CN100582822C - Absorption type multi-layer film neutral filter - Google Patents
Absorption type multi-layer film neutral filter Download PDFInfo
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- CN100582822C CN100582822C CN200510108571A CN200510108571A CN100582822C CN 100582822 C CN100582822 C CN 100582822C CN 200510108571 A CN200510108571 A CN 200510108571A CN 200510108571 A CN200510108571 A CN 200510108571A CN 100582822 C CN100582822 C CN 100582822C
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Abstract
The invention relates to an absorption type multiple layer film ND filter which arranges an absorption type multiple layer film which reduces transmitted light on thin film base board, the invention is characterized in that the absorption type multiple layer films (13, 16) are composed of dielectric layers (14, 17) which are composed of SiO2, A12O3 or a compound of the SiO2 and the A12O3 through laminating alternatively and multiple layer films which are formed by metal layers (15, 18) which are composed of Ni monomers or Ni type alloys, wherein the absorption type multiple layer films are respectively formed on two sides of the base board, thereby film structures which take the base board as a center and are symmetrical mutually, and the curvature semi diameter of bending of the base board is adjusted to be more than or equal to 500 mm.
Description
Technical field
The present invention relates to a kind of absorption-type multilayer film neutrality (ND) optical filter that makes the transmitted light decay of visibility region, particularly relates to the improvement of the absorption-type multilayer film nd filter that adopts thin substrate such as resin film, resin plate or sheets of glass.
Background technology
Known in this ND optical filter (Neutral Density Filter) have the reflection incident light and the reflection-type ND optical filter that makes it to decay, absorb incident light and the absorption-type ND optical filter that makes it to decay.And when in the debatable lens optical system of reflected light, enrolling the ND optical filter, usually use absorption-type ND optical filter, in this absorption-type ND optical filter, have to the own blended absorbent material of substrate (coloured glass ND optical filter) or the coating type of absorbing material and substrate itself and do not absorb but type that the film that forms in its surface absorbs.Also have, in the latter case, for the reflection that prevents film surface constitutes multilayer film with above-mentioned film, and the effect that has the function of decay transmitted light and prevent to reflect.
And the absorption-type multilayer film nd filter that constitutes by multilayer film as above-mentioned film, the multilayer film of combined electrical dielectric layer and titanium oxide layer is disclosed in No. 3359114 communique of JP patent, also have, disclose the multilayer film of combined electrical deielectric-coating and niobium rete in the TOHKEMY 2002-350610 communique.
Also have, disclose in the flat 10-133253 communique of TOHKEMY a kind of for avoiding since the mechanicalness contact scratch, and at least one side the most surperficial the method for the dielectric hard film layer of formation.
But, use the absorption-type multilayer film nd filter on little slim digital camera, need substrate self attenuation owing to interblock space is narrow and small, be suitable for extremely thin glass substrate or resin plate, resin film as substrate.
But, when being suitable for extremely thin glass substrate or resin plate, resin film as substrate, distinctive problem as follows can take place.
That is, if on every side single face of extremely thin glass substrate or resin plate, resin film, form the different multilayer film of structure, then because the membrane stress of formed each multilayer film and substrate can be to a lateral bending song.At this moment, even if the desirable membrance casting condition that comprehensive membrane stress is cancelled on each of each one-sided multilayer film, just on single face only during film forming substrate can not carry out film forming under the crooked condition yet, although then form multilayer film on the two sides, substrate can be not crooked yet.And the said method that can be cancelled as comprehensive membrane stress, having on each layer the method for eliminating membrane stress, eliminate the method for membrane stress by the film of alternately laminated drawing stress and compression stress, is very difficult in reality but make the situation of the membrane stress vanishing of multilayer film.
For example, as shown in Figure 1, forming absorption-type multilayer film 1 on the face of substrate 3 under the situation of the general absorption-type multilayer film nd filter that forms antireflection film 2 on another face, if absorption-type multilayer film 1 is bad with the membrane stress balance of antireflection film 2, then under the situation that substrate 3 is made of extremely thin glass substrate or resin plate, resin film, substrate can be crooked.And, very thin and nearly all be at metal film by SiO
2Under the situation of the above-mentioned absorption-type multilayer film 1 shown in Figure 1 that constitutes,, can not use because metal film is very thin by with the alternately laminated method of eliminating membrane stress of the film of above-mentioned drawing stress and compression stress, need be with SiO
2The membrane stress of film is adjusted into zero.But with SiO
2The membrane stress of film is adjusted into zero membrance casting condition and sets difficulty in reality.
And when curved substrate, bonding or deposited time operation becomes difficult problem with this ND optical filter in existence, and, when using near imaging apparatus also the disadvantage that image can be distorted might take place.
Summary of the invention
The present invention is conceived to such problem and finishes, its objective is provides a kind of absorption-type multilayer film nd filter, even under the situation of the film substrate of where-used tree membrane of lipoprotein, resin plate or sheets of glass etc., also be difficult to take place the bending of substrate, and the property produced in batches is good, and can obtain transmissivity decay stably for wavelength.
Also have, other purpose of the present invention provides a kind of absorption-type multilayer film nd filter of can the steady production characteristic when making by magnetron sputtering method unified optical filter.
That is, a kind of absorption-type multilayer film nd filter of the present invention, be will make the absorption-type multilayer film of transmitted light decay be arranged on absorption-type multilayer film nd filter on the substrate that constitutes by resin film, resin plate or sheets of glass, it is characterized in that:
Above-mentioned absorption-type multilayer film is to be made of as follows multilayer film, and this multilayer film is by SiO by alternately laminated
2, Al
2O
3Perhaps the dielectric layer of their potpourri formation and the metallic diaphragm that is made of Ni monomer or Ni class alloy form, and, this absorption-type multilayer film forms respectively on the two sides of aforesaid substrate, thereby becoming with this substrate is center and symmetrical membrane structure, and the radius-of-curvature of the bending of substrate is adjusted to more than or equal to 500mm simultaneously.
As above-mentioned Ni class alloy, be that the element more than a kind or a kind that will select from Ti, Al, V, W, Ta, Si adds the Ni class alloy material among the Ni to.
And, according to absorption-type multilayer film nd filter of the present invention, because forming with this substrate on the two sides of the substrate of being made up of resin film, resin plate or sheets of glass is center and the absorption-type multilayer film of symmetrical membrane structure, and the membrane stress on two sides is cancelled out each other, therefore, even very thin substrate also can be realized its radius-of-curvature is adjusted into flatness excellent absorption type multilayer film nd filter more than or equal to 500mm.
Also have, owing to the wavelength dependency that uses the spectral-transmission favtor in visibility region as the metallic diaphragm in the absorption-type multilayer film little Ni monomer or Ni class alloy, can obtain the absorption-type multilayer film nd filter of transmissivity decay stably so can realize relative wavelength.
Further, because having formed with this substrate on the two sides of substrate is center and the absorption-type multilayer film of symmetrical membrane structure, so the productivity excellence when making absorption-type multilayer film nd filter, and owing to be eliminated the difference at the table back side, so management also becomes simple.
Particularly, constitute under the situation of above-mentioned metallic diaphragm at the Ni class alloy material that adds among the Ni by a kind that will from Ti, Al, V, W, Ta, Si, select or element more than it, because the strong magnetic characteristic of Ni target weakens, therefore, can pass through the unified absorption-type multilayer film nd filter of magnetron sputtering method steady production characteristic.
In addition, a kind of absorption-type multilayer film nd filter of the present invention, be will make the absorption-type multilayer film of transmitted light decay be arranged on absorption-type multilayer film nd filter on the substrate that constitutes by resin film, resin plate or sheets of glass, it is characterized in that:
Above-mentioned absorption-type multilayer film is to be made of as follows multilayer film, and this multilayer film is by SiO by alternately laminated
2, Al
2O
3Perhaps the dielectric layer of their potpourri formation and the metallic diaphragm that is made of Ni monomer or Ni class alloy form, and, this absorption-type multilayer film forms respectively on the two sides of aforesaid substrate, thereby becoming with this substrate is center and symmetrical membrane structure, the radius-of-curvature of the bending of substrate is adjusted to more than or equal to 500mm simultaneously, and above-mentioned Ni class alloy is that the element more than a kind or a kind that will select from Ti, Al, V, W, Ta adds the Ni class alloy among the Ni to.
Description of drawings
Fig. 1 is the section of structure of the absorption-type multilayer film nd filter of example in the past.
Fig. 2 is the section of structure of the absorption-type multilayer film nd filter of example (comparative example) in the past.
Fig. 3 represents the curve map of the theoretical spectral transmissison characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of example in the past.
Fig. 4 represents the curve map of the theoretical spectral reflection characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of example in the past.
Fig. 5 represents that the reflection multilayer of the absorption-type multilayer film nd filter of example in the past prevents the curve map of the theoretical spectral reflection characteristic of film.
Fig. 6 is the section of structure of the present invention's (embodiment) absorption-type multilayer film nd filter.
Fig. 7 is the curve map of theoretical spectral transmissison characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of the present invention shown in the expression table 2.
Fig. 8 is the curve map of theoretical spectral reflection characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of the present invention shown in the expression table 2.
Fig. 9 is the curve map of spectral-transmission characteristics of the absorption-type multilayer film nd filter of expression embodiment 1.
Figure 10 is the curve map of spectral-transmission characteristics of the absorption-type multilayer film nd filter of expression comparative example.
Figure 11 is the curve map of the relation of the transmissivity of expression Ni film, Cr film, Nb film and Ta film and wavelength.
Figure 12 is the curve map of theoretical spectral transmissison characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of the present invention shown in the expression table 3.
Figure 13 is the curve map of theoretical spectral reflection characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of the present invention shown in the expression table 3.
Figure 14 is the curve map of spectral-transmission characteristics of the absorption-type multilayer film nd filter of expression embodiment 3.
Figure 15 is the curve map of theoretical spectral transmissison characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of the present invention shown in the expression table 4.
Figure 16 is the curve map of theoretical spectral reflection characteristic of the absorption-type multilayer film of the absorption-type multilayer film nd filter of the present invention shown in the expression table 4.
Figure 17 is the curve map of spectral-transmission characteristics of the absorption-type multilayer film nd filter of expression embodiment 4.
Embodiment
Below, utilize accompanying drawing that absorption-type multilayer film nd filter of the present invention is elaborated.
In addition, utilization is when the substrate that approaches that uses the wave band zone not absorb, form identical membrane structure on the substrate two sides and have reflection and prevent the absorption-type multilayer film of function and realize desirable transmissivity that needs are considered all absorptions of each absorption-type multilayer film and set.
That is, be 25% ND optical filter for making transmissivity, need on the two sides, form transmissivity respectively and be
Absorption-type multilayer film, also have, be 12.5% ND optical filter for making transmissivity, need on the two sides, form transmissivity respectively and be
Absorption-type multilayer film.
At first, Fig. 2 represents that transmissivity is the absorption-type multilayer film nd filter of 12.5% example in the past.I.e. this absorption-type multilayer film nd filter of example in the past, (PC: polycarbonate) substrate 5, the reflection that has that forms on the surface of this substrate 5 prevent that the absorption-type multilayer film of function is (particularly by " the metallic diaphragm 9/SiO that the Ni monomer is formed by film
2The dielectric layer 8/ above-mentioned metallic diaphragm 9/ above-mentioned dielectric layer 8/ above-mentioned metallic diaphragm 9/ above-mentioned dielectric layer of being formed 8 " constitute) 6, the reflection multilayer that forms at the back side of substrate 5 prevents that film from (particularly being by " Ta
2O
5The metallic diaphragm 11/SiO that is formed
2The dielectric layer 10/ above-mentioned metallic diaphragm 11/ above-mentioned dielectric layer of being formed 10 " constitute) 7 its major parts of formation.In addition, in the table 1 below, represent that respectively above-mentioned absorption-type multilayer film and reflection multilayer prevent concrete membrane structure, the constituent material of film, the thickness and the refractive index of each layer.In addition, to in Fig. 3, represent with the theoretical spectral transmissison characteristic of the absorption-type multilayer film 6 of the absorption-type multilayer film nd filter of preceding example, the theoretical spectral reflection characteristic of absorption-type multilayer film 6 is represented in Fig. 4, also have, above-mentioned reflection multilayer is prevented the theoretical spectral reflection characteristic of film 7 from representing in Fig. 5.
Table 1
On the other hand, absorption-type multilayer film nd filter of the present invention, be to make the absorption-type multilayer film of transmitted light decay be formed on absorption-type multilayer film nd filter on the substrate that constitutes by resin film, resin plate or sheets of glass, it is characterized in that above-mentioned absorption-type multilayer film is by stacked by SiO mutually
2, Al
2O
3Perhaps the dielectric layer formed of the potpourri of these grades constitutes with multilayer film by the metallic diaphragm of Ni monomer or Ni class alloy composition, and, this absorption-type multilayer film is respectively formed on the two sides of aforesaid substrate, make that become with this substrate is center and symmetrical membrane structure, simultaneously the radius-of-curvature of curved substrate is adjusted to 500mm or more than it.
And, aforesaid substrate is made of resin film, resin plate or sheets of glass, and its material is not special to be limited, but material transparent preferably, consider batch process, be preferably the substrate with flexibility of the roll coating that can carry out dry type described later.Have flexible substrate, compare also very excellent aspect cheapness, light weight, the deformability with in the past glass substrate etc.Especially, as substrate, preferred resin plate or resin film.
As the resin plate that constitutes aforesaid substrate or the object lesson of sheets of glass, can list the resin plate from the resin material of dimethyl ester (PET), polyethersulfone (PES), polyacrylate (PAR), polycarbonate (PC), polyene (PO) and norbornane, selected or the monomer of resin film, or the complex of the monomer of resin plate of from above-mentioned resin material, selecting or resin film and the propylene class organic membrane on single face that covers this monomer or two sides.Particularly, for the norbornane resin material, the representative Nuo A (ゼ オ ノ ア) (trade name) that can list Japan father-in-law's (ゼ オ Application) company and Ah 's (ア one ト Application) (trade name) of JSR company etc.
Also have, above-mentioned metallic diaphragm is made of aforesaid Ni monomer or Ni class alloy, but preferably is made of the Ni class alloy material that selecteed element a kind of or more than it from Ti, Al, V, W, Ta, Si is added among the Ni especially.
About the detailed content narration more later on of this reason, its summary is as follows.That is, during with sputtering method plating Ni film, along with the continuous use of Ni target, the thickness attenuation of Ni target, thereby at the part of Ni target attenuation, the leakage field grow in plasma space.And when the leakage field grow in plasma space, flash-over characteristic (sparking voltage, discharge current etc.) changes and the film forming velocity variations.When producing in a word, use, the problem that the film forming speed of Ni film changes along with the consumption of Ni target will take place, thereby be difficult to the unified absorption-type multilayer film nd filter of steady production characteristic if same Ni target is long-time continuously.For avoiding this problem, as mentioned above, as long as use the Ni class alloy material that the element of selecting from Ti, Al, V, W, Ta, Si a kind of or more than it is added among the Ni to constitute above-mentioned metallic diaphragm.
Secondly, an object lesson of expression absorption-type multilayer film nd filter of the present invention in Fig. 6, this absorption-type multilayer film nd filter, be that (PC: polycarbonate) substrate 12 and the reflection that has that forms respectively on the two sides of this substrate 12 prevent that the absorption- type multilayer film 13,16 of function from constituting its major parts, and its transmissivity is 12.5% by film.In addition, in following table 2, represent concrete membrane structure, the constituent material of above-mentioned absorption- type multilayer film 13,16, the thickness and the refractive index of each layer respectively.Also have, the theoretical spectral transmissison characteristic of the absorption- type multilayer film 13,16 of absorption-type multilayer film nd filter of the present invention is illustrated among Fig. 7, and its theoretical spectral reflection characteristic is illustrated among Fig. 8.
Table 2
And as shown in table 2, above-mentioned absorption- type multilayer film 13,16 is from the respectively alternately laminated in order metallic diaphragm of being made up of the Ni monomer 15,18 of substrate 12 sides with by SiO
2The dielectric layer of forming 14,17 and constitute.In addition, these the number of plies is arbitrarily.But in Fig. 6, expression is two-layer by metallic diaphragm 15,18, dielectric layer 14,17 and adds up to 4 layers and the absorption- type multilayer film 13,16 formed.Also have, in table 2, metallic diaphragm 15,18 and dielectric layer 14,17 are set at same thickness respectively, are that the symmetrical membrane structure in center is a condition above-mentioned absorption- type multilayer film 13,16 is formed with substrate 12 still, can adjust each thickness arbitrarily.
, confirmed to constitute the wavelength dependency of transmissivity of the Ni film of above-mentioned metallic diaphragm 15,18 here, compared little with Cr film, Ta film and Nb film.Just, the amplitude of fluctuation of the transmissivity of Cr film, Ta film and the Nb film of wavelength in 0.400～0.800 μ m, shown in the curve map of Figure 11, be respectively 14.7%, 13.5% and 11.8%, but the amplitude of fluctuation of the transmissivity in the Ni film is 1.5% and very low.
But the reflection on absorption-type multilayer film nd filter surface becomes parasitic light, and brings bad influence to the image quality of digital camera etc.For this reason, for the absorption-type multilayer film nd filter surface also being had prevent the effect that reflects, above-mentioned absorption- type multilayer film 13,16 is made of multilayer film.
And, in absorption-type multilayer film nd filter of the present invention, by the thickness of the metallic diaphragm of Ni monomer or Ni class alloy composition Be Controlled well, and, wavelength dependency by the transmissivity of Ni class film in visibility region of Ni monomer or Ni class alloy composition is less, so absorption-type multilayer film that constitutes by metallic diaphragm and dielectric layer, the number of plies does not need overlapping in a large number, and the wavelength dependency of the spectral-transmission favtor in the visibility region is little, can obtain transmissivity decay stably for wavelength.
In addition, above-mentioned dielectric layer (wherein shown in the table 2) 14, the 17th is by SiO
2The film of forming preferably has alap refractive index materials (above-mentioned SiO by the metallic diaphragm of being made up of the Ni monomer relatively 15,18
2Al in addition
2O
3Perhaps SiO
2And Al
2O
3Potpourri) constitute.Also have, preferably control the thickness of dielectric layer 14,17 for making reflection preventing effect with absorption-type multilayer film.
And the metallic diaphragm of forming by the Ni monomer 15,18 and by SiO
2Each thickness of the dielectric layer of forming 14,17, preestablish into above-mentioned absorption- type multilayer film 13,16 and keep necessarily at the transmissivity and the reflectivity of visibility region (for example 0.400 μ m～0.800 μ m degree) with regulation, each thickness of preferred especially above-mentioned metallic diaphragm 15,18 is 2～15nm.In this absorption-type multilayer film nd filter, above-mentioned absorption-type multilayer film the 13, the 16th comprises the metallic diaphragm of being made up of the Ni monomer 15,18 and forms, therefore, even 4 layers of number of plies so seldom for example also have Optical transmission spectrum characteristic fully stably.
Secondly, above-mentioned absorption-type multilayer film of the present invention can form by vacuum vapour deposition, sputtering method, ion plating method.
For example, sputtering method is when the material that utilizes steam to force down forms film on substrate, or the effective film formation method when needing accurate control thickness, operates very easy and is widely used.Usual way is under about 10Pa or the Ar Pressure below it, with substrate as anode, the target that will become the pleurodiaphragmatic in terspace material is as negative electrode, between this, cause glow discharge and argon plasma takes place, and, make argon kation collision in the plasma on the target of negative electrode and make the particle of its sputtering target composition, and with this build-up of particles on substrate and film forming.
Above-mentioned sputtering method is to classify by the method for generation of argon plasma, will use the high-frequency sputtering that is called of high frequency (RF) plasma, will use the dc sputtering that is called of direct-current plasma.Also have, at the back side of target distributed magnet, and argon plasma is concentrated directly over target, the method for carrying out film forming even infrabar also improves the collision efficiency of argon ion is called as magnetron sputtering method.
And the metallic diaphragm in the absorption-type multilayer film of the present invention is by for example adopting the direct current magnetron sputtering process of the target of Ni metalloid (Ni monomer or Ni class alloy) to form in the environment of Ar.Also have, dielectric layer passes through for example at Ar and O
2Environment in adopt the high frequency magnetron sputtering method of Si or Al target to form.By utilizing high-frequency sputtering to carry out film forming above-mentioned dielectric layer, can prevent the paradoxical discharge that takes place in the reactive sputtering, thereby can carry out stable film forming.
But, because pure Ni material is the ferromagnetism body, therefore, when above-mentioned metallic diaphragm is utilized the direct current magnetron sputtering process film forming, be used for the magnetic force from the magnet at the back side that is configured in target of the plasma that is used between target and the substrate, blocked by the Ni target material and to the field weakening of surface leakage, thereby be difficult to make plasma to concentrate and carry out film forming efficiently.For avoiding this problem, the magnetic force of the magnet that is configured in back face of target the is strengthened negative electrode (high-intensity magnetic field negative electrode) of (400 Gausses or more than it), and will strengthen and carry out spatter film forming by the magnetic field of Ni target.
But, even adopted this method, the problem of as described below other also can take place when producing.That is, if the thickness of target reduces along with the continuous use of Ni target, then as mentioned above, at the leakage field in the part plasma space of the thickness attenuation of target grow thereupon.And when the leakage field grow in plasma space, flash-over characteristic (sparking voltage, discharge current etc.) changes and film forming speed also changes.When production, use in a word, the problem of the film forming speed generation degree variation of the Ni film along with the consumption of Ni target then can take place, thereby be difficult to the unified absorption-type multilayer film nd filter of production characteristic stably if same Ni target is long-time continuously.For avoiding this problem, as mentioned above, utilize the Ni class alloy material formation metallic diaphragm that the element of selecting from Ti, Al, V, W, Ta, Si a kind of or more than it is added among the Ni to get final product.
And in the present invention, for example, the preferred use contained the Ti element at the Ni of the scope of 5～15 weight % class alloy material.The lower limit of Ti amount is made as the reason of 5 weight %, be because by making it to contain 5 weight % or more than it and strong magnetic characteristic is extremely weakened, and also can carry out the magnetically controlled DC sputtering film forming even disposed the negative electrode of the low common magnet of magnetic field intensity.Also have, because the screening capacity in the magnetic field of target is low, so it is also little to depend on the variation of leakage field in the plasma space that target consumes, thus can keep certain film forming speed, thus can stably carry out film forming.Also having, the upper limit of Ti amount is made as the reason of 15.0 weight %, is owing to if contain the Ti that surpasses 15.0 weight %, then can form a large amount of intermetallicss, thereby may become the little material of wavelength dependency that is not transmissivity.Also have, the addition of Al element, V element, W element, Ta element, Si element also is to determine according to same reason, when adding these Al elements, V element, W element, Ta element, Si element etc., the adding proportion that preferably becomes adding proportion with the Al element and be 3～8 weight %, V element is that the adding proportion of 3～9 weight %, W element is that the adding proportion of 18～32 weight %, Ta element is that the adding proportion of 5～12 weight %, Si element is that the scope of 2～6 weight % is added and the Ni class alloy material that constitutes.
But, add element among the Ni to and be 2 kinds or its when above, it is low and make it not form a large amount of intermetallicss preferably to adjust to addition higher limit than each element.For example, when adding to Ti and two kinds of elements of Si among the Ni, if with respect to the Ti addition of 7.5 weight % and the addition of Si element when surpassing 5 weight %, (the Ti element is 5～15 weight % even the numerical value of these additions is at above-mentioned compositing range, the Si element is 2～6 weight %), the formation of intermetallics sometimes is also clearly.
Also have, except elements such as above-mentioned Ti, Al, V, W, Ta, Si, the interpolation element that the conducts such as Cu, Cr of can giving an example weaken the strong magnetic characteristic of Ni.But, the Cu element when adding element, is compared with elements such as above-mentioned Ti, Al, V, have shortcoming with respect to the poor adhesion of the Ni-Cu film of oxidation film.For example, relate in the TOHKEMY 2000-96167 communique of the target material in the electrode material that uses with ND optical filter different field, think and the ceramic substrate of oxide between cohesive problem is arranged, and proposed to utilize Ni-Ti class alloy to replace the target of Ni-Cu class alloy.Therefore, as interpolation element of the present invention, the Cu element is not the material that is fit to.Also have, the Cr element does not go wrong for above-mentioned cohesive, so but owing to bring bad influence undesirable to environment.
In addition, above-mentioned metallic diaphragm and SiO
2, Al
2O
3Perhaps the dielectric layer of these potpourri also can utilize dry type roll coating method and form on the substrate of film like.
And, for absorption-type multilayer film by adopting aforesaid structure, can provide in a kind of whole zone of the visibility region at 0.400 μ m～0.800 μ m reflectivity be 5% or below it and the amplitude of fluctuation of transmissivity 10% or it is with interior absorption-type multilayer film nd filter.
Also have, numerical value from be documented in table 1 and table 2 can be confirmed, absorption-type multilayer film nd filter of the present invention, compare with ND optical filter in the past, (its absorption-type multilayer film was that 270nm, reflection multilayer prevent that film from being 256nm to the total thickness separately on substrate two sides in the ND optical filter of example in the past, with respect to this, each one-sided absorption-type multilayer film of substrate is 154nm in the absorption-type multilayer film nd filter of the present invention) be thinned to approximately half degree, and, also very outstanding because of only using 2 kinds of membrane material productivitys.
Also have, in absorption-type multilayer film nd filter of the present invention, improve productivity in order to simplify membrance casting condition, as shown in table 2, will be by SiO
2The dielectric layer of forming is designed to the two sides and all has all identical thickness (70nm), and all to have whole identical thickness (7nm) also passable and also be designed to the two sides by the metallic diaphragm that the Ni monomer is formed.And, when forming absorption-type multilayer film on the substrate two sides, because membrane stress is crooked, be fixed on framework and to carry out film forming by each single face also passable, but film forming is even more ideal simultaneously on the two sides for not making very thin substrate.
By such structure, the radius-of-curvature that can realize making the bending of substrate is 500mm or more than it.If the radius-of-curvature of the bending of substrate is less than 500mm, then in absorption-type multilayer film nd filter cut-out, bonding, deposited such manufacturing procedure, utilize the processing of machine to become difficult, further, also may cross absorption-type multilayer film nd filter and cause figure to be distorted owing to transmission, this be also unsatisfactory.
And, as shown in Figure 6 absorption-type multilayer film nd filter of the present invention is placed on platform (with reference to the Reference numeral 4 of Fig. 1) when going up, substrate does not almost bend, and the gap of core only is 0.2mm or its following such degree that can not accurately measure.
On the other hand, (wherein the absorption-type multilayer film 6 of absorption-type multilayer film nd filter is positioned at upside when being placed on the absorption-type multilayer film nd filter of as shown in Figure 2 example in the past on the platform, and reflection multilayer prevents that film 7 is positioned at downside), substrate has bending, observes the gap of about 2mm at core.And substrate size is when being Φ 60mm, if in the gap that 0.9mm takes place central part, then Wan Qu radius-of-curvature is 500mm.
In addition, about the dielectric layer of absorption-type multilayer film nd filter of the present invention and the thickness of metallic diaphragm, preferably set: by SiO
2, Al
2O
3Perhaps the total thickness of the one-sided dielectric layer of the substrate formed of these potpourris be 100nm or its above, be 30nm or below it by the total thickness of the one-sided metallic diaphragm of the substrate of Ni or Ni class alloy composition.If this be since the total thickness of the one-sided dielectric layer of substrate less than 100nm, then may make absorption-type multilayer film be difficult to have the function that reflection prevents, and, if the total thickness thickening of the metallic diaphragm that substrate is one-sided surpasses 30nm, then can predict if will be with respect to the metallic diaphragm thickening of dielectric layer softness, then membrane stress can relax, but may spectral-transmission favtor extremely reduce.
Here, in absorption-type multilayer film nd filter of the present invention, on the substrate two sides, form and have with the substrate when being the absorption-type multilayer film of center and symmetrical membrane structure, might not want necessary and satisfy the condition of symmetry fully, and as long as the condition of the roughly symmetry of the degree of the satisfied membrane stress of can repealing by implication is just passable.For example, after the face side of substrate forms absorption-type multilayer film, assess the result of its optical characteristics, can by if the transmissivity on surface than predetermined value height then the transmissivity of rear side is reduced, on the contrary if the transmissivity on surface is lower then with the transmissivity raising of rear side etc. than predetermined value, come the membrane structure of the absorption-type multilayer film of inching rear side, thereby revise transmissivity.
Also have, between substrate and absorption-type multilayer film, be provided with by Si, SiO
x(wherein x≤2), SiN
x(wherein x≤1), Ti, TiO
x(wherein x≤2) or TiN
xThe bonding coat that (wherein x≤1) constitutes, and the cohesive of raising substrate and absorption-type multilayer film also can.
Below embodiments of the invention are described in detail.In an embodiment, compare evaluation for the absorption-type multilayer film nd filter of embodiment 1,3 and 4 and the absorption-type multilayer film nd filter of comparative example.
Embodiment 1
Substrate has adopted and has been cut into Φ 60mm and thickness is PC (polycarbonate) film of 100 μ m.This film is fixed with the metal framework of pushing from the position of the about 5mm in its edge, and carried out film forming by each single face.Utilized RF magnetic control sputtering device (Aruba storehouse (ア Le バ Star Network) corporate system) during film forming, at the SiO of dielectric layer
2Film forming speed be that the film forming speed of the Ni of 0.2nm/ second, metallic diaphragm is to carry out film forming under the 0.1nm/ state of second.Also have, this absorption-type multilayer film nd filter is because the two sides all is identical membrane structure, so each single face carries out the film forming of same processes respectively.
The membrane structure of the absorption-type multilayer film that on above-mentioned film two sides, forms, identical with as shown in Figure 6 absorption-type multilayer film nd filter, the SiO of its dielectric layer
2Thickness be 70nm, the thickness of the Ni of metallic diaphragm is 7nm.
And, when being placed on the absorption-type multilayer film nd filter of this embodiment 1 on the platform, almost there is not bending as the above-mentioned film of substrate, the gap of core is 0.2mm or its following such degree that can't accurately measure.
Embodiment 2
The Ni target that the Ni class alloys target (Sumitomo Metal Industries mine (share) corporate system) that contains the Ti of 7.5 weight % except use replaces using in embodiment 1, other carry out similarly to Example 1, and have made the SiO of dielectric layer
2Thickness be that the thickness of the Ni class alloy of 70nm, metallic diaphragm is the absorption-type multilayer film nd filter of the embodiment 2 identical with absorption-type multilayer film nd filter as shown in Figure 6 7mm.
And, when being placed on the absorption-type multilayer film nd filter of this embodiment 2 on the platform, above-mentioned film as substrate in this absorption-type multilayer film nd filter does not almost have bending yet, and the gap of core is 0.2mm or its following such degree that can't accurately measure.
Embodiment 3
The Ni class alloys target (Sumitomo Metal Industries mine (share) corporate system) that contains the Ti of 7.5 weight % except use replaces the Ni target of use in embodiment 1, and as shown in the following table 3, replaces SiO
2Dielectric layer and adopted Al
2O
3In addition, other and embodiment 1 carry out in the same manner, and have made the Al of dielectric layer
2O
3Thickness be that the thickness of the Ni class alloy (Ni-Ti) of 60nm, metallic diaphragm is the absorption-type multilayer film nd filter of the embodiment 3 of 7.7nm and absorption-type multilayer film nd filter same structure Fig. 6.
Table 3
That is, substrate adopts and to be cut into Φ 60mm and thickness is PC (polycarbonate) film of 100m, this film is fixed with the metal framework of pushing from the position of the about 5mm in its edge, and carry out film forming by each single face.In addition, adopt RF magnetic control sputtering device (Aruba storehouse (ア Le バ Star Network) corporate system) during film forming, at the Al of dielectric layer
2O
3Film forming speed be that the film forming speed of the above-mentioned Ni class alloys target (Sumitomo Metal Industries mine (share) corporate system) of 0.2nm/ second, metallic diaphragm is to carry out film forming under the 0.1nm/ situation of second.Also have, as shown in table 3, because the two sides all is identical membrane structure, so carry out the film forming of same processes respectively at each single face.And, the theoretical spectral transmissivity of absorption-type multilayer film when the single face film forming represented, and the theoretical spectral reflectivity is represented in Figure 13, also has that the spectral-transmission favtor of the absorption-type multilayer film nd filter of the embodiment 3 of actual film forming is represented in Figure 14 in Figure 12.
And, when being placed on the absorption-type multilayer film nd filter of this embodiment 3 on the platform, almost there is not bending as the above-mentioned film of substrate, the gap of core is 0.2mm or its following such degree that can't accurately measure.
Embodiment 4
The Ni class alloys target (Sumitomo Metal Industries mine (share) corporate system) that contains the Ti of 7.5 weight % except use replaces the Ni target of use in embodiment 1, and is such as shown in the following Table 4 in addition, replaces SiO
2Dielectric layer and adopt SiO
2And Al
2O
3Potpourri (mol ratio 1: 1) in addition, other carries out similarly to Example 1, and has made the SiO of dielectric layer
2And Al
2O
3The thickness of potpourri be that the thickness of the Ni class alloy (Ni-Ti) of 67nm, metallic diaphragm is the absorption-type multilayer film nd filter of the embodiment 4 of 7.3nm and absorption-type multilayer film nd filter same structure Fig. 6.
Table 4
That is, substrate adopts and to be cut into Φ 60mm and thickness is PC (polycarbonate) film of 100m, this film is fixed with the metal framework of pushing from the position of the about 5mm in its edge, and carried out film forming by each single face.In addition, adopt RF magnetic control sputtering device (Aruba storehouse (ア Le バ Star Network) corporate system) during film forming, at the SiO of dielectric layer
2And Al
2O
3The film forming speed of potpourri be that the film forming speed of the above-mentioned Ni class alloys target (Sumitomo Metal Industries mine (share) corporate system) of 0.2nm/ second, metallic diaphragm is to have carried out film forming under the 0.1nm/ state of second.Also have, as shown in table 4, because the two sides all is identical membrane structure, so carry out the film forming of same processes respectively at each single face.And, the theoretical spectral transmissivity of absorption-type multilayer film when the single face film forming represented in Figure 15 the theoretical spectral reflectivity is represented also have in Figure 16, the spectral-transmission favtor of the absorption-type multilayer film nd filter of the embodiment 4 of actual film forming is represented in Figure 17.
And, when being placed on the absorption-type multilayer film nd filter of this embodiment 4 on the platform, almost there is not bending as the above-mentioned film of substrate, the gap of core is 0.2mm or its following such degree that can't accurately measure.
Comparative example
At first on the PC film, form absorption-type multilayer film, thereafter, form reflection multilayer and prevent film, and obtain the absorption-type multilayer film nd filter of comparative example.
Adopt RF magnetic control sputtering device (Aruba storehouse (ア Le バ Star Network) corporate system), the SiO of the dielectric layer in above-mentioned absorption-type multilayer film during film forming
2Film forming speed be that the film forming speed of the Ni of 0.2nm/ second, metallic diaphragm is to have carried out film forming under the 0.1nm/ situation of second.In addition, prevent the SiO of the dielectric layer in the film at above-mentioned reflection multilayer
2Film forming speed with the Ta of 0.2nm/ second, metallic diaphragm
2O
3Film forming speed also carried out film forming under the situation for 0.2nm/ second.
Be formed at the film structure of the absorption-type multilayer film on the PC film single face, identical with as shown in Figure 2 absorption-type multilayer film nd filter, and the SiO of dielectric layer
2Thickness be that the thickness of the Ni of 80nm, metallic diaphragm is 10nm.Also have, the membrane structure that the reflection multilayer that forms on the another side of PC film prevents film is also identical with as shown in Figure 2 absorption-type multilayer film nd filter, and its thickness is the thickness shown in the above-mentioned table 1.
And, (wherein the absorption-type multilayer film of this absorption-type multilayer film nd filter is positioned at upside when being arranged on the absorption-type multilayer film nd filter of comparative example on the price fixing, reflection multilayer prevents that film is positioned at downside), as the PC film of substrate bending is arranged, and observe the gap of about 2mm at core.And when substrate size was Φ 60mm, if in the gap that 0.9mm takes place central part, then Wan Qu radius-of-curvature was 500mm, and therefore, this result represents that radius-of-curvature is littler than it.
Estimate:
Below, the spectral-transmission characteristics of the absorption-type multilayer film nd filter of the absorption-type multilayer film nd filter of embodiment 1,3 and 4 and comparative example is estimated.Spectral-transmission characteristics is that the automatic recording spectrophotometer that utilizes Hitachi company to make is measured.
And, the spectral-transmission characteristics of the absorption-type multilayer film nd filter of embodiment 1,3 and 4 is represented in Fig. 9, Figure 14 and Figure 17 respectively, and with the spectral-transmission characteristics of the absorption-type multilayer film nd filter of comparative example shown in Figure 10.
Consequently, embodiment 1,3 and 4 absorption-type multilayer film nd filter and the absorption-type multilayer film nd filter of comparative example have transmissison characteristic about equally in the use wavelength band of 0.4～0.7 μ m.
Like this, the absorption-type multilayer film nd filter of each embodiment has the identical optical characteristics of absorption-type multilayer film nd filter with conventional example (comparative example), and can obtain substrate does not have crooked ND optical filter.And, all be on the basis of same membrane structure on the two sides, the thickness of each dielectric layer on two sides all constitutes with identical thickness in addition, and the thickness of each metallic diaphragm all constitutes with identical thickness, so also outstanding on the productivity.
Claims (5)
1. absorption-type multilayer film neutral colour filter is to make the absorption-type multilayer film of transmitted light decay be arranged on absorption-type multilayer film neutral colour filter on the substrate that is made of resin film, resin plate or sheets of glass, it is characterized in that:
Above-mentioned absorption-type multilayer film is to be made of as follows multilayer film, and this multilayer film is by SiO by alternately laminated
2, Al
2O
3Perhaps the dielectric layer of their potpourri formation and the metallic diaphragm that is made of Ni monomer or Ni class alloy form, and, this absorption-type multilayer film forms respectively on the two sides of aforesaid substrate, thereby becoming with this substrate is center and symmetrical membrane structure, the radius-of-curvature of the bending of substrate is adjusted to more than or equal to 500mm simultaneously, and above-mentioned Ni class alloy is that the element more than a kind or a kind that will select from Ti, Al, V, W, Ta adds the Ni class alloy among the Ni to.
2. absorption-type multilayer film neutral colour filter as claimed in claim 1 is characterized in that: by above-mentioned SiO
2, Al
2O
3Perhaps the total thickness of the one-sided dielectric layer of the substrate that constitutes of their potpourri is set to more than or equal to 100nm, and the total thickness of the metallic diaphragm that the substrate that is made of Ni monomer or Ni class alloy is one-sided is set to smaller or equal to 30nm.
3. absorption-type multilayer film neutral colour filter as claimed in claim 1 or 2 is characterized in that: by above-mentioned SiO
2, Al
2O
3Perhaps the thickness of each dielectric layer of constituting of their potpourri is set to all identical thickness, and the thickness of each metallic diaphragm that is made of Ni monomer or Ni class alloy also is set to all identical thickness.
4. absorption-type multilayer film neutral colour filter as claimed in claim 1 is characterized in that: in the adding proportion of Ti element is that the adding proportion of 5～15 weight %, Al element is that the adding proportion of 3～8 weight %, V element is that the adding proportion of 3～9 weight %, W element is that the adding proportion of 18～32 weight %, Ta element is to set respectively in the scope of 5～12 weight %.
5. absorption-type multilayer film neutral colour filter as claimed in claim 1 or 2 is characterized in that: above-mentioned absorption-type multilayer film is to form by the one-tenth embrane method of selecting from vacuum vapour deposition, sputtering method or ion plating method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004338587 | 2004-11-24 | ||
| JP2004338587 | 2004-11-24 | ||
| JP2005180936 | 2005-06-21 |
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| Publication Number | Publication Date |
|---|---|
| CN1779493A CN1779493A (en) | 2006-05-31 |
| CN100582822C true CN100582822C (en) | 2010-01-20 |
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ID=36769887
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510108571A Expired - Fee Related CN100582822C (en) | 2004-11-24 | 2005-10-12 | Absorption type multi-layer film neutral filter |
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| Country | Link |
|---|---|
| JP (1) | JP4984101B2 (en) |
| CN (1) | CN100582822C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007083833A1 (en) * | 2006-01-20 | 2007-07-26 | Sumitomo Metal Mining Co., Ltd. | Absorption-type multilayer film nd filter and process for producing the same |
| US9796619B2 (en) * | 2010-09-03 | 2017-10-24 | Guardian Glass, LLC | Temperable three layer antirefrlective coating, coated article including temperable three layer antirefrlective coating, and/or method of making the same |
| US9588266B2 (en) | 2011-05-17 | 2017-03-07 | Canon Denshi Kabushiki Kaisha | Optical filter and optical apparatus |
| WO2014077399A1 (en) | 2012-11-16 | 2014-05-22 | キヤノン電子株式会社 | Optical filter and optical apparatus |
| US9581742B2 (en) * | 2012-11-20 | 2017-02-28 | Corning Incorporated | Monolithic, linear glass polarizer and attenuator |
| CN103612430A (en) * | 2013-11-14 | 2014-03-05 | 中山市创科科研技术服务有限公司 | Preparation method of dielectric-metal interference type selective absorption film |
| CN103744138B (en) * | 2013-12-13 | 2015-10-21 | 浙江大学 | The preparation method of the insensitive color filter of a kind of incident angle |
| WO2015196326A1 (en) * | 2014-06-23 | 2015-12-30 | 孙义昌 | Neutral density filter having multiple film layers, manufacturing device thereof and manufacturing method therefor |
| CN104297833B (en) * | 2014-11-06 | 2017-01-18 | 沈阳仪表科学研究院有限公司 | Low-reflection and neutral-density filter |
| CN107502865B (en) * | 2017-08-22 | 2019-04-23 | 苏州京浜光电科技股份有限公司 | A kind of production method of wide-angle imaging mould group optical filter |
| CN114075650A (en) * | 2020-08-18 | 2022-02-22 | 群创光电股份有限公司 | Coating device and coating method for curved substrate |
| CN113549888A (en) * | 2021-07-29 | 2021-10-26 | 浙江水晶光电科技股份有限公司 | Medium gray mirror and preparation method and preparation device thereof |
| CN113795131B (en) * | 2021-08-13 | 2024-03-01 | 深圳市志凌伟业光电有限公司 | Electromagnetic shielding member and display |
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| US3826728A (en) * | 1970-05-20 | 1974-07-30 | Shatterproof Glass Corp | Transparent article having reduced solar radiation transmittance and method of making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5938701A (en) * | 1982-08-30 | 1984-03-02 | Asahi Optical Co Ltd | Nd filter |
| JP3654388B2 (en) * | 1996-07-15 | 2005-06-02 | フジノン株式会社 | Optical light attenuation filter |
| JPH11202126A (en) * | 1998-01-12 | 1999-07-30 | Japan Aviation Electron Ind Ltd | Dielectric multilayer film filter |
| JP2004037545A (en) * | 2002-06-28 | 2004-02-05 | Nisca Corp | Nd filter and diaphragm device using the same |
-
2005
- 2005-10-12 CN CN200510108571A patent/CN100582822C/en not_active Expired - Fee Related
-
2010
- 2010-07-05 JP JP2010153069A patent/JP4984101B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3826728A (en) * | 1970-05-20 | 1974-07-30 | Shatterproof Glass Corp | Transparent article having reduced solar radiation transmittance and method of making the same |
| US3826728B1 (en) * | 1970-05-20 | 1986-06-10 | ||
| US3826728B2 (en) * | 1970-05-20 | 1994-07-12 | Boc Group Plc | Transparent article having reduced solar radiation transmittance and method of making same |
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| CN1779493A (en) | 2006-05-31 |
| JP4984101B2 (en) | 2012-07-25 |
| JP2010277094A (en) | 2010-12-09 |
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