CN109809689A - Substrate and optical filter for optical filter - Google Patents
Substrate and optical filter for optical filter Download PDFInfo
- Publication number
- CN109809689A CN109809689A CN201811397056.XA CN201811397056A CN109809689A CN 109809689 A CN109809689 A CN 109809689A CN 201811397056 A CN201811397056 A CN 201811397056A CN 109809689 A CN109809689 A CN 109809689A
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- China
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- weight
- filter
- glass
- filter glass
- optical
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- 230000003287 optical effect Effects 0.000 title claims abstract description 111
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- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to a kind of improved substrates and a kind of optical filter for optical filter.Substrate includes filter glass, which contains SiO2、ZnO、K2The chalkogenide of O and cadmium, the filter glass are based on oxide, TeO2Content is that 0.1 weight % to 3 weight %, CoO contents is 1.0 weight % to 7.0 weight %, preferably > 1.0 weight % to 7.0 weight %.Filter glass have in the visible light region of spectrum first stop range, the passband in the near infrared region of spectrum, the first transmission edge and the filter glass thickness based on 0.3mm between 700nm and 840nm edge wavelength X 'i0.5。
Description
Technical field
The present invention relates to a kind of substrate, a kind of optical filter and its use for optical filter including filter glass
On the way.
Background technique
Optical filter is famous with distinctive transmission performance.There is this filter at least one to stop range, and (German is
" Sperrbereich ") and a passband (German is " Durchlassbereich ").Stop range be have it is alap
The region of transmissivity, and passband (also referred to as passing through region) refers to the region with high-transmission rate of spectrum.If transmissivity exists
High-transmission rate is risen to from low transmission rate in narrow spectral region, then referred to as transmission edge (transmission edge).With steep
The filter of high and steep transmission edge is also referred to as brink filter.Second blocking range can abut passband.
Transmission edge is realized in glass by absorbing, and transmission edge is realized in interference filter by interference.
Optics (brink) filter is characterized by specific feature.For example, for the transmission edge of this filter
Position, can report the so-called edge wavelength X for internal transmission (German " Reintransmission ")i0.5.It is right
It should be in the spectrum internal transmittance τ between the blocking range and passband for limiting thicknessiValue τi=50% (Ti50) when wavelength (ginseng
See DIN 58131).
Optics brink filter generally includes that the substrate of filter glass form can be used.In addition there may be at least
One for establishing the coating of required optical property.
Filter glass (also referred to as coloured glass or capacity filter) includes more or less colourless parent glass, wherein mixing
Enter colouring component (chromophore), according to the property of the component mixed, selectively absorbs special ratios or bigger region
Incident light spectrum makes glass have colored appearance.In the case where these coloured glass, ion coloring glass and annealed glass it
Between distinguish, it is different in terms of coloring process and absorption characteristic.
In the case where ion coloring glass, usually having passed through solidifying for liquid glass realizes required spectral transmission
Curve.According to the property of used colouring component (its compound typical from the transition element of the periodic table of elements) with
And the property of parent glass, absorb specific SPECTRAL REGION.The absorbent properties of coloured glass are caused by the absorption band of coloring ion
And caused by parent glass itself, wherein absorption band has greater or lesser width.Due to the amorphous of glass and do not advise
The intensive formation region of then structure, coloring ion is non-uniform.This leads to different excitation energy and transmission curve edge
Less steep progress.(short wavelength regions of the edge towards spectrum position " shortwave " transmission edge, i.e., hereinafter referred to as " the first transmission
First rising edge at edge ", have edge wavelength X 'i0.5；Also see Fig. 1) steepness can not be adjusted to any precipitous.
Annealed glass (also referred to as " Semiconductor doped glasses " or " colloidal state coloured glass " or " brink coloured glass ",
German is " Anlaufglas " or " Steilkantenfarbglas ") there are parent glass, one or more semiconductor components
(dopant) has been used as colouring component to be added to parent glass.The dopant used is usually semiconductor dopant, especially cadmium
Chalkogenide (CdS, CdSe, CdTe, individually or with any combination) and/or zinc (ZnS, ZnSe, ZnTe, individually or with
Any combination).One special characteristic of annealed glass is, after production (by fusing approach or passing through sintering) and cooling, it
Be usually colourless or shallow glass form.Subsequent heat treatment process (annealing) makes glass coloration.Since glass being heated
(tempering) is to (transition temperature (Tg) -70 DEG C) and (Tg+ 200 DEG C), preferably (Tg+ 150 DEG C), particularly preferred TgBetween+120 DEG C
Suitable temperature (such as being tempered in the range of 530 DEG C to 730 DEG C) continues a few minutes to the time in several weeks, and phase occurs in glass
Separation, and nanocrystal is formed in a phase, so the absorption of annealed glass is attributable to this.Depending on mixing accordingly
It is miscellaneous, for example, formation chalkogenide crystal (cadmium sulfide/zinc sulphide, cadmium selenide/zinc selenide, and/or cadmium telluride/zinc telluridse, and
Solid solution, if possible).Therefore, colourless or shallow glass the first transmission edge is increased to precipitous rising, this is
The characteristic of annealed glass, it means that the first transmission edge becomes steeper, and is moved to greater or lesser wavelength.
Depending on the component of parent glass, the component of semiconductor doping and the control of temperature/time-program(me), can produce not
With the nanocrystal of chemical constituent and size, to change the marginal position of filter glass.Due to semiconductor crystal formation and
Its electric conductivity (energy gap between band structure, valence band and conduction band), annealed glass are almost absorbed in quantitative mode from UV range
Until the visible-range and in some cases incident white light of even higher wavelength, and (also referred to as more than the first transmission edge
For annealing border) wavelength quantitatively transmitted.Due to absorption region (stop range) and transmission region (passband) pass through it is precipitous
Edge defines each other, therefore annealed glass realizes especially pure color, therefore has particularly preferred optical filtering performance.
Due to the first precipitous transmission edge, position can be by component, melting condition and tempered condition with high precision
It reproducibly adjusts, so annealed glass can be used as the base of optical filter (referred to as brink filter) and optical filter
Plate.
The various glass ingredients for being suitable as annealed glass in principle have been described in patent document.From DE 2621741
The typical anneal glass of the known chalkogenide based on cadmium in 10141105 C1 of A1 and DE.JP 50-11924 B, which is described, to be contained
Li2The glass of O and glass containing high BaO content, these glass contain CdS, Se and Te.
The glass of JP 44-23821 A not only needs CdS, it is also necessary to iron oxide.
The glass of SU 192373 not only contains CdO, Se, S and C, also contains PbO and Cu2O.However, in PbO, CuO or
Cu2There is apparent undesirable discoloration in the case that O and chalkogenide exist simultaneously, in glass.
US 5,059,561 describes the annealed glass of the absorption ultraviolet light for sunglasses, is being tempered and is being formed crystallite
After there is no annealing color.By adding colouring component such as NiO, CuO, V2O5、Ce2O3、CoO、Nd2O3、Er2O3And/or
Sm2O3It is coloured.
It is known that based on alumina silicate glass without cadmium annealed glass (for example, DE 4231794C2), wherein crystallite is main
By TiO2And ZrO2Composition.Add a large amount of coloring oxide (such as Cr2O3、MnO2、Fe2O3、CoO、NiO、CuO、V2O5、CeO2、
TiO2、Pr2O3、Nd2O3、Er2O3) form color site (colour locus).The shortcomings that this glass, is that they are mentioned really
It has supplied to be sufficient to signaling system and has illuminated the red of purpose, but the feelings of the low thickness of glass in < 1mm, particularly < 0.5mm
Under condition, precipitous edge is not provided and stops the stringent blocking in range.
EP 0536572 A1, EP 0496943 A1 describe coloring jealous glass ceramics, contain small scale
Coloring oxide is (for example, Cr2O3、NiO、Co3O4、V2O5) for colouring.This glass ceramics cannot act as optical filter.
For some applications, may be advantageous using the optical filter with high-transmission rate, especially only for light
The characterizing portion of spectrum, for example, visible spectrum red area end and spectrum the near infrared region (NIR to such as 1000nm
Region) wavelength, have high-transmission rate.In general, the NIR region of spectrum includes the wavelength of 780nm to 3000nm.
Specific optical application requirement, when filter with sensor by use, for example, when being used in combination, filter exists
There is extra high transmissivity in the specific region of spectrum, and there is alap transmissivity in other regions, therefore
Should the light only to specific wave-length coverage be transparent.For example, using hair for the application in the red area and NIR of spectrum
The LED that wave-length coverage is the radiation of about 700nm to about 980nm is penetrated, wave-length coverage will be detected by sensor.In order to improve sensor
Measurement result, be previously inserted into optical filter in sensor, the optical filter is to required wavelength highly transparent, and to light
Other regions are composed with alap transparency.There is this optics of the passband limited by blocking range to filter on either side
Wave device is referred to as bandpass filter.
Up to the present the bandpass filter used is usually multilayer system or interference filter, has (colourless) substrate
With multiple filter layers of application, filter effect is based on reflection.Since light is not absorbed in these layers, corresponding saturating
Multiple reflections frequent occurrence in mirror system, this leads to " ghost image " (German is " Geisterbilder ").Pass through setting for filter layer
Meter, may be implemented multiple filter curves, and a feature of filter curve is that they in passband and stop model on either side
There is precipitous edge between enclosing.The shortcomings that interference filter, is that they have very strong dependence to the incidence angle of incident light
Property, and wide and high blocking only may be implemented by very more layers.Therefore, there is the required filter with brink
The multilayer system of function is very expensive.
In the range of component miniaturization, in the case where filter, it is also necessary to the realization of smaller filter overall thickness
Required performance of filter.Foot is even realized within the scope of the blocking with a thickness of 1mm to 3mm (up to the present common thickness)
The coloured glass enough stopped shows undesirable residual transmission rate within the scope of the blocking compared with low thickness (thickness < 1mm), i.e., one
Fixed transmissivity.In the case where the low substrate thickness or filter thickness of < 0.3mm, even if in the case where annealed glass, resistance
The transmissivity kept off in range is usually still 20%, it means that need additional measure (for example, with the filter layer additionally applied,
Such as the form of interference filter layer), to stop to realize the abundant blocking to transmission in range.
Summary of the invention
From this problem, it is an object of the present invention to provide a kind of filter glasses based on for optical filter
Substrate, the filter glass in NIR region have passband, wherein substrate have brink optical filtering performance, have in 700nm
The first transmission edge between 840nm, and by stopping to absorb to have in range to change at low substrate thickness (< 1mm)
Kind blocking.
The purpose is by the substrate according to claim 1 for optical filter and according to claim 10
Optical filter including substrate realize.
It according to the present invention, include containing SiO for the substrate of optical filter2、ZnO、K2The filter of the chalkogenide of O and cadmium
Light glass, the filter glass are based on oxide, TeO2Content be 0.1 weight % to 3 weight %, CoO contents be 1.0 weight % extremely
7.0 weight %, preferably > 1.0 weight % are to 7.0 weight %.The filter glass has first to stop in the visibility region of spectrum
Range has passband, and the filter glass thickness based on 0.3mm, in 700nm and 840nm in the near infrared region of spectrum
Between edge wavelength X 'i0.5Place has the first transmission edge.
For the first transmission edge, edge wavelength X 'i0.5Refer under 0.3mm thickness first stop range and passband it
Between spectrum internal transmittance τiValue τi=0.5 (corresponding to 50%) (or Ti50I value) when wavelength.
Substantially it is known that transmission edge edge wavelength X 'i0.5Thickness depending on glass.Number described below
(figures) it is related to the filter glass thickness of 0.3mm.Those skilled in the art will be inferred to for other filter glasses thickness
The position of transmission edge for degree.
Substrate for optical filter may include filter glass and be optionally applied to other component (example thereon
Such as, adhesion promoter layer, the layer for improving chemical stability, absorbed layer).In an advantageous embodiment, optical filtering glass
Glass constitutes the substrate for being used for optical filter, apply on substrate one or two or more coatings (in filter glass side or
Two sides coating) to manufacture optical filter.
In the context of the present invention, filter glass includes parent glass, which is based on being used as Network former
SiO2, as the ZnO of Network former and Network modifier and as the K of Network modifier2O.As mixing for coloring
Miscellaneous dose, filter glass includes chalkogenide (CdS, CdSe, CdTe and the chalkogenide such as (Zn, Cd) with zinc for forming cadmium
The solid solution of (S, Se, Te)) semiconductor dopant substance.Therefore, filter glass is annealed glass.In filter glass,
Color glass ingredient exists especially in the form of restoring.But hereinafter all glass ingredients are indicated with the weight % of oxide.
TeO2Effect of the content in the filter glass of the chalkogenide containing cadmium can be built by being heat-treated accordingly
It is vertical between 700nm and 840nm edge wavelength X 'i0.5The first transmission edge.One work of the high CoO content in glass
With being the additional absorbent within the scope of the blocking except the first transmission edge.Under low filter glass thickness, this causes stopping
Lower residual transmission rate in range, i.e., higher optical density, higher blocking.
According to design, the edge wavelength X of the first transmission edge 'i0.5, i.e. the position of the first transmission edge, in the filter of 0.3mm
Under light thickness of glass, 700nm, preferably 720nm can be, be further preferably 740nm, it is advantageously that 760nm, into one
Advantageously 780nm is walked, is additionally advantageously 800nm, is advantageously further 820nm, it is advantageously that 840nm.It is advantageously based on
The filter glass thickness of 0.3mm, the first transmission edge edge wavelength X 'i0.5It can be between 740nm and 820nm.
Optical filtering performance about filter glass or optical filter, it is advantageous to when filter glass is with a thickness of 0.3mm,
First transmission edge is in width≤150nm, preferably≤130nm, preferably≤120nm, preferably≤110nm, particularly preferably≤
From internal transmission rate≤15% in the section 100nm, further preferably≤80nm, preferably≤10%, rise to internal transmission rate >=
90%.This causes to stop the especially narrow transitional region between range and passband, this is for the subsequent use of optical filter
It is advantageous.Therefore, filter glass has the first precipitous transmission edge.
Advantageously, the thickness of filter glass can < 1mm, preferably≤0.75mm, preferably≤0.5mm, further preferably≤0.3mm,
Particularly preferably≤0.25, further preferably≤0.2mm.Therefore, filter glass is the annealing filter glass of thin glass form.Low thickness
Degree is make it especially suitable for production mini filter for optical application and other application.
In Favourable implementations of the invention, the filter glass based on 0.3mm thickness is between 400nm and 680nm
In wave-length coverage, i.e., in a section of the first blocking range, have less than 15%, it is preferably≤10%, more preferably≤5%, special
Internal transmission rate or spectrum internal transmittance not preferably≤1%.Low residual transmission rate in visible spectral range allows to
It significantly reduces or even completely left out up to the present for extra charge needed for stopping residual transmission (for example, the volume of application
Outer filter layer, such as interference filter layer).In the Advantageous variants of filter glass, the filter glass thickness based on 0.3mm,
In wave-length coverage between 300nm and 700nm, exist less than 15%, preferably≤10%, more preferably≤5%, particularly preferably≤
1% internal transmittance.
It is advantageously improved in scheme at of the invention one, the high CoO content in filter glass realizes filter glass and exists
Has the effect of the second blocking range near infrared region (NIR region), wherein the filter glass thickness based on 0.3mm, has
The edge IR wavelength X "i0.5The second transmission edge (IR transmission edge) between 950nm and 1300nm.It therefore, especially include TeO2
It is formed in the bandpass filter in NIR region with passband with the annealed glass of the chalkogenide containing cadmium of high CoO content,
Middle passband (position depending on the first transmission edge) can also include the part of the red spectral region of visible light.In spectrum
Adjacent with passband the second blocking range can be obviously reduced on infrared region direction, or according to corresponding application or even complete
It totally disappeared except the expense up to the present reduced in NIR region needed for transmiting is (for example, apply additional filter layer, such as interference filter
Photosphere).
For the second transmission edge, edge wavelength X "i0.5Indicate under 0.3mm thickness, passband and second stop range it
Between spectrum internal transmittance τiValue τi=0.5 (corresponding to 50%) (or Ti50II value) when wavelength.
According to each embodiment, the edge wavelength X of the second transmission edge "i0.5, i.e. the position of the second transmission edge,
Under the filter glass thickness of 0.3mm, 950nm, preferably 975nm can be, further preferably 1000nm, advantageously
1025nm, advantageously further 1050nm, additionally advantageously 1075nm, advantageously further 1100nm, advantageously 1125nm, favorably
Ground 1150nm, advantageously 1175nm, advantageously 1200nm, advantageously 1225nm, advantageously 1250nm, advantageously 1275nm, have
Sharp ground 1300nm.
The passband of filter glass or optical filter should have internal transmission rate (τ as high as possiblei).Of the invention one
It is a to be advantageously improved in scheme, the filter glass thickness based on 0.3mm, the internal transmission rate in section in passband, i.e., for
Wave-length coverage in passband, at least 85%, more preferably at least 90%, more preferably at least 91% are further preferably at least
95%.When the wave-length coverage with above-mentioned specified high internal transmission rate is in > 100nm, preferably > 130nm, preferably > 150nm model
It is more favorable when enclosing interior extension.Preferably for specific application, the passband with desired high internal transmission rate can be
Between 720nm and 1100nm, preferably between 750nm and 1000nm, particularly preferably the wave between 780nm and 950nm
In long range.
In Favourable implementations of the invention, the filter glass of substrate of the invention includes consisting of (based on oxidation
The weight % of object):
。
The following detailed description of the glass ingredient of filter glass.These components describe in the form of an oxide in a usual manner.So
And this is not the raw material form and the shape of the respective components actually existed in glass about respective components for glass production
(such as selenium can be used as SeO for the statement of formula2, can also be used as Se2-It is present in glass).
Silica (SiO2) it is used as Network former, and by weight 39% to 50%, preferably by weight 40%
To 46%, the main component of glass is constituted.The level (level) is not lower than the lower limit of 39 weight %, because of otherwise glass
Chemical stability can reduce.Another advantageous lower limit can be 40 weight % or 41 weight %.SiO2The upper limit of content should not
Greater than 50 weight %.The upper limit is not to be exceeded because otherwise fusion temperature can excessively significantly rise and volatility coloring Cd (S,
Se, Te) degree that evaporates from glass of compound increases.The Favourable implementations of glass include at most 46 weight %, preferably
The at most SiO of 45 weight %2.In preferred embodiments, glass of the invention includes the SiO less than 45 weight %2。
Another important component is zinc oxide (ZnO).The knot that is uniformly distributed in region realization dopant of the ZnO in glass
It is brilliant.Therefore, the Spindle-type α-FeOOH of semiconductor dopant occurs in the subsequent tempering of glass, and being formed has very narrow size
The crystallite of distribution.This leads to very pure " color " and the first precipitous transmission edge of filter glass of the invention.High Zn contains
Amount is also advantageous in glass production, because therefore the solid solution of cadmium and zinc is formed together with chalkogenide.Since zinc is to sulphur
High-affinity, it facilitate by chalkogenide keep in the melt.Due to reducing burn-up (burnoff), as a result, glass
Sulphur during glass melts loses reduction.The component is present in glass with 20 weight % to 32 weight %.Advantageous range may be used also
To be 22 weight % to 31 weight %, preferably 23 weight % to 31 weight %.The upper limit of 32 weight % is not to be exceeded, because having
The glass of high ZnO content has the trend for forming droplet-like precipitation zone.Advantageously, the upper limit therefore be also possible to 31 weight % or
30 weight %.For ZnO, which is not lower than the lower limit of 20 weight %, because above-mentioned desired effect otherwise cannot be reached.
Further advantageous lower limit can be 22 weight %, it is advantageously that 23 weight %, preferably 25 weight %.For some advantageous
Variant, 27 weight % can be advantageous lower limit.
Since " zinc silicate glass " has high score from tendency, filter glass advantageously contains potassium oxide (K2O) conduct
Network modifier, its ratio be 15 weight % to 35 weight %.Advantageous range is also possible to 18 weight % to 30 weight %, excellent
Select 18 weight % to 25 weight %.The microdeposit object in the region rich in ZnO in order to prevent, in order to increase the sulfur family in filter glass
Compound solubility, in order to reduce the processing temperature of glass and in order to matched coefficients of thermal expansion, filter glass is advantageously wrapped
Containing at least K of 15 weight %2O.Further advantageous lower limit can be 18 weight %, preferably 20 weight %.35 weights are not to be exceeded
The upper limit for measuring %, because otherwise chemical stability becomes too poor and thermal expansion coefficient is too high.Therefore, advantageously, K2The upper limit of O
It is also possible to 30 weight %, preferably 27 weight %, preferably 25 weight %.
Potassium oxide can in parent glass in relatively small degree by sodium oxide molybdena (Na2O it) replaces.Na2O can be advantageous
Ground is present in glass with 0 weight % to 5 weight %.Containing TeO2Annealed glass and annealed glass with high ZnO content
In, Na2O is not so good as K2O is suitable for establishing required optical filtering performance.There are the risks that undesirable Na-Zn silicate crystalline comes out.
In addition, higher Na2O content can reduce chemical stability.Therefore, the upper limit of 5 weight % is not to be exceeded.Further it is advantageous on
Limit can be 4 weight %, preferably 3 weight %, preferably 2 weight %, further preferably 1 weight %.Work as Na2When O is present in glass,
0.01 weight % can be advantageous lower limit.Na2What O was preferably intentionally added not as the component of batch of material (batch), but it is logical
It crosses and enters in glass for the raw material (such as cationic components as selenium raw material) of another glass ingredient.In such case
Under, Na2O not instead of raw material impurity, adjoint raw material, but be not mandatory glass ingredient.However, ought be for example using different
Na when selenium raw material, without addition other than customary impurities2The variant of O is also feasible.
In preferred variants of the invention, the Na of filter glass2O/K2O ratio (the weight % based on oxide) < 1, advantageously
< 0.5, also advantageously < 0.3, preferably < 0.2, preferably < 0.1, particularly preferably < 0.08, further preferably < 0.05.Na2O/K2O ratio is conducive to
Establish thermal expansion coefficient.
In some variants, filter glass (preferably passes through replacement K2O it) may include the Rb no more than 5 weight %2O and/or
No more than the Cs of 5 weight %2O and/or Li lower than 1 weight %2O.However, this is less preferred about material cost.Have
The variant of benefit can be free of Rb2O and/or Cs2O and/or Li2O.If at least one of these components are present in filter glass
In, then 0.01 weight % can be advantageous lower limit in each case.In a kind of variant, exists no more than 2 weight %, have
It is no more than the Rb of 1 weight % sharply2O, and/or it is no more than 2 weight %, advantageously not more than the Cs of 1 weight %2O。Li2O's has
The sharp upper limit can be < 1 weight %.
It, can be with content ratio > 0% to 4 weight % boron oxide (B in order to improve the meltbility of filter glass2O3).Favorably
Lower limit can be 1 weight %.However, the B with < 1 weight %2O3Variant or be free of B2O3Variant be also feasible.When
Filter glass contains no more than 4 weight %, the B of preferably shorter than 4 weight % (such as 3 weight % or 2 weight %)2O3When, it may be possible to
It is advantageous.B2O3The too high chemical stability that can make glass of content is deteriorated.
In the context of the present invention, filter glass preferably can be free of the alkaline earth oxide RO of addition (i.e. not
Containing MgO, CaO, SrO and BaO).Some variants can contain one or more alkaline earth oxides (calcium oxide (CaO), magnesia
(MgO), strontium oxide strontia (SrO), barium monoxide (BaO)) to adjust viscosity and thermal expansion coefficient, and improve meltability and machinability.
Just as alkali metal oxide, they are Network modifiers.In the context of the present invention, content (that is, RO (R=Mg,
Ca, Sr, Ba) summation) at most 10 weight %, the preferably up to value of 8 weight % are not to be exceeded because softening temperature can excessively be shown
The solubility for writing rising and chalkogenide can be significantly reduced excessively.The lower limit of RO summation can be 0.01 weight %.
Some variants may exist MgO and/or CaO and/or BaO and/or SrO, such as respectively at least 0.01 weight %
Ratio exist.The upper limit of every kind of component is 7 weight %.
The other components that can be optionally present in parent glass:
Fluorine (F) optionally can be present in glass.If it does, lower limit can be 0.01 weight %.The presence of F can reduce
Fusion temperature, to reduce the evaporation of volatility glass ingredient.3 weight %, advantageously 2 weight %, preferably 1 weight are not to be exceeded
The upper limit for measuring %, because the evaporation of F can lead to striped.Moreover, high fluorine concentration may cause melting vessel dissolution.Therefore, especially
Advantageous variant is free of F.
The glass can further contain the at most TiO of 3 weight %2, at most 3 weight % Al2O3And/or at most 10 weights
Measure the P of %2O5.The suitable lower limit of every kind of mentioned component can be 0.01 weight %.TiO2The blocking of UV can be improved,
But also had adverse effect as the nucleating agent for undesirable crystal phase, and bad coloring effect can be caused, because
The upper limit of 3 weight % is not to be exceeded in this.Advantageous variant can be free of TiO2.Al can be used2O3To improve acid resistance and reduce
Melting temperature.But the Al of 3 weight % is not to be exceeded2O3The upper limit, because therefore parent glass can become more crystallization sensitivity.
In an advantageous embodiment, it may be present in filter glass no more than 2 weight %, preferably more than 1 weight %, preferably not
More than 0.5 weight %, particularly preferably it is no more than the Al of 0.1 weight %2O3.Variant can be without the Al of addition2O3。P2O5It improves
Meltability/agglutinating property.But since it has adverse effect thermal expansion coefficient and chemical stability, preferably it is used only at most
5 weight %, particularly preferably only at most 3 weight %.Particularly preferred variant is free of P2O5。
For example, refractory oxide, i.e. zirconium, niobium, tantalum and lanthanum oxide, can be used for improving chemical stability and/or influence
Thermal expansion coefficient, TgWith operating temperature (VA).Since their meltability/sinterability is poor, their crystallization in some cases
Tendency and undesirable coloring effect and their high cost, at most 5 weight %, preferably up to 3 weight % are only added in they.
The suitable lower limit of every kind of mentioned component can be 0.01 weight %.Advantageous variant is free of zirconium oxide and/or niobium oxide
And/or tantalum oxide and/or lanthana.
The dopant ingredient for coloring being present in filter glass according to the present invention is preferably CdO, SeO2、TeO2
And SO3.Crystal or solid solution by as cationic components cadmium (Cd) and zinc (Zn) and as the anionic component sulphur (S),
Selenium (Se) and tellurium (Te) formation.The crystal of formation can be described as (Cd, Zn) (S, Se, Te), wherein with funny in one group of bracket
Number separated component can be substituted for one another in a wide range.
Cadmium oxide (CdO) is advantageously present in filter glass, and content is 0.1 weight % to 3 weight %.Preferred model
It encloses and can be 0.2 weight % to 2 weight %, preferably 0.3 weight % to 1 weight %.The level is not lower than under 0.1 weight %
Limit, otherwise available CdO is very little in coloring process.The Advantageous lower limits of CdO are also possible to 0.2 weight %, preferably 0.3 weight
Measure %, more preferable 0.4 weight %.The upper limit of 3 weight % is not to be exceeded because in process and product in CdO content by
It should keep relatively low in its toxicity.It is no more than 2.5 weight % when existing in filter glass, preferably more than 2 weight % are more excellent
Choosing is no more than 1.5 weight % and is also possible to advantageous when being particularly preferably no more than the CdO of 1 weight %.
Sulfur trioxide (SO3) be advantageously present in filter glass, content is 0.05 weight % to 1 weight %.It is preferred that
Range can be 0.07 weight % to 0.7 weight %, preferably 0.1 weight % to 0.5 weight %.The level is not lower than 0.05
The lower limit of weight %, otherwise very little SO3It can be used for coloring process.In addition, sulphur or the sulfur-bearing raw material components of addition are in the melt
Play reducing agent.The burning of S generates volatility SO2, passing through bubble formation serves as clarifying agent (refining simultaneously
agent)。SO3Advantageous lower limits be also possible to 0.07 weight %, preferably 0.1 weight %.The upper limit of 1 weight % is not to be exceeded, because
For K2SO4Or Na2SO4The destructive of (sulfate gallbladder) may be mutually precipitated out from glass.Do not surpass when existing in filter glass
0.7 weight %, preferably more than 0.5 weight %, more preferably no more than 0.4 weight % are crossed, 0.3 weight % is particularly preferably no more than
SO3When, it is also possible to advantageous.
Selenium dioxide (SeO2) be advantageously present in filter glass, content is 0.1 weight % to 1.5 weight %.It is excellent
The range of choosing can be 0.2 weight % to 1 weight %, preferably 0.3 weight % to 0.7 weight %.The level is not lower than 0.1 weight
The lower limit of % is measured, otherwise very little SeO2It can be used for coloring process.In chalkogenide crystal, due to corresponding lattice structure,
CdS and CdSe forms solid solution.SeO2Advantageous lower limits be also possible to 0.2 weight %, preferably 0.25 weight %, more preferable 0.3
Weight %.The upper limit of 1.5 weight % is not to be exceeded, because of SeO2It is easy evaporation at relatively high temperatures, and in other colder positions
Point distils again.SeO2It is also toxic and expensive one of component, therefore its content should keep relatively low.When in filter glass
In the presence of no more than 1 weight %, preferably more than 0.7 weight %, the preferably more than SeO of 0.5 weight %2When, it is also possible to have
Benefit.
Tellurium dioxide (TeO2) for desired end or NIR region in visible spectrum in the context of the present invention
Realize that the position of the first transmission edge is important in beginning.Therefore, TeO2Content in filter glass be 0.1 weight % extremely
3 weight %.Preferred range can be 0.15 weight % to 2 weight %, preferably 0.2 weight % to 1 weight %.The level is not answered
Lower than the lower limit of 0.1 weight %, otherwise very little TeO2It can be used for required coloring process.In chalkogenide crystal, CdS and
CdSe forms solid solution due to its similar lattice.CdTe is impregnated in these solid solution.TeO2Advantageous lower limits can also be with
It is 0.15 weight %, preferably 0.2 weight %.The upper limit of 3 weight % is not to be exceeded, because of the TeO of high level2It not will lead to
The position of one transmission edge is moved to even higher wavelength.In addition, being similar to SeO2, TeO2Be it is toxic and relatively expensive,
Therefore it should not be used with higher concentration.It is no more than 2.5 weight %, preferably more than 2 weight % when existing in filter glass,
Preferably more than 1.5 weight % are further preferably no more than the TeO of 1 weight %2When, it is also possible to advantageous.Advantageous variant can contain
Have no more than 0.7 weight % or is no more than 0.5 weight %.
Other than the chalkogenide of cadmium, the filter glass of substrate or filter according to the present invention contains 1 weight % to 7
The cobalt oxide (CoO) of weight %, preferably > 1 weight % to 7 weight %.
The optical filtering performance of filter glass according to the present invention is primarily based on the typical color Forming Mechanism of annealed glass, secondly
Typical color Forming Mechanism based on ion coloring glass., it is surprising that in the context of the present invention it has been found that working as
When filter glass is used as optical filter as thickness < 1mm thin substrate, contain TeO2Annealed glass in this high CoO contain
Amount is feasible and advantageous.Due to the absorption band of the CoO in thermal radiation area, up to the present have recognized that containing TeO2
Annealed glass in so (it is intended to be suitable for filter and therefore has height to optical property and homogeney for high CoO content
It is required that) it is impossible.The blocking in visibility region in order to obviously increase spectrum and in order to generate second in NIR region
Stop range, CoO should be present in filter glass at least 1 weight %, preferably greater than 1 weight %.Further it is advantageous under
Limit can be 1.25 weight %, preferably 1.5 weight %, more preferable 1.7 weight %, further preferably 2 weight %.7 weights are not to be exceeded
% is measured as the upper limit, otherwise high internal transmission needed for passband can deteriorate.In advantageous variant, there may also be no more than
6 weight %, the preferably more than CoO of 5 weight %.
Optionally, manganese oxide (II) (MnO) can be used as colouring component and is present in the ratio of 0 weight % to 5 weight %
In filter glass.It can be advantageous in the case where thin filter glass using MnO, to support the assimilation effect of CoO.When
When MnO is present in glass, advantageous lower limit can be 0.05 weight %, preferably 0.1 weight %, more preferable 0.5 weight %, also
It is preferred that 1 weight %.The advantageous upper limit is also possible to 4 weight %, 3 weight % or 2 weight %.
In one embodiment, glass is by component SiO2、ZnO、K2O、B2O3、CdO、SO3、SeO2、TeO2It is formed with CoO
To 95 weight %, preferably 98 weight %, the degree of more preferable 99 weight %.
Glass according to the present invention, as filter glass, preferably without other colouring components (such as Cu, Fe, Cr and/or
Ni the oxide of oxide and/or optical activity component (such as laser active component)), for example, Ce, Pr, Nd, Sm, Eu,
The oxide of Tb, Dy, Ho, Er and/or Tm.In addition, glass is preferably free of the component of insalubrity, such as Hg, Pb and TI
Oxide.Glass of the invention is further preferably free of radioactive composition, such as the oxide of Th and U.
Glass according to the present invention is preferably free of any bismuth oxide, is free of rare-earth oxide, such as niobium oxide, oxidation
Yttrium, ytterbium oxide, gadolinium oxide and tungsten oxide and/or zirconium oxide, the exception are, as set forth above, it is possible to which there are lanthana La2O3。
Niobium oxide can dissolve on a small quantity in the melt.In addition, niobium is a kind of multivalent ion for participating in redox equilibrium in melt.Zirconium oxide
And/or ytterbium oxide increases the risk of glass crystallization.Yttrium oxide can make the weathering stability of glass be deteriorated.In addition, glass is preferred
Not platiniferous (Pt).Platinum and other metals (Ru, Os, Rh, Ir, Pd) from Pt group have damaging influence to optical property.This
It can lead to scattering effect and color change.Therefore, should exist in glass and be less than 3ppm, preferably less than 2ppm, preferably less than 1ppm.
In one embodiment of the invention, glass according to the present invention is further preferably free of in claim or specification
Unmentioned other components；In other words, in such embodiments, glass is substantially made of said components, possible
Exception is that mentioned each component is not preferred or less preferred.Statement is " substantially ... by forming (consisting
Essentially of) " it in this article refers to other components and exists in the form of being not more than impurity, but have not as independent component
Meaning is added in glass component.
If description says glass without a component or without certain component, this means that the component at most can be used as impurity
It is present in glass.This means that it will not be added using significant quantity or add (if any) as glass ingredient.According to this
Invention, non-significant amount are less than 100ppm, preferably smaller than 50ppm, the more preferably less than amount of 10ppm.However, these limitations are not
Suitable for Na2O can be used as and is present in glass with raw material with higher ratio, but advantageously below 2 weight %, preferably
Less than 1 weight %.
In the case where glass according to the present invention, clarification is preferably mainly realized by physics clarification, it means that
Glass under fusing/clarifying temp has enough mobility so that bubble (such as volatility SO2) can rise.
Glass according to the present invention may include a small amount of conventional clarifying agent.Preferably, the total amount of the clarifying agent of addition is extremely
More 1.0 weight %, more preferably up to 0.5 weight %.Sb2O3And As2O3It can reside in glass, but since glass is also
It is melted under old terms, so not showing any clarifying effect.Besides chalcogenides, it can wrap in glass according to the present invention
Containing at least one following components as clarifying agent (in terms of weight %):
Sb2O30-1 and/or
As2O30-1 and/or
Halide (Br, Cl, F) 0-1.
Filter glass according to the present invention for substrate can be existed by the melting method conventionally used for annealed glass
About 1100 DEG C -1550 DEG C, under the reducing condition of preferably 1220 DEG C -1360 DEG C of temperature, by melting sources and clarification.In cooling phase
Between, glass is preferably made to required shape.In order to form coloring (i.e. for annealing), in temperature/time-program(me) of restriction
(tempering) thus obtained blank is heated again.
For this purpose, filter glass is in [Tg- 70 DEG C] to [Tg+ 150 DEG C] in the range of undergo further heat treatment, example
A few houres to several weeks are such as tempered in the range of 530 DEG C -730 DEG C.Here it is formed by the color component for dissolving in glass
The nano microcrystalline being made of Cd and Zn and S, Se, Te, the band gap between valence band and conduction band form decision by crystallite first,
It is secondary to be determined by the size of crystallite.This depends on annealing temperature and annealing time again.Temperature is higher and/or annealing time is longer, micro-
Crystalline substance will be bigger, and band gap will be smaller, and the inherent colour wavelength of glass will be longer.Band gap is in asymptotic mode close to same composition
The limiting value of macroscopical crystal.After annealing process, form the typical transmission characteristic of glass, i.e. brink filter
Transmissison characteristic.It is characterized in that in the blocking range (absorption region) of shortwave strong point, and at slightly higher wavelength fairly abruptly
It is transitioned into and almost transmits, referred to as passband or pass through region.Stopping preferably smaller than 150nm between range and passband.
It is also feasible for producing substrate according to the present invention by known sintering approach.For this purpose, for example, from containing
The green compact that the suspension of necessary glass ingredient obtains are dried after hardening, and are sintered at a temperature of between 600 DEG C and 1200 DEG C
And/or fusing.Sintering process based on powder method is also feasible.Glass blank production after made annealing treatment with
The chalkogenide crystal of cadmium is formed in temperature/time-program(me) needed in each case.
The present invention also provides a kind of optical filter, including substrate according to the present invention and for adjusting optically filtering
At least one optical layer of the spectral-transmission favtor of device, the substrate include filter glass, which has the first precipitous transmission
Edge (that is, brink filter, preferably bandpass filter) has the passband limited.At least one optical layer can be
Increase within the scope of desired blocking and stops and/or increase the steepness for stopping the transition between range and passband and/or increase passband
In transmission and/or generate narrow band filter in the pass-band.Narrow band filter tool in the context of the present invention
There is the interval with EO-1 hyperion transmissivity limited by brink, wherein interval width (FWHM, referring also to DIN ISO
9211-2) it is not more than 150nm, preferably no greater than 80nm, preferably no greater than 25nm, more preferably no more than 15nm.
Preferably substantially uniform, the flat and thin element of substrate, it means that it has, and there are two opposite sides
Face, in each case, the substrate surface of substrate are big relative to the thickness of substrate.
The substrate or filter glass of optical filter can be coated in one or both sides.In the case where side coats,
Only one substrate surface has optical layer.In the case where two sides coat, two opposite each of substrate surfaces all have
There is optical layer.Two or more optical layers can certainly be provided for each substrate surface.
In the first Favourable implementations, optical layer is interfering layer, preferably multi-coated interference system.It is advantageous at another
Embodiment in, optical layer is the coating comprising absorbent components.Optical layer has the one or more restriction areas for increasing spectrum
The function of the blocking in the one or more regions of spectral-transmission favtor (anti-reflection effect) and/or increase in section.It can also be used
In increasing the steepness for stopping the transition between range and passband and/or generate narrow band filter in the pass-band.Meanwhile at least
One optical layer may be used as protective layer, to increase the stability of filter glass effect on environment.In the blocking model of filter glass
The optical layer that undesirable residual transmission in enclosing (especially in the second blocking range) can also be properly configured stops；?
In this case, which also can have assimilation effect.
At least one optical layer can be preferably designed to multi-coated interference system, to facilitate the optical filtering of filter glass
Effect simultaneously realizes above-mentioned function.However, interference filter has the relevant edge of angle: in other words, optical filter has
" color " depending on incidence angle deviates.
Advantageously, the thickness of optical filter can < 1mm, preferably≤0.75mm, more preferably≤0.5mm, further preferably≤
0.3mm, particularly preferably≤0.25, further preferably≤0.2mm.
The optical property of optical filter is determined by the performance and substrate of optical layer or the performance of filter glass.
As described above, red area and/or NIR area of the filter glass according to the present invention in optical filter in spectrum
There is passband in domain, there is the first precipitous transmission edge.In a section in passband, with a thickness of the optical filtering glass of 0.3mm
The internal transmission rate of glass preferably reaches at least 85%, preferably 90%.The section, i.e., with the area of extra high internal transmission rate
Domain, advantageously in the wave-length coverage of 750nm to 950nm.
Filter glass according to the present invention has the first precipitous transmission edge due to its composition and heat treatment, this is advantageous
In manufacturing optical filter according to the present invention, because of the first precipitous transmission towards spectrum short wavelength regions of optical filter
Edge can be provided by filter glass itself, and not needed by complicated optical layer (for example, complicated angle is relevant
Multilayer system) it generates.Certainly, the first transmission edge of optical filter still can be by applying multilayer system and/or coating
To modify.The precipitous transmission edge of the first of filter glass has the advantage that the shortwave edge of optical filter no longer by being applied
The layer system added significantly affects.
It is also known that had the drawback that by many optical band pass filters that multi-coated interference system is formed, in addition to
Except desired and specially designed passband, they can also have and have raised transmissivity in the visibility region of spectrum
Other regions (referred to as secondary maximum value).It, should because optical filter according to the present invention includes filter glass according to the present invention
Filter glass has in the visibility region of spectrum stops range, so these secondary maximum values can not adversely influence optically filtering
The transmission performance of device.Thus, for example, can simplify the design of multi-coated interference system.
By means of being applied to one or more optical layers of substrate according to the present invention, therefore for the spy of optical filter
Fixed application, thus it is possible to vary the passband limited by filter glass, for example, specifically narrowing.At least one optical layer for changing
The spectrum of filter glass.Therefore, the filter effect of glass is assisted by least one optical layer, which especially interferes series of strata
The form of system.
In the Favourable implementations of the substrate according to the present invention for optical filter, filter glass is near infrared region
Have second to stop range (seeing above) in domain (NIR region).Therefore, this filter glass selectively only transmits red color area
The spectrum of narrow wave-length coverage in domain near infrared region.Second transmission edge in filter glass towards the region IR can also pass through
One or more optical layers are adjusted, to adjust the spectral-transmission favtor of optical filter.
By combining filter glass substrate according to the present invention at least one suitable optical layer, therefore root can be made
Most preferably cooperate according to optical filter of the invention by each corresponding requirements generated using field.By using with the filter
The substrate of the invention of optical property and an optical layer or multiple optical layers, can produce in various ways for various applications
Multiple optical filters being individually adapted to.
Optical filter can be preferred that the filter with band logical performance, have in the visibility region of spectrum
First stops range and the second blocking range in the NIR region of spectrum.There is very effective blocking in optical filter
Blocking range between, there are passband, the width of passband and exact position depend on later individual uses.Optical filter
Passband is in the wave-length coverage between 700nm and 1100nm.
In a preferred embodiment, filter glass substrate according to the present invention is provided as thin fuel plate, and
And interference filter system is present on one or two (advantageously, polishing) side, so that the following band general character of filter glass
At least one of energy is improved: being stopped the blocking in range needed for increasing and/or is increased the mistake from blocking range to passband
The steepness crossed and/or transmission in passband needed for increasing and/or narrow band filter is generated in the pass-band.By means of according to this
The filter glass of invention and the inventive combination of at least one optical layer, it is particularly possible to generate narrow band filter, the narrowband
Bandpass filter is impossible under the form of pure filter glass, and can only the barrier properties of reduction (if there is
Words) in the case where as pure interference filter implement.
As described above, optical filter leads to by means of the layer system (such as interference layer system) of the application specially designed
Band can individually match various applications.For example, this optical filter is used in mobile device (such as smart phone), it is excellent
Selection of land has alap total height.Optical filter be frequently used for by " transmitter " (such as narrow-band LED or laser) and
In the integrated system that sensor is constituted, and aim to ensure that the light for being substantially only from transmitter hits sensor and ambient light
(such as sunlight) is blocked.Optical filter with preferably at least 90% high internal transmission range passband should with made
Transmitter accurately matches as far as possible.The commercial LED being commonly used can have its spectral maximum, for example, 750nm,
780nm, 830nm, 850nm, 905nm, 940nm etc..
Optical layer according to the present invention can advantageously interference filter layer system.This interference filter layer system can be with
Known mode is individually designed, therefore can satisfy various requirement.Interference filter layer system is characterized in that can be in transmitted light
Especially precipitous side is established in spectrum.It is often necessary to which multiple interference filter layers generate the required transmission performance of filter；Cause
This, with reference to multi-coated interference system.
Interfering layer or multi-coated interference system can be applied, such as pass through physical vapour deposition (PVD), PVD (German
" physikalische Gasphasenabscheidung "), such as pass through thermal evaporation, sputtering, electron beam evaporation.It is used to form
The suitable dielectric material of interfering layer can be such as fluoride (for example, MgF2、CeF3), oxide is (for example, TiO2、SiO2、
Ta2O5), nitride, carbide, semiconductor material, special metal (element form or alloy).Thin oxide layer is frequently used for doing
It relates in the multilayer system of filter, such as multiple TiO2-SiO2Layer, wherein TiO2Ta can also be used2O5Instead of.This field skill
Art personnel are also realized that many other materials and method for generating suitable multi-coated interference system on substrate.
As the substituted or supplemented of interference filter layer, optical filter can have the light including at least one absorbent components
Learn layer.Therefore, optical filter includes absorbed layer.There is the absorption of suitable absorption properties according to the wave-length coverage to be changed selection
Component.
Absorbed layer may include the dyestuff (such as pigment or organic dyestuff) that may be present in matrix.However, absorbed layer can also
It can be without individual matrix.Substrate according to the present invention can be applied to by absorbing optical layer, for example, passing through spin coating, spraying, leaching
Painting, casting, japanning, silk-screen printing, bat printing, ink jet printing, hectographic printing, roller coating or its other party well known by persons skilled in the art
Method.
Invention additionally provides optical filter according to the present invention range measurement, iris recognition, gesture identification,
Purposes in LIDAR (light/laser detection and ranging) application field.Specifically, in these areas, using in NIR spectra
High internal transmission rate is needed in region and the system of blocking as high as possible is needed in other wave-length coverages.
The following table 1 lists the concrete composition of the Working Examples (WE) of filter glass (in terms of weight %).
Table 1
| WE1 | WE2 | WE3 | WE4 | WE5 | WE6 | WE7 | |
| Weight % | Weight % | Weight % | Weight % | Weight % | Weight % | Weight % | |
| SiO2 | 42.72 | 42.54 | 40.54 | 42.64 | 42.91 | 40.37 | 45.54 |
| B2O3 | 2.50 | 2.70 | 2.60 | 2.80 | 1.00 | 3.20 | 0.50 |
| Al2O3 | 0.06 | 0.05 | 0.07 | 0.05 | 0.05 | 0.04 | 0.06 |
| Na2O | 0.60 | 0.40 | 0.60 | 0.50 | 0.50 | 0.70 | 0.40 |
| K2O | 21.60 | 21.90 | 22.00 | 21.80 | 24.30 | 19.30 | 21.80 |
| Rb2O | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.03 | 0.04 |
| ZnO | 28.80 | 29.10 | 28.90 | 27.10 | 28.30 | 31.00 | 25.60 |
| As2O3 | 0.46 | 0.48 | 0.47 | 0.49 | 0.42 | 0.41 | 0.44 |
| Sb2O3 | 0.09 | 0.07 | 0.06 | 0.08 | 0.07 | 0.09 | 0.08 |
| CoO | 1.70 | 1.30 | 3.30 | 3.10 | 1.10 | 2.90 | 4.30 |
| CdO | 0.54 | 0.48 | 0.51 | 0.49 | 0.44 | 0.99 | 0.52 |
| SeO2 | 0.32 | 0.35 | 0.33 | 0.35 | 0.35 | 0.42 | 0.33 |
| TeO2 | 0.24 | 0.25 | 0.26 | 0.23 | 0.23 | 0.27 | 0.19 |
| SO3 | 0.16 | 0.16 | 0.16 | 0.16 | 0.16 | 0.14 | 0.08 |
| Cl | 0.17 | 0.18 | 0.16 | 0.17 | 0.13 | 0.14 | 0.12 |
| It amounts to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| Tg[℃] | 552 | 550 | 545 | 553 | 540 | 560 | 567 |
Table 1 (continuation)
In order to produce the filter glass with the composition corresponding to Working Examples 1, it is vigorously mixed corresponding preparing glass charge.Match
Material is under the reducing conditions with about 1300 DEG C -1360 DEG C of temperature from melting sources and clarification.During cooling, institute is made in glass
The shape needed.In order to form color, thus obtained blank is heated into (tempering) again.In Working Examples 1, two stages are used
Annealing process.For nucleation, glass is maintained to 620 DEG C of the first temperature (T in nucleation stagegAdd 68 DEG C) 1 hour.Hereafter,
Glass is directly heated to 640 DEG C of (TgAdd 88 DEG C) second temperature so that required microcrystalline growth (microcrystalline growth stage) and
It is kept for 24 hours at this temperature.In the process, the color component dissolved in glass forms nanometer by Cd and Zn and S, Se, Te
Crystallite (solid solution).
In other Working Examples, corresponding annealing temperature is in (Tg- 70 DEG C) to (Tg+ 150 DEG C) in the range of, the retention time
It is 2-48 hours.In general, before the microcrystalline growth stage being 1 to 2 hour nucleation stage, the first temperature of selection is than the second temperature
Spend low 10 DEG C to 150 DEG C.However, nucleation stage is optional.According to the desired locations of the first transmission edge, nucleation can be saved
Stage.
Detailed description of the invention
With reference to attached drawing, by embodiment, the present invention is furture elucidated.Attached drawing is shown:
Fig. 1 is the internal transmission curve of the filter glass (working Examples 1) of substrate according to the present invention；With
Fig. 2 is optical filter according to the present invention.
Specific embodiment
Fig. 1 show passband according to the present invention and stop range definition and filter glass according to the present invention
λi0.5Value.λi0.5Value describes spectrum internal transmittance value τiWavelength when=0.5 (corresponding to 50%).It is according to the present invention
Filter glass is by the internal transmission rate in passband (passing through region) and the internal transmission rate in range is stopped to limit.According to this hair
Bright, passband is understood to mean λ 'i0.5With λ "i0.5Between region.Passband should have internal transmission rate as high as possible.More
Body, in the context of the present invention, for the filter glass thickness of 0.3mm, i.e., for wave-length coverage/section in passband,
Internal transmission rate in passband should be at least 85%, preferably at least 90%, more preferably at least 91%, particularly preferably at least 95%.
According to the present invention, first blocking range be interpreted as edge wavelength X 'i0.5Region before, and second stops range to be edge wave
Long λ "i0.5Region later.
Stop range that there should be alap internal transmission rate.More specifically, in the context of the present invention, for
The filter glass thickness of 0.3mm, first stops the internal transmission rate in range should at least partly, i.e., for stopping in range
Wave-length coverage, preferably≤15%, preferably≤10%, more preferably≤5%, particularly preferably≤1%.Stop in range second, base
In the filter glass thickness, i.e., for stopping the wave-length coverage in range, internal transmission rate can be at most 45%, preferably extremely
More 40%, more preferably up to 35%, further preferably most 30%.Preferably, second stops the average transmittance in range
It can be at most 50%, preferably up to 40%, more preferably up to 30%.
From figure 1 it appears that filter glass (working Examples 1) according to the present invention has the thickness of 0.3mm, have
Band logical performance.About internal transmission rate, filter glass has the first transmission edge and the second transmission edge, and the first transmission edge exists
At 788nm have edge wavelength X 'i0.5, the second transmission edge at 1136nm have edge wavelength X "i0.5.These positions it
Between there are the passbands of filter glass according to the present invention.There is the section of at least 90% extra high internal transmission rate in passband
It is obtained in the range of 833nm to 959nm.The first of filter glass stops range in the wave-length coverage less than 788nm.?
One stops in range, and there are the sections of internal transmission rate < 1%.In the working Examples, this high impedance is in 695nm
It realizes and extends in the region UV in place.It can also be seen that towards spectrum short wavelength regions the first transmission edge 712nm extremely
In the range of 833nm, i.e., in the interval of about 120nm, 90% internal transmission rate is risen to from 10% internal transmission rate.Therefore,
This is a precipitous transmission edge.
Since wavelength 1136nm, passband is the second blocking range of filter glass later.Towards the Long wavelength region of spectrum
The second transmission edge be reduced to 25% internal transmission from 90% internal transmission rate in the wave-length coverage of 959nm to 1282nm
Rate, therefore steeply extend unlike the first transmission edge.However, second stops the interior of range for many conventional applications
Portion's transmission performance is not too important.
Fig. 2 shows the spectral-transmission favtor of optical filter according to the present invention (solid-line curves).For example, this is
Interference bandpass filter at 905mm.In the passband defined by brink, exist with extra high spectral-transmission favtor (>
85%) section (about 890nm to 924nm).
Optical filter includes the filter glass according to the present invention (working Examples 1) of the 0.3mm thickness as substrate,
Internal transmission rate is indicated by imaginary curve.As optical layer, optical filter has multi-coated interference system, the light of multi-coated interference system
Spectrum transmissivity is indicated by point curve.It is obvious that internal multi-coated interference system has multiple especially in visible wavelength region
Troublesome secondary maximum value (section with EO-1 hyperion transmissivity).Because filter glass according to the present invention is less than 695nm's
There is high impedance under wavelength, so entire optical filter also has high impedance in the wave-length coverage, therefore do not need complexity
Measure (such as passing through extra play) eliminate these secondary maximum values.If have raised spectral-transmission favtor (here, for example,
In about 785nm, about 1073nm) not (complete) by remaining section that filter glass inhibits should be trouble for specific application
, these sections can be stopped by one or more additional optical layers.
Claims (13)
1. a kind of substrate for optical filter, including filter glass, the filter glass contain SiO2、ZnO、K2O and cadmium
Chalkogenide, the filter glass are based on oxide, TeO2Content is that 0.1 weight % to 3 weight %, CoO contents is 1.0 weights
% to 7.0 weight %, preferably > 1.0 weight % to 7.0 weight % are measured, wherein the filter glass has the visible light in spectrum
First in region stops range, the passband in the near infrared region of the spectrum, the first transmission edge and based on 0.3mm's
Filter glass thickness between 700nm and 840nm edge wavelength X 'i0.5。
2. substrate according to claim 1, wherein the filter glass under the filter glass thickness of 0.3mm exists
Have in wave-length coverage between 400nm and 680nm less than 15%, preferably≤10%, more preferably≤5%, particularly preferably≤1%
Internal transmission rate.
3. substrate according to claim 1 or 2, wherein the filter glass includes the consisting of (weight based on oxide
Measure %):
4. substrate according to any one of the preceding claims, wherein first transmission edge is in≤150nm, advantageously
≤ 130nm, preferably≤120nm, more preferably≤110nm, particularly preferably≤100nm, in the interval further preferably≤80nm, from inside
Transmissivity≤15% preferably≤10% rises to internal transmission rate >=90%.
5. substrate according to any one of the preceding claims, wherein the filter glass thickness based on 0.3mm, the optical filtering
Glass in a section of the passband have at least 85%, preferably at least 90%, more preferably at least 91%, particularly preferably at least
95% internal transmission rate τi。
6. substrate according to any one of the preceding claims, wherein the filter glass is in the near infrared region (NIR
Region) in have second to stop range, wherein the filter glass thickness based on 0.3mm, have the edge IR wavelength X "i0.5IR it is saturating
Edge is penetrated between 950nm and 1300nm.
7. substrate according to any one of the preceding claims, wherein the filter glass includes one of following components
Or it is a variety of, based on the weight % of oxide:
8. substrate according to any one of the preceding claims, wherein the Na of the filter glass2O/K2O ratio is (to be based on oxygen
The weight % of compound is counted) < 1, advantageously < 0.5, additionally advantageously < 0.3, preferably < 0.2, preferably < 0.1, particularly preferably < 0.08, also
It is preferred that < 0.05.
9. substrate according to any one of the preceding claims, wherein the filter glass is free of F, and/or without Pb,
The oxide of Hg, TI, Bi, Zr, Nb, Y, Yb, Gd, W, La and/or Ta, and/or other colouring components are free of, such as Ce, Fe,
The oxide of Cu, Cr and/or Ni, and/or be free of optical activity component, such as laser active component, such as Pr, Nd, Sm, Eu,
The oxide of Tb, Dy, Ho, Er and/or Tm, and/or be free of radioactive element, such as the oxide of Th, U.
10. a kind of optical filter, including substrate according to any one of the preceding claims and at least one optical layer,
Wherein at least one described optical layer increases blocking in desired blocking range, and/or increases the blocking range and institute
The steepness of the transition between passband is stated, and/or increases the transmission in the passband, and/or generates narrow band filter.
11. optical filter according to claim 10, wherein at least one described optical layer is interference layer system.
12. optical filter according to claim 10, wherein at least one described optical layer includes at least one absorbs
Component.
13. optical filter according to any one of claims 10 to 12 is in range measurement, iris recognition, gesture identification
With the purposes in LIDAR (light/laser detection and ranging) field.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102017127579.7 | 2017-11-22 | ||
| DE102017127579.7A DE102017127579B3 (en) | 2017-11-22 | 2017-11-22 | Substrate for an optical filter and optical filter |
Publications (2)
| Publication Number | Publication Date |
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| CN109809689A true CN109809689A (en) | 2019-05-28 |
| CN109809689B CN109809689B (en) | 2020-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811397056.XA Active CN109809689B (en) | 2017-11-22 | 2018-11-22 | Substrate for optical filter and optical filter |
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| Country | Link |
|---|---|
| KR (1) | KR102001788B1 (en) |
| CN (1) | CN109809689B (en) |
| DE (1) | DE102017127579B3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110837145A (en) * | 2019-11-21 | 2020-02-25 | 天津津航技术物理研究所 | Method for regulating and controlling spectrum of narrow-band filter |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210023565A (en) * | 2019-08-23 | 2021-03-04 | 현대자동차주식회사 | Optic filter integrated with lidar window |
| DE102022121122A1 (en) | 2022-08-22 | 2024-02-22 | Schott Ag | Laminated glass and its use |
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| KR20190059240A (en) | 2019-05-30 |
| CN109809689B (en) | 2020-12-15 |
| KR102001788B1 (en) | 2019-07-18 |
| DE102017127579B3 (en) | 2019-02-07 |
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