. due to the static is difficult to adhere to and in case adheres to the filtrator that dust also can easily be removed.
[application examples 3]
The preferred aforesaid substrate of optical multilayer film filter of above-mentioned application examples is glass substrate or quartz wafer.
According to this formation, by substrate is made of glass substrate, can accesses the dustproof glass of for example CCD image elements such as (charge bonded elements) that is difficult to adhere to as dust and have for example optical multilayer film filter of the function of UV-IR cutoff filter and IR cutoff filter of desired filter function simultaneously.In addition, by substrate is made of quartz wafer, can accesses for example optical low-pass filter that is difficult to adhere to as dust and have for example optical low-pass filter of the function of UV-IR cutoff filter and IR cutoff filter of desired filter function simultaneously.And then, should use-case also can be applied to the formation of anti-reflective film.
[application examples 4]
The manufacture method of optical multilayer film filter that should use-case is the manufacture method that has the optical multilayer film filter of the inorganic thin film that is made of plural layer at substrate, it is characterized in that, the highdensity titanium dioxide layer of surperficial lamination and highdensity silicon dioxide layer at aforesaid substrate, form the high density forming portion, then, being 280nm on the surface of above-specified high density forming portion with the total film thickness by vacuum vapour deposition is low-density titanium dioxide layer by the titanium dioxide layer with respect to above-specified high density and/or is the low-density forming portion that low-density silicon dioxide layer constitutes with respect to the silicon dioxide layer of above-specified high density with interior formation, and then, form fluorine-containing organo-silicon compound film on the surface on the top layer of above-mentioned low-density forming portion.
Manufacture method according to this optical multilayer film filter, form low-density titanium dioxide layer and/or low-density silicon dioxide layer by vacuum vapour deposition on the cambial surface of high density, can access the top layer that constitutes inorganic thin film thus or comprise the low-density forming portion of the plural layer on this top layer.Therefore, showed the top layer of high-insulativity or comprise that the insulativity of the plural layer on this top layer reduces originally.Thereby the electric charge that is present in the surface because of static etc. can or comprise in the plural layer on this top layer mobile on top layer.By with this electric charge ground connection (ground wire), can access the optical multilayer film filter that dust due to the most surperficial and static that electric charge is difficult to accumulate in the optical multilayer film filter etc. is difficult to adhere to.And then, be in the 280nm by the total film thickness that makes the low-density forming portion, can obtain above-mentioned effect.
In addition, be formed with fluorine-containing organo-silicon compound film by the silicon dioxide layer on the top layer that constitutes inorganic thin film, can reduce surface energy, suppress adhering to of dust, and in case adhered to dust, also can easily be removed.The fluorine-containing organo-silicon compound film that forms be film (＜10nm), compare with inorganics, density is also lower, so electric charge penetrates into lower floor easily, and to dichroism also not influence.And the density of the silicon dioxide layer on the top layer of inorganic thin film is low, thereby the surface area of silicon dioxide layer increases (being equivalent to concavo-convex increase on the microcosmic), and the bond area of fluorine-containing organo-silicon compound film increases.Therefore can obtain the optical multilayer film filter that adaptation improves, permanance improves of fluorine-containing organo-silicon compound film.
[application examples 5]
The manufacture method of the optical multilayer film filter of above-mentioned application examples is preferred: the density of above-mentioned low-density silicon dioxide layer is set at 1.9～2.1g/cm
3, the density of above-mentioned low-density titanium dioxide layer is set at 4.1～4.8g/cm
3, the number of plies of above-mentioned low-density forming portion is selected from any number of plies of 2 layers to 4 layers, thereby forms the optical multilayer film filter.
According to the manufacture method of this optical multilayer film filter, use vacuum vapour deposition to form titanium dioxide layer and the silicon dioxide layer that constitutes the low-density forming portion, can access density thus is 1.9～2.1g/cm
3Low-density silicon dioxide layer and density be 4.1～4.8g/cm
3Low-density titanium dioxide layer.And, when the layer that constitutes top layer in the low-density forming portion is set at the 1st layer, by forming low-density titanium dioxide layer or low-density silicon dioxide layer to the 4th layer-selective ground at the 1st layer, as mentioned above, can access dust due to the static etc. is difficult to adhere to and in case adheres to the optical multilayer film filter that dust also can easily be removed.
[application examples 6]
The manufacture method of the optical multilayer film filter of above-mentioned application examples is preferred: the pressure when carrying out the film forming of above-mentioned low-density silicon dioxide layer by above-mentioned vacuum vapour deposition is 5 * 10
-4～5 * 10
-2Pa, the pressure when carrying out the film forming of above-mentioned low-density titanium dioxide layer by above-mentioned vacuum vapour deposition is 1.4 * 10
-2～3 * 10
-2Pa.
According to the manufacture method of this optical multilayer film filter, the pressure in the time of will carrying out the film forming of silicon dioxide layer by vacuum vapour deposition is set at 5 * 10
-4～5 * 10
-2Pa is 1.9～2.1g/cm thereby can access density
3Low-density silicon dioxide layer.And the pressure in the time of will carrying out the film forming of titanium dioxide layer by vacuum vapour deposition is set at 1.4 * 10
-2～3 * 10
-2Pa is 4.1～4.8g/cm thereby can access density
3Low-density titanium dioxide layer.
[application examples 7]
Being characterized as of electronic apparatus that should use-case is assembled with the optical multilayer film filter, and above-mentioned optical multilayer film filter being made of the inorganic thin film that is made of plural layer on substrate and the fluorine-containing organo-silicon compound film that is formed at this inorganic thin film surface; Above-mentioned inorganic thin film is made of low-density forming portion and high density forming portion; In the above-mentioned low-density forming portion, the top layer of above-mentioned inorganic thin film or comprise that the plural layer on this top layer is formed by low-density titanium dioxide layer and/or low-density silicon dioxide layer; Above-specified high density forming portion lamination between above-mentioned low-density forming portion and aforesaid substrate is highdensity silicon dioxide layer with respect to above-mentioned low-density silicon dioxide and is that highdensity titanium dioxide layer forms with respect to above-mentioned low-density titanium dioxide layer; The total film thickness of above-mentioned low-density forming portion is in the 280nm.
According to this electronic apparatus, because it is assembled with following optical multilayer film filter, thereby the dust due to the static etc. is difficult to adhere to.And, in case adhered to dust, also can easily be removed, can suppress the electronic apparatus of effect of dust effectively for the mobile phone of for example camera head such as digital camera, Digital Video, band camera, the PC (Personal computer) of band camera etc.This optical multilayer film filter has the inorganic thin film that is made of plural layer and the fluorine-containing organo-silicon compound film that is formed at this inorganic thin film surface at substrate, the top layer of inorganic thin film or comprise that the plural layer on this top layer is formed by low-density titanium dioxide layer and/or low-density silicon dioxide layer in the low-density forming portion, the high density forming portion is between low-density forming portion and the substrate and by highdensity silicon dioxide layer and/or highdensity titanium dioxide layer and forms, and the total film thickness of above-mentioned low-density forming portion is in the 280nm.
[application examples 8]
In the electronic apparatus of above-mentioned application examples, preferred group is equipped with the optical multilayer film filter, and the density of above-mentioned low-density silicon dioxide layer is 1.9～2.1g/cm in the formation of this optical multilayer film filter
3, above-mentioned low-density titanium dioxide layer density be set at 4.1～4.8g/cm
3, above-mentioned low-density forming portion the number of plies from 2 layers to 4 layers the number of plies, select.
According to this electronic apparatus, because it is assembled with following optical multilayer film filter, thereby the dust due to the static etc. is difficult to adhere to.And, in case adhered to dust, also can easily be removed, can suppress the electronic apparatus of effect of dust effectively for the mobile phone of for example camera head such as digital camera, Digital Video, band camera, the PC (Personal computer) of band camera etc.The density of low-density silicon dioxide layer is 1.9～2.1g/cm in this optical multilayer film filter
3, the density of low-density titanium dioxide layer is 4.1～4.8g/cm
3, in the low-density forming portion, when the layer that constitutes top layer is made as the 1st layer, at the 1st layer to the 4th layer-selective ground low-density titanium dioxide layer of formation or low-density silicon dioxide layer.
Description of drawings
Fig. 1 is the sectional view of formation of the optical multilayer film filter of expression present embodiment.
Fig. 2 is the sectional view when the optical multilayer film filter of present embodiment is provided with ground wire.
Fig. 3 is the key diagram of mode of the surface resistance of expression working sample.
Fig. 4 is the key diagram of mode of the surface potential of expression working sample.
Fig. 5 is the curve map of the relation of the number of plies of low-density forming portion of expression validation test 2 and square resistance.
Fig. 6 is the curve map of the relation of the total film thickness of low-density forming portion of expression validation test 2 and square resistance.
Fig. 7 is the curve map of wavelength dispersion characteristic of the embodiment 3 of expression validation test 1.
Fig. 8 be expression UV side the half value correspondence wavelength through the time curve map that changes.
Fig. 9 be expression IR side the half value correspondence wavelength through the time curve map that changes.
Figure 10 is the key diagram of formation of the digital camera of the expression optical multilayer film filter that used present embodiment.
Symbol description
1... the fluorine-containing organo-silicon compound film of glass substrate, 2... inorganic thin film, 5..., 10... optical multilayer film filter, 100... photographing module, 110... optical low-pass filter, 115... protection eyeglass (cover glass), 120...CCD, 130... drive division, 140... stationary fixture, 150... earthing cable, 200... lens as substrate.
Embodiment
Below based on accompanying drawing the embodiment that the present invention is specialized is described.In addition, present embodiment be applicable to the light that makes visible light wave range by and have an example of the optical multilayer film filter (UV-IR cutoff filter) of good reflection characteristic at the ultraviolet band below the provision wavelengths and the infrared band more than the provision wavelengths.
(formation of optical multilayer film filter)
Fig. 1 is the sectional view of formation that schematically shows the optical multilayer film filter of present embodiment.In the formation of optical multilayer film filter 10, have as the glass substrate 1 of the substrate that sees through light and inorganic thin film 2 and the fluorine-containing organo-silicon compound film 5 of multilayer.
Aspect the material of inorganic thin film 2, in constituting, it has as lower floor: will be set to the TiO of titanium dioxide layer by the high refractive index layer (H) that high-refraction material forms
2Layer (n=2.40), will be set to the SiO of silicon dioxide layer by the low-index layer (L) that low refractive material forms
2Layer (n=1.46).
For this inorganic thin film 2, begin the at first TiO of lamination high-index material from glass substrate 1 side
2Layer 2H1 is at the TiO of the high-index material of institute's lamination
2The SiO of the top lamination low-index material of layer 2H1
2Layer 2L1.Then, at the SiO of low-index material
2The top TiO that replaces the lamination high-index material successively of layer 2L1
2The SiO of layer and low-index material
2Layer, inorganic thin film 2 that go up the rete lamination most is the SiO of low-index material
2Layer 2L30, thus TiO formed
2Layer and SiO
2Each 30 layers on layer, amount to 60 layers inorganic thin film 2.
Describe the formation of this inorganic thin film 2 below in detail.
For the mark that the thickness of following explanation constitutes, use the value of blooming nd=1/4 λ.Specifically, the thickness of high refractive index layer (H) is expressed as 1H, similarly the thickness with low-index layer (L) is expressed as 1L.In addition, the mark S among (xH, yL) S is the multiplicity that is called as the number that superposes, the formation in the repetition bracket of indication cycle's property.
The thickness of inorganic thin film 2 constitutes in (blooming), and design wavelength lambda is 550nm, the TiO of the 1st layer high-index material
2Layer 2H1 is 0.60H, the 2nd layer the SiO of low-index material
2Layer 2L1 is 0.20L, secondly is followed successively by 1.05H, 0.37L, (0.68H, 0.53L) 4,0.69H, 0.42L, 0.59H, 1.92L, (1.38H, 1.38L) 6,1.48H, 1.52L, 1.65H, 1.71L, 1.54H, 1.59L, 1.42H, 1.58L, 1.51H, 1.72L, 1.84H, 1.80L, 1.67H, 1.77L, (1.87H, 1.87L) 7,1.89H, 1.90L, 1.90H, the SiO of the low-index material on top layer
2Layer 2L30 is 0.96L, amounts to 60 layers, forms inorganic thin film 2 with this.
And, the SiO on the top layer of inorganic thin film 2
2Layer 2L30 goes up and forms fluorine-containing organo-silicon compound film 5 by vacuum vapour deposition with the about 5nm of thickness.
The optical multilayer film filter 10 of Gou Chenging has following function like this.Fig. 2 is the sectional view when the optical multilayer film filter is provided with ground wire.
The thickness of the fluorine-containing organo-silicon compound film 5 of optical multilayer film filter 10 is thinner, and its SiO that forms down
2Layer 2L30 is in the state that density is low, insulativity is low.
Therefore, the electric charge that produces on the surface of fluorine-containing organo-silicon compound film 5 sees through fluorine-containing organo-silicon compound film 5 and SiO
2Layer 2L30, thus move to TiO
2Layer 2H30.This TiO
2The resistance ratio SiO of layer 2H30
2Resistance low, so electric charge can be at this TiO
2Mobile in the layer 2H30.And, connecting earthing cable 150 by the surface at fluorine-containing organo-silicon compound film 5, electric charge can be by TiO
2Layer 2H30 sees through SiO
2Layer 2L30 and fluorine-containing organo-silicon compound film 5 are discharged into the outside through earthing cable 150.
Like this, can reduce the quantity of electric charge (carried charge) that produces on the surface of the fluorine-containing organo-silicon compound film 5 of optical multilayer film filter 10.
In addition, the surface of optical multilayer film filter 10 is fluorine-containing organo-silicon compound film 5, so surface energy is little, in case adhered to dust, can easily be removed.
(manufacture method of optical multilayer film filter)
Below the manufacture method of optical multilayer film filter is described.
At first, by having used the auxiliary electron beam evaporation plating (so-called IAD method, i.e. ion assisted deposition) of common ion) form inorganic thin film 2 at glass substrate 1.
Specifically, glass substrate 1 is installed in the vacuum evaporation chamber (not shown), the crucible of deposition material has been filled in the configuration of the bottom in the vacuum evaporation chamber then, utilizes electron beam to evaporate.Accelerate irradiation simultaneously and utilize the Ionized oxygen (TiO of ion gun
2Film forming the time add argon), thus, be formed in glass substrate 1 TiO that hockets with above-mentioned thickness
2High-index material layer 2H1～2H30 and SiO
2The film forming of low refractive index material layer 2L1～2L30.
Provide SiO below
2Layer and TiO
2The membrance casting condition of layer, the high density forming portion is with following standard conditions film forming.
＜SiO
2The membrance casting condition (standard conditions) of layer 〉
Film forming speed: 0.8nm/sec
Accelerating potential: 1000V
Accelerate electric current: 1200mA
Oxygen (O
2) flow: 70sccm
Film-forming temperature: 150 ℃
＜TiO
2The membrance casting condition (standard conditions) of layer 〉
Film forming speed: 0.3nm/sec
Accelerating potential: 1000V
Accelerate electric current: 1200mA
Oxygen (O
2) flow: 60sccm
Argon (Ar) flow: 20sccm
Film-forming temperature: 150 ℃
Herein, at the SiO on the top layer of carrying out inorganic thin film 2
2During the film forming of layer (2L30 of Fig. 1), with the accelerating potential of ion gun with accelerate under the state that current settings is 0 (zero) (oxygen flow that imports by control) and make the pressure change in the film formation device, control density.That is the SiO on top layer,
2The film forming of layer is undertaken by vacuum vapour deposition, rather than is undertaken by ion assisted deposition.The SiO of this moment
2Pressure during layer film forming is 5 * 10
-4～5 * 10
-2Pa.In addition, not by ion assisted deposition but carry out the SiO of film forming by vacuum vapour deposition
2Layer forms than using the ion assisted deposition method to carry out the SiO of film forming
2The low density SiO of layer
2Layer.
Secondly, in order to seek the SiO on top layer
2The raising of the adaptation of layer (2L30 of Fig. 1) and fluorine-containing organo-silicon compound film (symbol 5 of Fig. 1) is to the SiO on top layer
2Surface treatment is carried out on the surface of layer.Then, at the SiO that has carried out the top layer of surface-treated
2The film forming of fluorine-containing organo-silicon compound film is carried out on the surface of layer.Finally, obtained optical multilayer film filter 10 as shown in Figure 1.The SiO on top layer
2The surface treatment of layer is to use ion gun to carry out with following condition.
＜SiO
2The surface treatment condition of layer 〉
Oxygen (O
2) flow: 50sccm
Accelerating potential: 1000V
Accelerate electric current: 1000mA
Temperature in the chamber: 150 ℃
Processing time: 3 minutes
In the film forming of fluorine-containing organo-silicon compound film, (3M Co., Ltd. in Sumitomo makes for example to use the fluorine kind solvent; NOVEC HFE-7200) the fluorine-containing organo-silicon compound (goods name KY-130) of dilution Shin-Etsu Chemial Co., Ltd manufacturing, the preparation solid component concentration is 3% solution, particle with this solution infiltration porous ceramics of 1g is made carries out the drying back as evaporation source.
In addition, for other fluorine-containing organo-silicon compound, can use fluorine-containing organo-silicon compound KP-801 (goods name) that Shin-Etsu Chemial Co., Ltd makes, fluorine-containing organo-silicon compound OPTOOL DSX (goods name) that Daikin Ind Ltd makes and Demnum SeriesS-100 (goods name) etc.
In the film forming of fluorine-containing organo-silicon compound film 5, glass substrate 1 and the evaporation source that at first will be formed with inorganic thin film 2 place in the vacuum plant, carry out decompression exhaust.Then, be set under about 60 ℃ state in the temperature with substrate evaporation source is heated to about 600 ℃, make fluorine-containing organo-silicon compound evaporation, film forming on substrate.
In the present embodiment, in decompression atmosphere gas, use the vacuum deposition apparatus of 2 chambers that are connected, carry out surface treatment before the multilayer film film forming of inorganic thin film and fluorine-containing organo-silicon compound film form at the 1st chamber, carry out the film forming of fluorine-containing organo-silicon compound film at the 2nd chamber.
In addition, both can utilize the device of the separation that above-mentioned Room 2 are separated out, also can in same vacuum chamber, carry out surface treatment before the multilayer film film forming of inorganic thin film and fluorine-containing organo-silicon compound film form and the film forming of fluorine-containing organo-silicon compound film.
[validation test 1]
In the validation test 1, change the SiO on the top layer of inorganic thin film 2
2The formation condition of layer (2L30 of Fig. 1) is made a plurality of samples, and formed each sample (inorganic thin film 2) is carried out performance evaluation.
In the making of sample, form on the surface of the blank glass (refractive index n=1.52) of diameter 30mm, thickness 0.3mm and to have the different top layer SiO of formation condition
2The inorganic thin film 2 of layer.SiO except top layer
2Beyond the layer, carry out film forming with above-mentioned standard conditions, the SiO on top layer
2In the film forming of layer, by the O of control importing
2Gas flow changes over the pressure (vacuum tightness) in the film device, thereby carries out top layer SiO
2The film forming of layer.
For the sample of made, at the accelerating potential of ion gun with to accelerate under the state that current settings is 0 (zero) with the vacuum tightness in the film formation device be that 0.0005Pa, 0.0010Pa, 0.0030Pa, 0.0100Pa, 0.0300Pa, 0.0500Pa form top layer SiO
2Behind the layer, form fluorine-containing organo-silicon compound film with said method.The sample of made is expressed as embodiment 1～6 according to narrative order.
In addition, import gas so that make ion gun work (accelerating potential 1000V, acceleration electric current 1200mA) under the identical state of pressure and embodiment 1～6, carrying out the top layer SiO of inorganic thin film 2
2The film forming of layer is carried out the film forming of fluorine-containing organo-silicon compound film on its surface, be made into sample.To be expressed as comparative example 1～6 by narrative order with the vacuum tightness manufactured samples corresponding to embodiment 1～6.Wherein, in the comparative example 1～3 because hypotony, so therefore not work of ion gun fail to form the SiO on top layer
2Film.
And then, as a comparative example, make the sample that not form fluorine-containing organo-silicon compound film corresponding with embodiment 1～6 and comparative example 1～6.The sample corresponding with embodiment 1～6 and comparative example 1～6 is expressed as comparative example 7～18 by narrative order.Wherein, comparative example 13～15 is because hypotony, so therefore not work of ion gun fail to form the SiO on top layer
2Film.
For the sample of embodiment 1～6, comparative example 1～6 and the comparative example 7～18 of such making, by wipe test, surface resistance (square resistance) measure, the assessment item of surface potential detection, carry out performance evaluation.In addition, on the Si sheet with separately top layer SiO
2The formation condition of film is made SiO
2Film uses each sample that obtains, and carries out based on SiO in the lump
2The evaluation of the density measurement of film.
Each assessment item evaluation method separately is as follows.
(evaluation method)
(1) wipe test
Carry out in the wipe test before and after the wipe test contact angle determination, adhere to that number is measured and number mensuration is adhered to based on the bead of drifting dust (air blow, drifting dust test) in static test back based on the bead of static (static test).
(1-1) contact angle determination
Use contact angle meter (" CA-D type ", consonance science Co., Ltd. makes), utilize sessile drop method to measure the contact angle of pure water.
(1-2) static test
With BEMCOT (dust-free cleaning paper, cellulose 100%) inorganic thin film 2 surfaces are applied 1kg load and (standby 60 seconds) behind the reciprocating friction 30 times simultaneously, polyetylene beads (mean grain size 10 μ m) is contacted with this surface.Thereafter, the bead attachment surface is downward, leave standstill 10 seconds with this state after, with the zone of microscopic examination 3mm * 2.3mm, the bead that adheres to is counted.10 positions are counted, with mean value as adhesion amount.Environment during mensuration is 25 ℃ ± 3 ℃ of humidity 55% ± 5%, temperature.In addition, the mode that electrically contacts with multi-layer film surface and human body is measured.
(1-3) drifting dust test
After the static test, jet gun and the distance that is formed with each sample surfaces of inorganic thin film are set at 50cm, with the pressure of 0.1MPa substrate surface is blowed 10 seconds dry airs after, (adhering to) bead that remains in the surface is counted.Environment during mensuration is 25 ℃ ± 3 ℃ of humidity 55% ± 5%, temperature.
(2) surface resistance (square resistance) is measured
Measure the surface resistance of each sample.Fig. 3 is the key diagram of expression mode that the surface resistance of sample is measured.
Among Fig. 3, use surface resistance determinator (Mitsubishi Chemical makes, precision resister rate instrument UP MCP-HT45) 504 in the mensuration of surface resistance.The probe 501 of this surface resistance determinator 504 contacts with the surface of sample 502.The objective table 506 of mounting sample 502 is Teflon (registered trademark) system.Its condition determination is 1000V, 30sec.Environment during mensuration is 25 ℃ ± 3 ℃ of humidity 55% ± 5%, temperature.
(3) surface potential detection
Be formed with the surface of each sample of inorganic thin film with the powerful wiping of BEMCOT (dust-free cleaning paper, cellulose 100%), give static so that be the degree of 2000V as the surface potential of initial value, then through after 60 seconds, measure the surface potential of each inorganic thin film.
Fig. 4 is the key diagram of expression mode that the sample surfaces current potential is measured.
Among Fig. 4, the mensuration of surface potential is used surface potential instrument (TREK JAPAN manufacturing, Model341) 500.In the mensuration of utilizing this surface potential instrument 500, the distance between probe 501 and sample 502 surfaces is set at 10mm measures.In addition, the objective table 503 of mounting sample 502 is metal system, measures with the state of objective table 503 ground connection.Environment during mensuration is 25 ℃ ± 3 ℃ of humidity 55% ± 5%, temperature.
In addition, the SiO on the top layer of carrying out in the lump with above each assessment item
2In the density measurement of layer, on the Si sheet with each SiO on top layer
2Layer formation condition forms the SiO of thick about 200nm
2Behind the film, utilize GIXR (X ray reflection rate method determinator: motor manufacturing of science, ATX-G) measure density.
Above-mentioned table 1 is the form of evaluation result of expression validation test 1, the SiO that has wherein provided the inorganic thin film formation condition of embodiment 1～6 and comparative example 1～18 and comprised top layer
2The density measurement of layer is measured in interior wipe test (contact angle determination, static test and drifting dust test), surface resistance (square resistance), the evaluation result of surface potential detection.
In the table 1, utilizing the auxiliary SiO that forms down of ion gun
2The SiO of (comparative example 4～6, comparative example 16～18) during film (IAD method)
2The film density of film surpasses solid density 2.2g/cm
3It is believed that this is because the mixing of O (oxygen) atom of ion gun due to auxiliary caused.When the output power of ion gun was set at 0 (zero), density reduced.And, the pressure when density also depends on film forming (vacuum tightness), pressure is more high, and density is more low.It is believed that this be because, the pressure step-down can cause the mean free path of the particle that evaporates elongated, the energy when arriving base material increases.In addition, in this validation test 1, under the condition of the pressure that is higher than embodiment 6, film forming speed reduces, and can not keep the general film forming speed 0.8nm/sec that allows.
It is about 100～300 in embodiment 1～6 that bead before the wipe test adheres to number, is about 500～600 in comparative example 4～6 and the comparative example 16～18.So as can be known, compare with comparative example 16～18 with comparative example 4～6, it is few that the bead of embodiment 1～6 adheres to number.
It is believed that The above results is because the top layer SiO of inorganic thin film 2
2Due to the density difference of layer, the SiO on top layer
2Under the situation of the low density embodiment 1～6 of layer, square resistance is low, and surface potential is also low, thereby is caused the difference of bead adhesion amount by the difference of carried charge.Therefore in the comparative example 7～12 that does not have fluorine-containing organo-silicon compound film, bead adheres to number does not almost have difference with embodiment 1～6.
Secondly, the sample that has adhered to bead is carried out the drifting dust test, this is studied.For embodiment 1～6, carry out after the drifting dust test bead to adhere to number be 10～30, adhere to sharply minimizings of number.Relative therewith, for comparative example 7～12, the number that adheres to of bead reduces in the drifting dust test, but adheres to several many than the bead of embodiment 1～6.This is owing to whether the surface has due to the fluorine-containing organo-silicon compound film, and the surface energy of embodiment 1～6 that is formed with fluorine-containing organo-silicon compound film is little, so keep the ability of bead low, can easily accompanying bead be removed.On the other hand, the surface energy of comparative example 7～12 that does not have fluorine-containing organo-silicon compound film is big, so keep the ability height of bead, can not easily accompanying bead be removed.This can be known that also in embodiment 1～6, contact angle is 107 °～110 °, and is relative therewith by the measurement of contact angle result, and contact angle is 42 °～49 ° in the comparative example 7～12.In addition, owing to do not have bigger difference aspect square resistance and the surface potential between the two, so above-mentioned difference is not by the caused difference of carried charge as can be known.In addition, compare with comparative example 16～18, the adhesion amount after the drifting dust test of comparative example 4～6 also is because same reason less.
Just because of this, so we can say the SiO on the top layer that constitutes inorganic thin film 2
2The density of layer is preferably 1.9～2.1g/cm
3Scope.This is the SiO according to embodiment 6
2The density of film is 1.981g/cm
3, by the SiO of IAD method film forming
2The solid density of film surpasses 2.2g/cm
3(comparative example 4～7 and comparative example 16～18) draws.
In addition, aspect square resistance and surface potential, do not having than big difference between embodiment 1～6 and the comparative example 7～12 and between comparative example 4～6 and the comparative example 16～18.Therefore, fluorine-containing organo-silicon compound film is not to SiO
2The electric effect of removing due to the low-densityization of layer exerts an influence.
Like this, be attached to the surface in order to prevent dust and dust, with the SiO on the top layer of inorganic thin film 2
2Layer low-densityization, the electric charge of removing due to the static etc. are effectively, and then form fluorine-containing organo-silicon compound film on the surface in order to can easily remove adhered dust and dust is effective.
Under the situation of embodiment 1～6, there is not big difference aspect the bead attachment level before and after the wipe test after bead attachment level, the drifting dust test, the contact angle.Relative therewith, in the comparative example 4～6, contact angle reduces greatly before and after the wipe test, accompanies therewith, and the bead after the drifting dust test adheres to number also to be increased.Hence one can see that, under the situation of embodiment 1～6, and the permanance height of fluorine-containing organo-silicon compound film.
[validation test 2]
In the validation test 2, (constitute the top layer SiO of inorganic thin film 2 based on the result who obtains in the validation test 1
2The density of layer is preferably 1.9～2.1g/cm
3About), be formed on the top layer SiO that constitutes inorganic thin film 2 with low-density
2The lower floor of layer forms comprises TiO
2Layer is at interior SiO
2Layer is made such sample, and it is carried out performance evaluation.The low-density SiO on this top layer
2Layer, the low-density TiO that forms in its lower floor
2Layer and low-density SiO
2Layer is the low-density forming portion.
At first, before validation test 2, carry out low-density SiO
2Layer and low-density TiO
2The affirmation of the adaptation of layer.
Low-density SiO
2During the adaptation of layer is confirmed, on the surface of the blank glass of diameter 30mm, thickness 0.3mm with TiO as implied above
2The standard conditions of layer are carried out the TiO of the about 100nm of thickness
2The film forming of layer is carried out the low-density SiO of the about 100nm of thickness with the membrance casting condition (referring to table 1) identical with the embodiment 1～6 of validation test 1 on its surface
2The film forming of layer is made 6 kinds of such samples.Thereby, formed SiO
2The density and embodiment 1～6 identical (referring to table 1) of layer.The sample of made is called sample 1～6 according to the order corresponding to the formation condition of embodiment 1～6.
On the other hand, low-density TiO
2During the adaptation of layer is confirmed, use the blank glass of diameter 30mm, thickness 0.3mm equally, same with SiO as implied above on its surface
2The standard conditions of layer are carried out the SiO of the about 100nm of thickness
2The film forming of film is at this SiO
2The surface of film is with TiO
2The standard conditions of layer are carried out the TiO of the about 100nm of thickness
2The film forming of layer, make sample, in addition at the accelerating potential of ion gun with to accelerate electric current be under the state of 0 (zero), be that the membrance casting condition of 0.014Pa, 0.030Pa, 0.040Pa, 0.050Pa is carried out the low-density TiO that thickness is respectively about 100nm with the vacuum tightness in the film formation device
2The film forming of layer is made 4 kinds of samples, has made 5 kinds of samples sample as a comparison altogether.Also namely, low-density TiO
2Layer does not utilize ion assisted deposition method film forming, but utilizes the vacuum vapour deposition film forming.In addition, not TiO by ion assisted deposition but by the vacuum vapour deposition film forming
2Layer forms density than the TiO that uses ion assisted deposition method film forming
2The low density TiO of layer
2Layer.
The sample of made is called sample 11～15 with narrative order.
By the cross cut test based on JIS standard K 5600-5-6, sample 1～6 and the sample 11～15 of made carried out SiO
2Film and TiO
2The adaptation evaluation of film.In the cross cut test, the SiO that uses cutter that the surface at each sample is formed
2Film and TiO
2The surface of film forms in length and breadth at interval with 1mm and scratches (lattice of drawing that carry out 100 lattice), pull-up adhesive tape behind its surperficial Continuous pressing device for stereo-pattern, thus produce peeling off of film, with the metewand of following 3 grades peeling off of film estimated.
A: the edge of drawing lattice is smooth fully, and the eyelet of any grid is not all peeled off.
B: the film of drawing the crossing place of lattice has less peeling off (in 100 lattice, peeling off below 5%).
C: produce the peeling off of film (in 100 lattice, greater than 5% and peel off less than 15%) along the edge of drawing lattice and/or at crossing.
Table 2
Table 3
Table 2 is to provide to be formed with SiO
2The form of the adaptation evaluation result of the sample of layer and the formation condition of film has wherein provided the formation condition of film and has been formed with SiO
2The adaptation evaluation result of the sample 1～6 of layer.Table 3 is to have provided to be formed with low-density TiO
2The form of the adaptation evaluation result of the sample of layer and the formation condition of film has wherein provided the formation condition of film and has been formed with TiO
2The adaptation evaluation result of the sample 11～15 of layer.
In the table 2, be formed with low-density SiO for the surface
2The sample 1～6 of layer, it all demonstrates good adaptation (A) and has nothing to do with membrance casting condition.
On the other hand, in the table 3, for TiO
2Layer, TiO
2The density of film causes adaptation to reduce when reducing.And the adaptation evaluation result of sample 13 is A, so as low-density TiO
2TiO during layer
2The density of film is preferably 4.1g/cm
3More than.In addition, use ion to assist to form highdensity TiO
2TiO in the sample 11 of film
2The density of film is 4.89g/cm
3For this value, by changing the auxiliary condition of ion etc., also can further improve density, but increase in density makes that compression stress increases, turbidity value (HAZE, transparency) reduces, so be not preferred.Therefore, low-density TiO
2The preferable range of the density of layer is 4.1～4.8g/cm
3
Based on above result, for the SiO on top layer
2The low-density TiO that the lower floor of layer forms
2Layer for example adopts the formation condition (accelerating potential of ion gun and accelerate electric current be that 0 (zero), vacuum tightness are 0.014Pa) of sample 12, for the SiO that comprises top layer
2Layer and the low-density SiO that forms in its lower floor
2Layer adopts the formation condition (accelerating potential of ion gun and acceleration electric current be 0 (zero), vacuum tightness be 0.003Pa) identical with the above embodiments 3 to form, and makes new sample.
In the sample, with the TiO of standard conditions film forming
2Layer and with the SiO of standard conditions film forming
2Layer is lamination alternately successively, and top layer is low-density SiO
2Layer form to amount to 60 layers inorganic thin film 2 (referring to Fig. 1) thus, in this inorganic thin film 2, with the low-density SiO on top layer
2When layer (2L30) is made as the 1st layer, use low-density TiO
2Layer and low-density SiO
2Layer increases progressively one deck ground at every turn and forms in turn from the TiO with the standard conditions film forming the 2nd layer to the 6th layer of layer coming the 2nd layer (2H30) to the 6th layer (2H28) of its lower floor
2Layer and with the SiO of standard conditions film forming
2Layer is made 4 kinds of samples, and makes and adopt low-density TiO
2Layer and low-density SiO
2Whole formation layer that layer is formed for forming inorganic thin film 2 (comprises that top layer is low-density SiO
2Layer is at interior 60 layers) sample.
That is, the number of plies of low-density forming portion is that top layer (2L30) is by low-density SiO in 1 layer the sample
2Layer forms.This sample is identical with the embodiment 3 of validation test 1.The number of plies of low-density forming portion is that 2L30 is by low-density SiO in 2 layers the sample
2Layer forms, and 2H30 is by low-density TiO
2Layer forms.In addition, the number of plies of low-density forming portion is that 2L30 and 2L29 are by low-density SiO in 3 layers the sample
2Layer forms, and 2H30 is by low-density TiO
2Layer forms.Below, by low-density SiO
2Layer and low-density TiO
2The number of plies of the low-density forming portion that layer forms is formed into till the 6th layer successively.And then the low-density number of plies is that 2L30～2L1 is by low-density SiO in 60 layers the sample
2Layer forms, and 2H30～2H1 is by low-density TiO
2Layer forms.
For the sample that is formed with inorganic thin film like this, be that 1 layer sample is called embodiment 3 with the number of plies of low-density forming portion, be that the sample of 2 layers～6 layers and 60 layers is called sample 21～26 with narrative order with the low-density number of plies.
For each sample, identical with validation test 1, after the surface of the blank glass of diameter 30mm, thickness 0.3mm forms inorganic thin film, carry out the film forming of fluorine-containing organo-silicon compound film on its surface.
In addition, the SiO of low-density forming portion
2The refractive index (n) of layer is set at 1.43, the TiO of low-density forming portion
2Refractive index (n) be set at 2.28, when design wavelength lambda is set at 550nm, the SiO of the low-density forming portion of film forming in each sample
2The TiO of layer and low-density forming portion
2The physics thickness of each layer of layer (blooming provides in the thickness of above-mentioned inorganic thin film 2 constitutes) as follows.
The 1st layer of (2L30): 62.8nm, the 2nd layer of (2H30): 50.6nm, the 3rd layer of (2L29): 31.7nm, the 4th layer of (2H29): 50.9nm, the 5th layer of order (2L28): 32.2nm, the 6th layer of (2H28): 51.4nm.
That is, the number of plies is that the total film thickness of the low-density forming portion of 1 layer (sample 21)～6 layers (sample 25) and 60 layers (samples 26) is followed successively by 62.8nm, 113.4nm, 145.2nm, 196.0nm, 228.3nm, 279.7nm, 4374.6nm.
Then, for the sample of making 21～26, similarly carry out performance evaluation by the assessment item of wipe test (contact angle determination, static test and drifting dust test), surface resistance (square resistance) mensuration, surface potential detection with validation test 1.
Table 4 is forms of the evaluation result of expression validation test 2.
In the table 4, provided validation test 1 embodiment 3 evaluation result and comprise formed low-density SiO
2Layer and TiO
2The density measurement value of layer is in each interior inorganic thin film formation condition, and the wipe test, surface resistance (square resistance) that have provided sample 21～26 are measured, the evaluation result of surface potential detection.
In the table 4, along with the number of plies increase of low-density layer, square resistance reduces.But the number of plies is more than 4 layers the time, and square resistance does not almost change.
Fig. 5 is the curve map of relation of the number of plies and square resistance of the low-density forming portion of expression validation test 2, and Fig. 6 is the curve map of representing the relation of the total film thickness of low-density forming portion of validation test 2 and square resistance.
Among Fig. 5, transverse axis is represented the number of plies of low-density forming portion, the longitudinal axis is represented square resistance (ohm/), with the mapped point line of the square resistance of embodiment 3 (number of plies 1 of low-density forming portion) and sample 21～26 (number of plies of low-density forming portion is 2 layers～6 layers and 60 layers), represent with the line chart that connects.Among Fig. 6, transverse axis is represented the total film thickness of low-density forming portion, and the longitudinal axis is represented square resistance (ohm/), and is identical with Fig. 5, with the mapped point line of the square resistance of each sample, represents with the line chart that connects.
Obviously illustrated by this line chart shown in Figure 5: the number of plies of low-density forming portion is more than 4 layers the time, and square resistance is saturated, changes hardly.
When (sample 23) and 60 layers all were the low-density forming portion when number of plies of (embodiment 3) and low-density forming portion was 4 layers when secondly, the number of plies of low-density forming portion in these samples being 1 layer the wavelength dichroism of (sample 26) through the time variation confirm.The wavelength dichroism uses integrating sphere type spectrophotometric transmittance analyzer to measure.
Fig. 7 is the curve map of wavelength dispersion characteristic of the embodiment 3 of expression validation test 1.Among Fig. 7, transverse axis is represented wavelength (nm), and the longitudinal axis is represented transmitance (%), and Fig. 7 is the line chart that drafting obtains every the transmitance of 2nm wavelength in wavelength 300nm～1200nm (visible region to a part of near infrared light zone between).
Therefore, the inorganic thin film that forms in the sample of embodiment 3 and sample 23～26 all has IR by function.
Through the time affirmation that changes in, measures after wavelength after the firm film forming of each sample of half value correspondence of the half value (transmitance 50%) of UV (ultraviolet ray) side that A point is represented in the line chart shown in Figure 7 and IR (infrared ray) side that the B point is represented and the film forming through the wavelength after 30 days.
Fig. 8 for the wavelength of the half value of expression UV side through the time curve map that changes.
The line chart a1 that dots among Fig. 8 represent embodiment 3 (number of plies of low-density forming portion is 1 layer) through the time change, the line chart b1 that represents with solid line represent sample 23 (number of plies of low-density forming portion is 4 layers) through the time change, the line chart c1 that represents with dot-and-dash line represent sample 26 (60 layers all is the low-density forming portion) through the time variation.
On the other hand, Fig. 9 be expression IR side the half value correspondence wavelength through the time curve map that changes, the line chart a2 that dots among Fig. 9 represent embodiment 3 through the time change, the line chart b2 that represents with solid line represent sample 23 through the time change, the line chart c2 that represents with dot-and-dash line represent sample 26 through the time change.
In addition, in each curve map, the longitudinal axis of Fig. 8 is represented the wavelength coverage of 400～420nm, and the longitudinal axis of Fig. 9 is represented the wavelength coverage of 670～690nm.
Among Fig. 8 and Fig. 9, the wavelength of the half value correspondence of UV side through the time change and the wavelength of the half value correspondence of IR side through the time variation all become greatly with the increase of the number of plies of low-density film.So till represent to line chart b1 and line chart b2 4 layers, half value does not nearly all change, and number of plies square resistance saturated (referring to Fig. 5) when being 4 layers, so the number of plies of low-density forming portion is preferably 1 layer～4 layers.That is, inorganic thin film 2 preferably at least top layer by low-density SiO
2Layer forms or forms with the low-density forming portion SiO on top layer
2Layer also optionally is formed into top layer SiO
2Layer when being made as the 1st layer at the TiO of the 2nd layer～the 4th layer of formation of its lower floor
2Layer and SiO
2Layer.In other words, at the SiO on top layer
2When layer was the 1st layer, preferred low-density forming portion optionally was formed into the 1st layer～the 4th layer.
On the other hand, according to line chart shown in Figure 6, from the aspect of the total film thickness of low-density forming portion, the total film thickness of low-density forming portion (physics thickness) comprises the SiO on top layer
2Layer is interior, preferably at the SiO on top layer
2The lower layer side of layer is in the 280nm.
In the above embodiment, use blank glass to be illustrated as glass substrate 1, but be not limited to this, both can have used transparency carriers such as BK7, sapphire glass, borosilicate glass, blue or green glass sheet, SF3 and SF7, also can use general commercially available optical glass.And, to using TiO
2Situation as the material of high refractive index layer is illustrated, but also can use other Ta
2O
5, Nb
2O
5
And then, the SiO on the top layer of inorganic thin film 2
2Be provided with fluorine-containing organo-silicon compound film 5 on the layer (2L30), but also can use alkyl based compound (for example, the KF-96 that Shin-Etsu Chemial Co., Ltd makes) as waterproof membrane, to obtain the effect same with above-mentioned embodiment.
More than, according to present embodiment, will constitute the SiO on the top layer of inorganic thin film 2 at least
2The density of layer (2L30) is set at 1.9g/cm
3～2.1g/cm
3, thus, demonstrated the SiO of high-insulativity originally
2The insulativity of layer reduces (electric conductivity increases).Therefore, the electric charge that is present in the surface because of static etc. can pass the most surperficial SiO
2Layer reaches lower floor.With SiO
2Layer is compared, and the insulativity of the high-index material of lower floor is low, so electric charge can move on the surface of high refractive index film.By with this electric charge ground connection (ground wire), thereby electric charge is difficult to accumulate in the most surperficial of optical multilayer film filter, and dust due to the static etc. is difficult to adhere to.
In addition, at the SiO on the top layer that constitutes inorganic thin film 2
2Be formed with fluorine-containing organo-silicon compound film 5 on the layer (2L30), surface energy reduces thus, and adhering to of dust is inhibited, in case adhered to dust, also can easily dust be removed.And, formed fluorine-containing organo-silicon compound film 5 be film (＜10nm), compare with inorganics, density is lower, so electric charge is penetrated into lower floor easily, and to dichroism also not influence.
And, if the SiO on the top layer of inorganic thin film 2
2Density low, SiO then
2Surface area increase (being equivalent to concavo-convex increase on the microcosmic), the bond area of fluorine-containing organo-silicon compound film 5 increases.Therefore, the adaptation of fluorine-containing organo-silicon compound film 5 improves, and permanance improves.
And then, with the SiO on the top layer of inorganic thin film 2
2When layer is made as the 1st layer, at the 1st layer SiO
2The 2nd layer (2H30) and the 4th layer (2H29) of the lower floor of layer (2L30) optionally forms density is 4.1g/cm
3～4.8g/cm
3TiO
2Layer, and optionally to form density at the 3rd layer (2L29) be 1.9g/cm
3～2.1g/cm
3SiO
2Layer can obtain effect same as described above thus, can obtain simultaneously the wavelength dispersion characteristic through the time change little optical multilayer film filter.
In addition, except at the 1st layer (2L30) of inorganic thin film 2, the 2nd layer (2H30) and the 4th layer of (2H29) formed TiO
2Layer and the 3rd layer SiO
2Layer (2L29) owing to can form high-quality film, therefore also is easy to obtain the characteristic of optical multilayer film filter 10 necessary low wave length shifts and low turbidity in addition.
In addition, in the optical multilayer film filter 10 of present embodiment, by substrate is made of glass substrate 1, can accesses the dustproof glass of for example CCD image elements such as (charge bonded elements) that is difficult to adhere to as dust and have for example optical multilayer film filter of the function of UV-IR cutoff filter and IR cutoff filter of desired filter function simultaneously.In addition, by glass substrate 1 is made of quartz wafer, can accesses for example optical low-pass filter that is difficult to adhere to as dust and have for example optical low-pass filter of the function of UV-IR cutoff filter and IR cutoff filter of desired filter function simultaneously.And present embodiment also can be applied to the formation of anti-reflective film.
In addition, according to the manufacture method of the optical multilayer film filter of present embodiment, utilize vacuum vapour deposition to form to constitute at least the SiO on the top layer of inorganic thin film 2
2Layer (2L30), can access density thus is 1.9g/cm
3～2.1g/cm
3SiO
2Layer.Thereby, demonstrated the SiO of high-insulativity originally
2The insulativity of layer reduces (electric conductivity increases).Therefore, because static etc. former thereby the electric charge that is present in the surface can pass the most surperficial SiO
2Layer arrives lower floor.With SiO
2Layer is compared, and the insulativity of the high-index material of lower floor is low, so electric charge can move on the surface of high refractive index film.By with this electric charge ground connection (ground wire), can obtain the optical multilayer film filter that the most surperficial, dust that static causes that electric charge is difficult to accumulate in optical multilayer film filter 10 etc. is difficult to adhere to.
In addition, by using vacuum vapour deposition at the SiO on the top layer of inorganic thin film 2
2The lower floor of layer (2L30) forms TiO
2Layer, can access density is 4.1g/cm
3～4.8g/cm
3TiO
2Layer.And, at the SiO with the top layer of inorganic thin film 2
2Layer (2L30) is when being made as the 1st layer, optionally uses vacuum vapour deposition at the 1st layer SiO
2The 2nd layer (2H30) and the 4th layer (2H29) of the lower floor of layer forms TiO
2Layer and form SiO at the 3rd layer (2L29)
2Layer can access the SiO with the top layer that forms inorganic thin film 2 at least by vacuum vapour deposition thus
2The optical multilayer film filter that has effect same during layer.And then, the SiO on the top layer that constitutes inorganic thin film 2
2Form fluorine-containing organo-silicon compound film 5 on the layer, thus, can obtain adhering to of surface energy reduction, dust to be inhibited, in a single day to have adhered to the optical multilayer film filter that dust also can easily be removed.In addition, the film thickness of formed fluorine-containing organo-silicon compound film 5 is thinner, compares with inorganics, and density is also low, so electric charge penetrates into lower floor easily, and to dichroism also not influence.In addition, if the SiO on the top layer of inorganic thin film 2
2The density of layer is low, then SiO
2The surface area of layer increases, and the bond area of fluorine-containing organo-silicon compound film 5 increases.Therefore, can obtain the optical multilayer film filter that adaptation is improved, permanance is improved of fluorine-containing organo-silicon compound film 5.
In addition, by making the SiO to the top layer that constitutes inorganic thin film 2
2Layer (2L30) and SiO that will top layer
2Layer when being made as the 1st layer at the 1st layer SiO
2The SiO that the 3rd layer (2L29) of the lower floor of layer optionally forms
2Pressure when layer carries out film forming is 5 * 10
-4～5 * 10
-2Pa, can make its density is 1.9～2.1g/cm
3In addition, with the SiO on top layer
2Layer (2L30) is when being made as the 1st layer, by making at the 1st layer SiO
2The TiO that the 2nd layer (2H30) and the 4th layer (2H29) of the lower floor of layer optionally forms
2Pressure when layer carries out film forming is 1.4 * 10
-2Pa～3 * 10
-2Pa, can make its density is 4.1～4.8g/cm
3
Like this, the optical multilayer film filter 10 of the manufacture method manufacturing of the optical multilayer film filter by present embodiment can make the mobile phone of for example camera head such as digital camera, Digital Video, band camera, the PC conducts such as (Personal computer) of band camera suppress the electronic apparatus utilization of effect of dust effectively.
In these electronic apparatus, an example of applied optics multilayer film filter in the camera head of the digital camera of the shooting of carrying out rest image is described.
Figure 10 is the key diagram of formation of the digital camera of the expression optical multilayer film filter that uses present embodiment, has expressed photographing module 100 and has comprised the formation of the camera head of this photographing module 100.
Comprise the CCD (charge bonded element) 120 that protects eyeglass 115, optical low-pass filter 110 and optical imagery is carried out the imaging apparatus of opto-electronic conversion in the formation of photographing module 100.
The surface of optical low-pass filter 110 is formed with the UV-IR cutoff filter, in this UV-IR cutoff filter, constitutes the SiO on the top layer of above-mentioned inorganic thin film 2 (referring to Fig. 1)
2The density of layer (2L30) is 1.9～2.1g/cm
3, and at the SiO on the top layer that constitutes inorganic thin film 2
2Be formed with fluorine-containing organo-silicon compound film 5 on the layer.At this moment, the substrate of filtrator is quartz wafer.The part that the scioptics exchange that this optical low-pass filter 110 is digital cameras etc. directly contact with extraneous gas is the easiest part of adhering to dust.The stationary fixture 140 that is used for fixed optics low-pass filter 110 is made of conductive materials such as metals, and it is electrically connected with the outermost layer (surface) of optical low-pass filter 110.And stationary fixture 140 is by earthing cable 150 ground connection (ground wire).
Comprise this photographing module 100 in the formation of camera head, be configured in the lens 200 of light incident side, the drive division 130 of CCD120 that drives photographing module 100 and the body 300 that will carry out record-regeneration etc. from the image pickup signal of photographing module 100 outputs.In addition, body 300 comprises signal processing part be used to the correction of carrying out image pickup signal etc., be used for image pickup signal is recorded to record portion on the recording medium such as tape, be used for the reproducing unit that this image pickup signal is regenerated and the constitutive requirements such as display part that are used for demonstrating the screen picture of regenerating, and these do not illustrate in the drawings.The digital camera of Gou Chenging can provide the digital camera with following advantage like this: optical low-pass filter 110 surfaces of adhering to dust being easy to of directly contacting with extraneous gas are difficult to adhere to dust, and accompanying dust can be removed simply by drifting dust.
In addition, the structure with the photographing module 100 of lens 200 configured separate is illustrated, but also can in the formation of photographing module, comprises lens 200.
In addition, for the anti-reflective film on the surface that is formed at protection eyeglass 115, can use present embodiment.
In addition, can form multilayer film filter on the surface of protection eyeglass 115, implement.In addition, being quartzy system by making protection eyeglass 115, can be the protection eyeglass of part optical low-pass filter as dual-purpose.And, can be applied to formed anti-reflective film and multilayer film filter (UV-IR cutoff filter) etc. on the surface.
When in these protection eyeglasses, using present embodiment, can reduce the dust that adheres in the assembling procedure of camera head.
And then the formation that also can form anti-reflective film by the face side at optical low-pass filter is implemented.
Claims (8)
1. optical multilayer film filter, it is characterized in that for have the optical multilayer film filter of the inorganic thin film that is made of plural layer at substrate,
Above-mentioned inorganic thin film is made of low-density forming portion and high density forming portion,
Be formed with fluorine-containing organo-silicon compound film on the surface of above-mentioned inorganic thin film, described fluorine-containing organo-silicon compound film does not contain electric conductive polymer,
In the above-mentioned low-density forming portion, the top layer of above-mentioned inorganic thin film or comprise that the plural layer on this top layer is formed by low-density titanium dioxide layer and/or low-density silicon dioxide layer,
Above-specified high density forming portion lamination between above-mentioned low-density forming portion and aforesaid substrate is highdensity silicon dioxide layer with respect to above-mentioned low-density silicon dioxide layer and is that highdensity titanium dioxide layer forms with respect to above-mentioned low-density titanium dioxide layer
The total film thickness of above-mentioned low-density forming portion is in the 280nm.
2. optical multilayer film filter as claimed in claim 1 is characterized in that,
The density of described low-density silicon dioxide layer is 1.9g/cm
3～2.1g/cm
3, the density of described low-density titanium dioxide layer is 4.1g/cm
3～4.8g/cm
3,
The top layer of described inorganic thin film utilizes described low-density silicon dioxide layer to form,
The number of plies of described low-density forming portion is any number of plies of selecting from 2 layers to 4 layers, thereby forms described low-density forming portion.
3. as claim 1 or the described optical multilayer film filter of claim 2, it is characterized in that,
Described substrate is glass substrate or quartz wafer.
4. the manufacture method of an optical multilayer film filter, described optical multilayer film filter has the inorganic thin film that is made of plural layer at substrate, and this manufacture method is characterised in that,
Surface at aforesaid substrate forms the high density forming portion that lamination has highdensity titanium dioxide layer and highdensity silicon dioxide layer,
Secondly, be that 280nm is with interior formation low-density forming portion with the total film thickness on the surface of above-specified high density forming portion by vacuum vapour deposition, described low-density forming portion is to be low-density titanium dioxide layer and/or to be that low-density silicon dioxide layer forms with respect to the silicon dioxide layer of above-specified high density by the titanium dioxide layer with respect to above-specified high density
And then, forming fluorine-containing organo-silicon compound film on the surface on the top layer of above-mentioned low-density forming portion, described fluorine-containing organo-silicon compound film does not contain electric conductive polymer.
5. the manufacture method of optical multilayer film filter as claimed in claim 4 is characterized in that,
In the formation of described low-density forming portion, the density of described low-density silicon dioxide layer is set at 1.9g/cm
3～2.1g/cm
3, the density of described low-density titanium dioxide layer is set at 4.1g/cm
3～4.8g/cm
3, the number of plies of described low-density forming portion is any number of plies of selecting from 2 layers to 4 layers.
6. as the manufacture method of claim 4 or the described optical multilayer film filter of claim 5, it is characterized in that the pressure when carrying out the film forming of described low-density silicon dioxide layer by described vacuum vapour deposition is 5 * 10
-4Pa～5 * 10
-2Pa,
Pressure when carrying out the film forming of described low-density titanium dioxide layer by described vacuum vapour deposition is 1.4 * 10
-2Pa～3 * 10
-2Pa.
7. electronic apparatus, it is the electronic apparatus that is assembled with the optical multilayer film filter, it is characterized in that,
Above-mentioned optical multilayer film filter is by being made of plural the layer inorganic thin film that constitutes and the fluorine-containing organo-silicon compound film that is formed at this inorganic thin film surface on substrate, and described fluorine-containing organo-silicon compound film does not contain electric conductive polymer,
Above-mentioned inorganic thin film is made of low-density forming portion and high density forming portion,
In the above-mentioned low-density forming portion, the top layer of above-mentioned inorganic thin film or comprise that the plural layer on this top layer is formed by low-density titanium dioxide layer and/or low-density silicon dioxide layer,
Above-specified high density forming portion lamination between above-mentioned low-density forming portion and aforesaid substrate is highdensity silicon dioxide layer with respect to above-mentioned low-density silicon dioxide layer and is that highdensity titanium dioxide layer forms with respect to above-mentioned low-density titanium dioxide layer
The total film thickness of above-mentioned low-density forming portion is in the 280nm.
8. electronic apparatus as claimed in claim 7 is characterized in that,
In the formation of described low-density forming portion, the density of described low-density silicon dioxide layer is set at 1.9g/cm
3～2.1g/cm
3, the density of described low-density titanium dioxide layer is set at 4.1g/cm
3～4.8g/cm
3, the number of plies of described low-density forming portion is any number of plies of selecting from 2 layers to 4 layers.
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| JP2007297611 | 2007-11-16 | ||
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| JP2008201556 | 2008-08-05 | ||
| JP2008201556A JP2009139925A (en) | 2007-11-16 | 2008-08-05 | Optical multilayer film filter, method for producing optical multilayer film filter and electronic apparatus |
| JP2008-201556 | 2008-08-05 |
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| WO2013039215A1 (en) * | 2011-09-15 | 2013-03-21 | 富士フイルム株式会社 | Heat-ray shielding material |
| CN103383475B (en) * | 2012-05-03 | 2017-12-12 | 赛恩倍吉科技顾问（深圳）有限公司 | Ultraviolet cut-off filter and camera lens module |
| CN103576226B (en) * | 2012-08-10 | 2017-07-11 | 赛恩倍吉科技顾问（深圳）有限公司 | Infrared cut-off light filtering films, cutoff filter and camera lens module |
| JP6317875B2 (en) * | 2012-09-06 | 2018-04-25 | 日本板硝子株式会社 | Infrared cut filter, imaging device, and method of manufacturing infrared cut filter |
| KR101382209B1 (en) * | 2013-04-29 | 2014-04-07 | 주식회사 옵트론텍 | Manufacturing method of transparent electrode structure for touch screen using electron beam evaporation |
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| CN105849308B (en) * | 2013-12-31 | 2019-07-16 | 依视路国际公司 | The method of multilayer module and control layer thickness |
| WO2016017791A1 (en) * | 2014-08-01 | 2016-02-04 | Jsr株式会社 | Optical filter |
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| CN105738993A (en) * | 2014-12-09 | 2016-07-06 | 鸿富锦精密工业（深圳）有限公司 | Optical filter and lens module with optical filter |
| JP6630161B2 (en) * | 2016-01-21 | 2020-01-15 | 株式会社日本触媒 | Light selective transmission filter and method of manufacturing the same |
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| US20220155492A1 (en) * | 2019-03-13 | 2022-05-19 | Panasonic Intellectual Property Management Co., Ltd. | Optical element and method for manufacturing the same |
| US11314004B2 (en) | 2019-04-08 | 2022-04-26 | Visera Technologies Company Limited | Optical filters and methods for forming the same |
| CN110484869B (en) * | 2019-07-11 | 2021-07-16 | 湖北久之洋红外系统股份有限公司 | Mildew-proof and damp-proof optical film and preparation method thereof |
| JP2021026163A (en) * | 2019-08-08 | 2021-02-22 | Hoya株式会社 | Optical member with antireflection film and method for manufacturing the same |
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| CN101435888A (en) | 2009-05-20 |
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