CN107315212B - Dual-channel filter and method for preparing dual-channel filter by spin-coating blue dye - Google Patents
Dual-channel filter and method for preparing dual-channel filter by spin-coating blue dye Download PDFInfo
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- CN107315212B CN107315212B CN201710445446.9A CN201710445446A CN107315212B CN 107315212 B CN107315212 B CN 107315212B CN 201710445446 A CN201710445446 A CN 201710445446A CN 107315212 B CN107315212 B CN 107315212B
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Classifications
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- G—PHYSICS
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- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
Abstract
The invention discloses a double-channel filter and a method for preparing the double-channel filter by adopting spin-coated blue dye, wherein the double-channel filter comprises the following components: a glass substrate; a blue dye layer disposed on one side surface of the glass substrate; an adhesive layer disposed on the blue dye layer; an ultra-wideband antireflection film disposed on the adhesive layer; and a dual-channel filter disposed on the other side surface of the glass substrate. A method of making a dual channel filter comprising: a blue dye layer is coated on a glass substrate by adopting a spin coating method; adopting a vacuum plating method and combining low-energy ions to assist in depositing an adhesive layer; the ultra-wideband antireflection film and the double-channel optical filter are deposited by adopting a vacuum coating method and combining high-energy ions. The glass substrate with the spin-on dye layer and the double-channel filter thereof have wide application prospects in the fields of mobile phone shooting systems, security television systems and the like.
Description
Technical Field
The invention relates to a double-channel filter for a shooting system, in particular to a double-channel filter and a method for preparing the double-channel filter by adopting spin-coating blue dye.
Background
The prior art single channel filters generally require the following optical characteristics: visible light of 420-650 nm is transmitted, and ultraviolet light of 350-400 nm and infrared light of 700-1100 nm are cut off. The only way to achieve this has been to date by means of optical films, which however tend to have an angular effect in terms of interference principle, which causes the same object to undergo a distinct colour and brightness gradation due to the different angles of the incident light entering the camera system, for which purpose a piece of absorbing blue glass or blue plastic must be used to stabilize the transmission-cut-off transition wavelength at 650nm, in order to eliminate the wavelength drift caused by the angular effect, and thus the image colour differences and brightness non-uniformities.
In security television monitoring and other systems, a visible-infrared shooting system which continuously works around the clock is required, and the monitoring shooting system is widely applied to departments such as banks, vaults, museums, archives, literature libraries, prisons and the like, and is widely applied to general occasions such as road traffic, residential areas and the like, so that the monitoring shooting system is favored by the whole society. Because of the existence of the visible and infrared shooting channels, the visible-infrared shooting system is commonly called a two-channel filter for distinguishing a single-channel filter. The dual-channel filter only builds a narrow transmission band in the infrared cut-off region of the single-channel filter, for example, the transmission band of 940nm is about 40nm, but the infrared light region responded by the whole sensor from 700nm to 1200nm is still fully cut off except for the transmission band of 940nm, which is essentially as follows: and (3) closing an infrared light gate and opening a 940nm small window. Therefore, under the sunlight condition, as the dual-channel filter isolates all infrared light except 940nm narrow-pass, clear visible light color images can be shot without being interfered by broadband infrared rays; and under the night condition, the dual-channel filter can transmit 940nm infrared light, and clear infrared black-and-white images are obtained by means of 940nm LED illumination light supplementing.
Since blue glass has a certain degree of cut-off in the infrared region, it cannot be used for a dual-channel filter, but only the optical characteristics of the remaining blue plastic can be used as a substrate of the dual-channel filter, but the blue plastic substrate has obvious disadvantages: (1) The thickness of a typical blue plastic substrate is only 0.1mm, and although the aberration of a flat plate can be ignored, the deformation of the substrate caused by the stress of the dual-channel filter is brought; (2) The blue plastic substrate has poor rigidity, and the application is limited when the area of the image sensor is large; (3) Blue plastic is an organic material, and the optical film is an inorganic material, and both are difficult to attach, or the optical filter film is difficult to plate on the blue plastic substrate. For this reason, engineering technicians have been expecting to find a new material or technology that is excellent in performance and inexpensive to replace the blue plastic substrate of the existing dual-channel filter.
The invention proposes to replace blue plastic of the existing double-channel filter by using glass coated with diamine organic dye as a substrate, and the blue plastic is favored in the market because the diamine organic dye is low in price and the cost is low by adding spin coating method, and the main problems of the blue plastic can be overcome.
Disclosure of Invention
The invention aims to provide a dual-channel filter and a method for preparing the dual-channel filter by adopting spin-coated blue dye, which are used for a security television monitoring system. The glass substrate of the spin-coated blue pigment (namely diamine aqua blue dye or diamine Ha Wasu bluish jade dye) can reduce the wavelength drift of the transmission-cut transition region of the filter to be close to zero, and has stable mechanical and chemical properties, so that the spin-coated blue pigment can replace a blue plastic substrate in the existing double-channel filter.
The efficacy of the blue plastic substrate is to provide a stable transmission-cutoff transition region that does not vary with the angle of incidence of the light, with a 50% transmission at a wavelength of about 650nm. Since the transmission-cut-off transition region is formed by the characteristic absorption of the blue plastic substrate, the wavelength 650nm at which the transmittance is 50% does not drift due to the change of the light incidence angle of the target image, and thus uniform color and uniform brightness can be obtained for images entering the monitoring photographing lens at different incidence angles.
In order to maintain the efficacy of the blue plastic filter in stabilizing the transmission-cut-off transition while avoiding the drawbacks thereof, the inventors propose the following concept: coating a layer of organic dye similar to blue plastic on one side of a glass substrate by using a spin coating method to obtain the function of a stable transition region of the blue plastic filter, controlling the thickness of the glass substrate to ensure that the filter can still ignore the plate aberration of the filter, overcoming the strain of the filter by means of the rigidity of the glass substrate and improving the rigidity of the whole filter; in order to enhance the adhesive force between the organic dye and the inorganic ultra-wideband antireflection film, firstly, coating an adhesive layer on the dye layer by a vacuum coating method, and then coating the ultra-wideband antireflection film on the adhesive layer; and then coating the double-channel filter on the other side of the glass substrate by a vacuum coating method.
Based on the above concept, in the first step, it is first necessary to find an organic dye that creates an absorption transition region around 650nm and is transparent at 940nm in the infrared. Since blue plastic creates an absorption transition region just at 650nm and is transparent in the infrared, we know that the color coordinates have a correspondence to the transition wavelength, it is possible to find new materials with the color coordinates or color of blue plastic as a reference. In this way, the inventors have found organic dyes such as diamine water blue dye, diamine Ha Wasu blue jade dye, PR nardostachy blue dye, british gold 4001 turquoise dye, and the like. Second is that these dyes can be coated as films? The invention adopts the simplest spin coating method to prepare the dye film, and the principle of the spin coating method is that the centrifugal force generated by high-speed rotation causes dye sol to diffuse from the center of a glass substrate to the periphery to form a uniform dye film. The main equipment is a spin coater, and the thickness of the dye film is controlled by controlling spin time, rotating speed, liquid drop amount, concentration, viscosity, temperature and the like of the used solution. But determines the key to film formation: firstly, whether the surfaces of the glass substrate and the sol can be mutually wet or not; and if the expansion coefficients of the glass substrate and the gel dye film are close, the dye film is easy to crack. Experiments show that the film forming of the dye is better by diamine water blue dye and diamine Ha Wasu blue jade dye.
Secondly, in order to increase the adhesive force between the organic dye and the inorganic ultra-wideband antireflection film, a layer of Al is required to be plated on the dye layer 0.6 Si 0.7 O 2.3 An adhesive layer. The adhesion layer adopts vacuum evaporation coating, and low-energy ion is selected for auxiliary deposition of Al in order to increase adhesion as much as possible without damaging the structure of dye molecules 0.6 Si 0.7 O 2.3 An adhesive layer.
And thirdly, plating an ultra-wideband antireflection film on the adhesion layer. Because the working wave bands of the dual-channel filter are a visible light channel and a 940nm channel, the antireflection bandwidth is 400nm to 950nm, and compared with the broadband antireflection film of 410-680 nm in the prior art, the antireflection film can be called an ultra-wideband antireflection film. Clearly, the design and fabrication of such ultra-wideband antireflection films is extremely challenging.
And fourthly, designing and manufacturing a double-channel optical filter on the surface of the other side of the glass substrate. The dual-channel filter can transmit 400-650 nm visible light and 940nm infrared light, and is used for obtaining high-quality pictures with high contrast by inhibiting ghost and flare under the condition of backlight in order to increase the brightness of signal light and reduce background light as much as possible, selecting 940nm LED lamps with the spectral bandwidth as narrow as possible and the light intensity as high as possible, and then designing 940nm transmission bands which are completely matched with the spectral bandwidth of the LED lamps. For the filter of the present invention, the bandwidth of the 940nm transmission band is approximately 40nm, and the entire image sensor spectral response region from 700nm up to 1200nm is cut off except for the 940nm transmission band.
Specifically, in order to achieve the above object, the present invention adopts the following technical scheme:
a dual channel filter comprising:
a glass substrate;
a blue dye layer disposed on one side surface of the glass substrate;
an adhesive layer disposed on the blue dye layer;
an ultra-wideband antireflection film disposed on the adhesive layer;
and a dual-channel filter disposed on the other side surface of the glass substrate.
The following is a preferred technical solution of the present invention:
the glass substrate comprises K series crown glass, B270 glass, borofloat glass or D263T glass, a blue dye layer on any side surface of the glass substrate can adopt diamine aqua blue dye or diamine Ha Wasu blue jade dye, an adhesion layer on the blue dye layer consists of a mixed single-layer film of aluminum oxide and silicon oxide, an ultra-wideband antireflection film on the adhesion layer consists of a high refractive index film and a low refractive index film alternately, and a double-channel filter on the other side surface of the glass substrate consists of a matching film system, a first main film system and a second main film system which are sequentially arranged outwards from the glass substrate.
The thickness of the blue dye layer is 500 nm-2000 nm; further preferably, the thickness of the blue dye layer is 800nm to 1200nm.
The adhesive layer is prepared from aluminum oxide and silicon oxide with a molar mixing ratio of 3: al of 7 0.6 Si 0.7 O 2.3 The mixed monolayer film, i.e. the adhesive layer is Al 0.6 Si 0.7 O 2.3 A monolayer film is mixed.
The ultra-wideband antireflection film consists of high refractive index films and low refractive index films alternately, wherein the high refractive index films are Ti 3 O 5 The film with low refractive index is MgF 2 。
The total layer number of the ultra-wideband antireflection film is 10, and the first layer close to the adhesion layer is Ti 3 O 5 A high refractive index film layer, a second layer is MgF 2 The low refractive index films alternate in sequence with thicknesses of 5.6, 52.6, 19.6, 33.2, 39.5,7.3, 79.1, 21.5, 22.8, 108.3 in nm.
The dual-channel optical filter comprises: the glass substrate is provided with a matching film system, a first main film system and a second main film system which are arranged outwards in sequence;
the matching film system and the first main film system are alternately composed of a high refractive index film and a low refractive index film, and the second main film system is composed of a high refractive index film, a medium refractive index film and a low refractive index film; the high refractive index film is Ti 3 O 5 Film, intermediate refractive index film is HfO 2 Film, low refractive index film is SiO 2 And (3) a film.
The total number of layers of the dual-channel optical filter is 52, wherein the number of layers of the matching film system is 8, and the thicknesses of the film layers outwards from the glass substrate are as follows: 24.9 15.6, 51.1, 173, 42.4, 36.1, 12.6, 96.8 in nm, the odd layers being high refractive index films Ti 3 O 5 The even layer is a low refractive index film SiO 2 ；
The first main film system is 12 layers, and the thicknesses of the film layers outwards from the matching film system are as follows: 86.2 136, 78.8, 135.6, 77.7, 136.4, 78.2, 136.3, 79.5, 139.9, 88.2, 184.5 in nm, the odd layer being a high refractive index film Ti 3 O 5 The even layer is a low refractive index film SiO 2 ；
The number of layers of the second main film system is 32, the followingThe thickness of each film layer outwards of the first main film system is as follows in sequence: 15.1 49.2, 56.4, 72.1, 64.2, 73.6, 51.5, 85.4, 193.3, 15.1, 103.9, 185.1, 39.7, 88.4, 171.4, 89.9, 35.3, 174, 116.8,3.8, 167.4, 66.9, 32.5, 74.3, 173.6, 49.3, 68.5, 50.6, 157.6, 35.6, 82.6, 82.5 in nm, in the second main film system, the 1, 3, 7, 10, 14, 16, 20, 23, 27, 31 layers are high refractive index films Ti 3 O 5 The 5 th, 9 th, 12 th, 15 th, 18 th, 21 st, 25 th, 29 th and 32 th layers are low refractive index films SiO 2 The balance being intermediate refractive index film HfO 2 。
Further, a high refractive index film Ti 3 O 5 Refractive index at wavelength 550nm is 2.426, intermediate refractive index film HfO 2 A refractive index of 1.994 at a wavelength of 550nm, a low refractive index film MgF 2 A refractive index at a wavelength of 550nm of 1.38, a low refractive index film SiO 2 The refractive index at the wavelength of 550nm is 1.460.
A method for preparing a dual-channel filter by spin-on blue dye, comprising the following steps:
1) A blue dye layer is coated on a glass substrate by adopting a spin coating method;
2) Adopting a vacuum plating method and combining low-energy ions to assist in depositing an adhesive layer;
the condition of the low-energy ion auxiliary deposition is that the beam pressure is 350V-500V and the beam current is 300 mA-500 mA;
3) The ultra-wideband antireflection film and the double-channel optical filter are deposited by adopting a vacuum coating method and combining high-energy ions in an auxiliary way;
the conditions of the high-energy ion-assisted deposition are as follows: the beam pressure is 700V-900V, and the beam current is 700 mA-900 mA.
In the step 1), diamine water blue dye or diamine Ha Wasu blue jade dye is adopted in the spin coating method.
In the step 2), the conditions of the low-energy ion-assisted deposition are as follows: the beam voltage is 350V-450V, and the beam current is 350 mA-450 mA. Further preferably, the conditions of the low energy ion-assisted deposition are: the beam voltage is 400V, and the beam current is 400mA.
In the step 3), the conditions of the high-energy ion-assisted deposition are as follows: the beam voltage is 750V-850V, and the beam current is 750 mA-850 mA. Further preferably, the conditions of the high-energy ion-assisted deposition are as follows: the beam voltage is 800V, and the beam current is 800mA.
Compared with the prior art, the invention has the beneficial effects that:
1. the blue plastic substrate used in the prior art can provide a transmission-cut-off transition region around 650nm wavelength, which is not changed with the incident angle of light, for the dual-channel filter, but as described above, the blue plastic substrate is liable to cause coating strain and cannot be used for an image sensor with a large area due to poor rigidity. The glass substrate with the spin-on organic dye film provided by the invention has the function of stabilizing the transmission-cut-off transition region of blue plastic, so that the blue plastic in the prior art can be replaced in the double-channel filter, besides the defect that the adhesiveness of the organic-inorganic material of the blue plastic substrate is poor, the defects of large strain, poor rigidity and the like of the rest of the blue plastic can be overcome by means of the excellent rigidity of glass. Whereas the adhesion defects of the organic-inorganic material can be reduced by means of low-energy ion-assisted deposition of Al with high anchoring energy 0.6 Si 0.7 O 2.3 The adhesion layer is relieved. The glass substrate with the spin-coating organic dye film has lower cost than blue plastic because the dye and the glass are cheap; meanwhile, the defects of strain and rigidity of the blue plastic can be overcome, so that the performance is better than that of the blue plastic. This technique of the present invention provides a subversion of the dual-channel low-pass filter.
2. The bandwidth of the antireflection film in the prior art is most commonly 410-680 nm in the visible region, and if the bandwidth of the antireflection film is represented by B, b=λ max /λ min Wherein lambda is max Is the maximum wavelength of the antireflection wavelength region lambda min Is the minimum wavelength, and thus, the prior art antireflection film bandwidth b=1.66 is obtained. The dual-channel filter of the invention requires the antireflection wavelength to be from 400nm to 950nm, and the bandwidth b=2.38 of the ultra-wideband antireflection film is obtained. The design of such ultra-wideband antireflection films is very difficult, and the present invention has found that, first, increasing the refractive index difference between the two film materials and selecting the lowest possible outermost refractive index isOf critical importance, ti is therefore selected in the present invention for the highest refractive index 3 O 5 MgF having the lowest refractive index is selected as the high refractive index film H 2 As the first low refractive index film L 1 . Secondly, selecting proper initial structure is important to obtain excellent ultra-wideband antireflection performance, and different from the broadband antireflection film in the prior art, the third material for increasing the intermediate refractive index has no effect on the ultra-wideband antireflection film to reach the maximum bandwidth and the minimum reflectivity, the adoption of multiple materials does not have more superiority than two materials, the refractive index of the substrate has no direct relation with the maximum bandwidth and the minimum reflectivity, therefore, the invention constructs 10 layers of films G| (0.3H0.3L) 1 ) 4 0.3HL 1 I a as the initial structure, where G is the base and a is air. This provides a new design concept for creating ultra-wideband anti-reflective films.
3. The prior art dual-channel filter is usually transparent to 420-650 nm visible light and 850nm infrared light, and cuts off the rest of radiation light from 350-1100nm except the dual channels. In order to increase brightness and reduce background light as much as possible, and inhibit ghost and flare under the condition of backlight to obtain high-contrast high-quality picture, the dual-channel filter is designed to transmit 400-650 nm visible light and 940nm infrared light, and cut off the rest radiation light from 350-1200nm except the dual channels. Such an improvement may achieve the following effects: 1) And the LED lamp with the wavelength of 940nm is selected to replace the LED lamp with the wavelength of 850nm so as to eliminate the red storm problem of the 850nm LED lamp, thereby enabling the monitoring system to be more concealed. 2) The transmission band of visible light is extended from 420-650 nm to 400-650 nm, and the cut-off wavelength of infrared region is extended from 1100nm to 1200nm, so as to further improve the image quality. The reason is that: firstly, fully utilizing light with a spectral response wave band of 400-420 nm of an image sensor to participate in visible light imaging; second, the full cut-off image sensor has interference of 1100-1200 nm infrared light with spectral response to visible light color images and infrared 940nm black and white images. This is not done in the prior art, because the higher order interference cut-off band with wavelength 1200nm is exactly between 385-420 nm, so the designer has no way to shift the transmission band of the visible region to 420nm, and the cut-off wavelength of the infrared region is shortened to 1100nm. The dual-channel filter can increase the image shooting brightness, reduce the background light and inhibit the ghost and the vague light under the condition of backlight, thereby creating conditions for obtaining high-quality pictures with high contrast.
Drawings
FIG. 1 is a schematic diagram showing the comparison of optical characteristics of a single-channel filter and a dual-channel filter; wherein, (a) is the optical characteristic of a single-channel filter, and (b) is the optical characteristic of a double-channel filter;
FIG. 2 is a graph of the transmission spectrum of a blue plastic substrate of the prior art;
FIG. 3 is a graph of transmission spectra of a glass substrate having a spin-on dye layer according to the present invention;
FIG. 4 is a schematic diagram of the operation of a spin coater;
FIG. 5 is a schematic diagram of the dual channel filter of the present invention;
FIG. 6 is a graph of the reflection spectrum of an ultra-wide anti-reflective film of the present invention;
FIG. 7 is a graph showing the correspondence between the film thickness and refractive index of each film of the dual-channel filter of the present invention;
FIG. 8 is a spectral transmission characteristic of a dual-channel filter of the present invention;
fig. 9 is a final spectral transmission characteristic of the dual-channel filter of the present invention.
Detailed Description
Fig. 1 is a schematic diagram showing the comparison of optical characteristics of a single-channel filter and a dual-channel filter, wherein (a) is the optical characteristic of the single-channel filter and (b) is the optical characteristic of the dual-channel filter. The general required characteristics of a single channel filter are as follows: visible light of 420-650 nm is transmitted, and near infrared light of 700-1100 nm is cut off. The general required characteristics of a two-channel filter are as follows: visible light of 400-650 nm and infrared light of 940nm (or 850 nm) are transmitted, and other infrared light of 700-1200 nm except for a passband of 940nm (or 850 nm) is cut off. The important difference between the two filters is that: (1) The single channel with transmission of 420-650 nm is changed into a double channel with transmission of 400-650 nm and 940nm (or 850 nm), and the transmission bandwidth of 940nm is about 40nm, so that the aim of day and night dual-purpose is fulfilled, wherein a visible light channel acquires a color image, and an infrared light channel acquires a black-and-white image; (2) The visible light transmission band is expanded from 420-650 nm to 400-650 nm, so that the color cast of a color image can be reduced, the light energy utilization rate can be increased, and the contrast and the definition of the image can be improved; (3) The long wave cut-off region is extended from 1100nm to 1200nm to reduce infrared light interference and improve image contrast and definition.
Fig. 2 is a graph of transmission spectra of a blue plastic substrate (model FLXL100AA, manufactured by JSR japan) of a prior art two-channel filter. The thickness of the blue plastic substrate is only 0.1-0.2 mm, but the blue plastic substrate has a transmission-cut-off transition zone with good steepness near 650nm, and the transition zone cannot drift along with the change of an incident angle, so that the color gradient and the brightness gradient caused by different incident angles can be overcome; in addition, the blue plastic substrate has high transmittance in the infrared region, which creates a basic condition for a dual channel filter. Unfortunately, the blue plastic substrate is too strained and too stiff, limiting its wide application. For this purpose, the invention proposes to apply a layer of organic dye similar to blue plastic on the surface of a glass substrate with good rigidity by spin coating, so as to replace the blue plastic. FIG. 3 is a graph of transmission spectra of a glass substrate having a spin-on dye layer according to the present invention. As can be seen from fig. 3, the transmission spectrum curves of the spin-on dye layer are similar to those of the blue plastic of fig. 2, since they all belong to the organic plastic and the mechanism of characteristic absorption is essentially the same, so the shape of the absorption band is also quite similar. Thus, on the one hand, the blue plastic filter can still be kept with a stable transition zone function by means of an organic dye layer spin-coated on a glass substrate; on the other hand, by virtue of the excellent rigidity of the glass substrate, if the thickness thereof is controlled to be about 0.1mm, since the thickness of the dye layer is about 1000nm, it is almost negligible with respect to the glass substrate, it is possible to ignore the plate aberration as in the case of the blue plastic substrate, but it is possible to overcome the defects of too large strain and too poor rigidity of the blue plastic. Of course, similar to the blue plastic substrate, in order to overcome the problem of poor adhesion of the surface of the organic-inorganic material, to enhance the adhesion between the organic dye and the inorganic ultra-wideband anti-reflective film, it is necessary to first coat an adhesive layer on the dye layer by a vacuum coating method, and then coat the ultra-wideband anti-reflective film on the adhesive layer. The principle of coating a dye layer by spin coating can be described simply as: centrifugal force generated by high-speed rotation makes the dye sol liquid film diffuse from the center of the glass substrate to the periphery to form a uniform dye film. The spin coating method mainly comprises a spin coater, fig. 4 is a working principle diagram of the spin coater, and as can be seen from fig. 4, the dye sol nozzle 1 ejects sol to the center of the glass substrate 2, the glass substrate 2 tightly fixed on the tray 3 by means of the suction force of the vacuum pump 5 rotates at a high speed through the rotating shaft 4, the sol spreads radially on the glass substrate under the action of centrifugal force and shearing force generated along with the centrifugal force, the thickness of the film is precisely controllable between 30nm and 2000nm, the device is simple, the operation is easy, and the cost performance is excellent. Spin coating processes involve a number of physical and chemical processes, and the main performance parameters include the film area and film thickness, and along with the spreading and thickness reduction of the film, the solvent evaporation in the liquid film becomes an important factor for the dye layer to be thinned, so the operation parameters such as the rotating speed of high-speed rotation, the viscosity of the solvent, the evaporation rate and the like are all key to control the thickness of the dye layer. In addition, the multi-step spin coating can improve the flexibility and control precision of the spin coating process control; after spin coating, the dye layer is naturally dried in the atmosphere to ensure no crack.
Fig. 5 is a schematic structural view of a dual-channel filter of the present invention, including a glass substrate 6 and a dye layer 7, an adhesive layer 8, and an ultra-wideband antireflection film 9 provided on one side surface of the glass substrate. Glass substrates include K-series crown glass, B270 glass, borofloat glass, D263T glass, or the like. The dye layer includes diamine water blue dye or diamine Ha Wasu blue jade dye (specifically, AE-7 of japan catalyst company in this embodiment), and is coated by spin coating. In order to enhance the adhesive force between the organic dye layer and the inorganic ultra-wideband antireflection film, a layer of mixed monolayer film of aluminum oxide and silicon oxide, namely Al, is firstly coated on the organic dye layer by a vacuum coating method 0.6 Si 0.7 O 2.3 Adhesion layer 8 due to Al 0.6 Si 0.7 O 2.3 The refractive index of the mixed film is about 1.50, which is very close to that of glass and dye, so that the thickness thereof has an effect on the optical characteristicsAlmost negligible, in order to ensure the adhesion function, the invention takes Al 0.6 Si 0.7 O 2.3 The thickness of the film is 100nm; in addition, say Al 0.6 Si 0.7 O 2.3 The adhesion energy of (C) is relatively large, but because it is plated on the organic dye, ion assistance is needed in evaporation to strengthen Al 0.6 Si 0.7 O 2.3 The anchoring energy of the membrane is also assisted by low-energy ions with 400V beam pressure and 400mA beam current because the dye layer is tender. After the adhesion layer is coated, an ultra-wideband antireflection film 9 is coated on the adhesion layer, wherein the ultra-wideband antireflection film is composed of a high refractive index film Ti 3 O 5 And a first low refractive index film MgF 2 The two materials are alternately composed, and the thickness and refractive index of each layer are specifically set forth below. Then plating a two-channel filter 10 on the other surface of the glass substrate, wherein the two-channel filter is composed of a matching film system 11, a first main film system 12 and a second main film system 13 which are sequentially arranged outwards of the glass substrate, and the matching film system and the first main film system are composed of a high refractive index film Ti 3 O 5 And a second low refractive index film SiO 2 Alternately composed of a second main film made of high refractive index film Ti 3 O 5 Intermediate refractive index film HfO 2 And a second low refractive index film SiO 2 The thickness and refractive index of each layer of the two-channel filter are also described below. The vacuum coating method is adopted and is combined with the high-energy ion auxiliary deposition of an ultra-wideband antireflection film and a double-channel optical filter, and the high-energy ion auxiliary deposition conditions are as follows: beam voltage 800V, beam current 800mA
The antireflection film is one of the most widely used films in the technical field of engineering, the bandwidth of the antireflection film in the prior art is most commonly 410-680 nm in the visible light region, and a typical standard film is a multilayer film with a quarter-wavelength film thickness and a half-wavelength film thickness, which are composed of 3-4 film materials, and the antireflection bandwidth and the minimum reflectivity of the antireflection film are obviously dependent on the refractive index of a glass substrate. If the bandwidth of the antireflection film is denoted by B, b=λ max /λ min Wherein lambda is max Is the maximum wavelength of the antireflection wavelength region lambda min At the minimum wavelength, the prior art antireflection film bandwidth b=1.66 is then obtained, which is essentiallyThe widest bandwidth that can be achieved by existing antireflection films. The dual-channel filter of the invention requires an antireflection wavelength from 400nm to 950nm, and the bandwidth of the ultra-wideband antireflection film requires b=2.38. The design of such ultra-wideband antireflection films is very difficult, and the present invention finds that: 1) Increasing the refractive index difference of the two film materials and choosing the lowest possible refractive index of the outermost layer are the most important design parameters, so that in the present invention the highest refractive index Ti is chosen 3 O 5 MgF having the lowest refractive index is selected as the high refractive index film H 2 As the first low refractive index film L 1 . 2) The selection of a proper initial structure is very important to obtain excellent ultra-wideband antireflection performance, and the material with the intermediate refractive index is different from the broadband antireflection film in the prior art, and even the material with the intermediate refractive index is not effective to achieve the maximum bandwidth and the minimum reflectivity of the ultra-wideband antireflection film, so that the material with multiple materials is not more advantageous than the two materials. 3) The refractive index of the substrate is also not directly related to the achieved antireflection bandwidth and minimum reflectance. It can be seen that the existing design theory of the broadband antireflection film is not suitable for the design of the ultra-broadband antireflection film, so the invention provides 10 layers of films G| (0.3H0.3L) 1 ) 4 0.3HL 1 A is as an initial structure, where G is a glass substrate, A is air, H and L 1 Respectively Ti 3 O 5 And MgF 2 The refractive indices were 2.426 and 1.38, respectively. Optimizing by a commercial program TFcal, and finally obtaining: the first layer near the adhesive layer is Ti 3 O 5 High refractive index film with MgF as the second layer 2 The first low refractive index films, alternating in sequence, were 5.6, 52.6, 19.6, 33.2, 39.5,7.3, 79.1, 21.5, 22.8, 108.3 in nm in thickness. Fig. 6 is a graph of reflection spectrum of the ultra-wide antireflection film of the present invention, and as can be seen from fig. 6, the average reflectance is 0.27% in the wavelength range of 400 to 650nm for the first channel, while the average reflectance is 0.21% in the wavelength range of 830 to 960nm for the second channel of 850nm or 940nm, while the reflectance is about 4.2% without the antireflection film, and the antireflection effect is remarkable. This provides a new design concept for creating ultra-wideband antireflection films.
To this end, the dye layer provided on one side surface of the glass substrate, the adhesive layer on the dye layer, and the ultra-wideband antireflection film on the adhesive layer have all been completed.
Finally, the double-channel filter arranged on the other side surface of the glass substrate is designed and manufactured. As described above, the dual-channel filter design of the present invention is divided into three steps: the first step designs a short-wave pass film which transmits 400-650 nm and cuts off 700-900 nm, the second step designs a short-wave pass film which transmits 400-650 nm and 940nm and cuts off 1000-1200 nm, and then the third step combines the two designs of the first step and the second step to obtain a rudiment-shaped double-channel optical filter which transmits 400-650 nm and 940nm, and finally uses TFcal commercial thin film design software for thickness optimization until the double-channel optical filter meeting the requirements is obtained.
FIG. 7 is a graph of the correspondence between film thickness and refractive index for each film of an optimized dual-channel filter of the present invention. As can be seen from FIG. 7, the dual-channel filter is composed of three parts of a matching film system, a first main film system and a second main film system, wherein the matching film system and the first main film system are composed of a high refractive index film Ti 3 O 5 And a second low refractive index film SiO 2 Alternately composed of a second main film made of high refractive index film Ti 3 O 5 Intermediate refractive index film HfO 2 And a second low refractive index film SiO 2 Three materials. High refractive index film Ti 3 O 5 Refractive index at wavelength 550nm is 2.426, intermediate refractive index film HfO 2 Is 1.994, a second low refractive index film SiO 2 Is 1.460. The matching film system has 8 layers in total for matching the optical admittance between the glass substrate and the two main film systems. The first main film system has 12 layers, mainly comprises a visible light transmission band of 400-650 nm and a cut-off band of 700-900 nm, and provides a short wave side transition region of 940nm transmission band. The second main film system has 32 layers, and mainly provides a long wave side transition region of 940nm transmission band, thereby forming 940nm transmission band and forming 1000-1200 nm cut-off band. The design parameters of each layer of film of the dual-channel filter are shown in table 1.
TABLE 1
Table 1, below
| 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 |
| SiO 2 | Ti 3 O 5 | SiO 2 | Ti 3 O 5 | SiO 2 | Ti 3 O 5 | SiO 2 | Ti 3 O 5 | SiO 2 | Ti 3 O 5 | HfO 2 | Ti 3 O 5 | HfO 2 |
| 1.46 | 2.426 | 1.46 | 2.426 | 1.46 | 2.426 | 1.46 | 2.426 | 1.46 | 2.426 | 1.994 | 2.426 | 1.994 |
| 135.6 | 77.7 | 136.4 | 78.2 | 136.3 | 79.5 | 139.9 | 88.2 | 184.5 | 15.1 | 49.2 | 56.4 | 72.1 |
Table 1, below
| 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 |
| SiO 2 | HfO 2 | Ti 3 O 5 | HfO 2 | SiO 2 | Ti 3 O 5 | HfO 2 | SiO 2 | HfO 2 | Ti 3 O 5 | SiO 2 | Ti 3 O 5 | HfO 2 |
| 1.46 | 1.994 | 2.426 | 1.994 | 1.46 | 2.426 | 1.994 | 1.46 | 1.994 | 2.426 | 1.46 | 2.426 | 1.994 |
| 64.2 | 73.6 | 51.5 | 85.4 | 193.3 | 15.1 | 103.9 | 185.1 | 39.7 | 88.4 | 171.4 | 89.9 | 35.3 |
Table 1, below
| 38 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 | 49 | 50 |
| SiO 2 | HfO 2 | Ti 3 O 5 | SiO 2 | HfO 2 | Ti 3 O 5 | HfO 2 | SiO 2 | HfO 2 | Ti 3 O 5 | HfO 2 | SiO 2 | HfO 2 |
| 1.46 | 1.994 | 2.426 | 1.46 | 1.994 | 2.426 | 1.994 | 1.46 | 1.994 | 2.426 | 1.994 | 1.46 | 1.994 |
| 174 | 116.8 | 3.8 | 167.4 | 66.9 | 32.5 | 74.3 | 173.6 | 49.3 | 68.5 | 50.6 | 157.6 | 35.6 |
Table 1, below
| 51 | 52 | |
| Ti 3 O 5 | SiO 2 | Air-conditioner |
| 2.426 | 1.46 | 1.0 |
| 82.6 | 82.5 |
FIG. 8 is a spectral transmission characteristic of a dual-channel filter of the present invention. The curves were calculated according to the structure illustrated in table 1, as a preferred embodiment of the invention, the performances achieved were: the average transmittance of 300 to 380nm in the ultraviolet region is 1.5%, the average transmittance of 400 to 650nm in the visible region is 98.7%, the average transmittance of 700 to 900nm in the near infrared region is 0.76%, the average transmittance of 920 to 955nm is 98.5%, and the average transmittance of 1000 to 1200nm is 0.54%.
Fig. 9 is a graph showing the final spectral transmission characteristics of the entire dual-channel filter of the present invention, which is synthesized from the glass substrate of the spin-on dye layer of fig. 3, the ultra-wide anti-reflection film of fig. 6, and the dual-channel filter of fig. 8, and since the present invention has not only excellent ultra-wide band anti-reflection characteristics but also a function of inducing the transmission of the dye layer, the transmittance of the visible and infrared channels of the final filter, particularly the visible channel, is significantly higher than that of the spin-on dye layer of fig. 3. The results show that: in the first channel wavelength region 400-650 nm, tave=88.4%, and the central wavelength region 430-600 nm, tave=95.2%; in the second channel wavelength region 920-960 nm, tave=96.6%; in the ultraviolet cut-off region 350-390 nm, tave=1.61%; in the infrared first cut-off region 670-890nm, tave=0.37%; in the infrared second cut-off region 980-1200 nm, tave=0.65%. The above optical characteristics have been superior to the blue plastic substrate filter of the prior art, especially around wavelength 450nm, with transmittance rising from 88% of the blue plastic substrate filter to 94.3% of the present invention. Practical use shows that the characteristic completely meets the shooting requirement of day and night, the color gradient and the brightness gradient are basically eliminated, and because the shooting brightness is further improved and the stray light is further suppressed, a clearer visible light color image and an infrared black-and-white image can be obtained.
The glass substrate with the spin-on dye layer and the double-channel filter thereof have wide application prospects in the fields of security television systems, mobile phone shooting systems and the like.
Claims (9)
1. A dual channel filter, comprising:
a glass substrate;
the blue dye layer is arranged on one side surface of the glass substrate, and diamine water blue dye or diamine Ha Wasu blue jade dye is adopted for the blue dye layer;
the adhesion layer is arranged on the blue dye layer and is Al 0.6 Si 0.7 O 2.3 Mixing the single-layer film;
an ultra-wideband antireflection film disposed on the adhesive layer;
and a dual-channel filter disposed on the other side surface of the glass substrate.
2. The dual-channel filter of claim 1, wherein said ultra-wideband antireflection film is composed of alternating high refractive index films and low refractive index films, said high refractive index films being Ti 3 O 5 The film with low refractive index is MgF 2 。
3. The dual-channel filter of claim 2, wherein the total number of ultra-wideband antireflection film layers is 10, and the first layer adjacent to the adhesion layer is Ti 3 O 5 A high refractive index film layer, a second layer is MgF 2 The low refractive index films alternate in sequence with thicknesses of 5.6, 52.6, 19.6, 33.2, 39.5,7.3, 79.1, 21.5, 22.8, 108.3 in nm.
4. The dual-channel filter of claim 1, wherein the dual-channel filter comprises: the glass substrate is provided with a matching film system, a first main film system and a second main film system which are arranged outwards in sequence;
the matching film system and the first main film system are alternately composed of a high refractive index film and a low refractive index film, and the second main film system is composed of a high refractive index film, a medium refractive index film and a low refractive index film; the high refractive index film is Ti 3 O 5 Film, intermediate refractive index film is HfO 2 Film, low refractive index film is SiO 2 And (3) a film.
5. The dual-channel filter of claim 4, wherein the total number of layers of the dual-channel filter is 52.
6. The dual-channel filter of claim 5, wherein the number of the matching film layers is 8, and the thicknesses of the film layers from the glass substrate to the outside are as follows: 24.9 15.6, 51.1, 173, 42.4, 36.1, 12.6, 96.8 in nm, the odd layers being high refractive index films Ti 3 O 5 The even layer is a low refractive index film SiO 2 ；
The first main film system is 12 layers, and the thicknesses of the film layers outwards from the matching film system are as follows: 86.2 136, 78.8, 135.6, 77.7, 136.4, 78.2, 136.3, 79.5, 139.9, 88.2, 184.5 in nm, the odd layer being a high refractive index film Ti 3 O 5 The even layer is a low refractive index film SiO 2 ；
The number of layers of the second main film system is 32, and the thicknesses of the film layers from the first main film system to the outside are as follows: 15.1 49.2, 56.4, 72.1, 64.2, 73.6, 51.5, 85.4, 193.3, 15.1, 103.9, 185.1, 39.7, 88.4, 171.4, 89.9, 35.3, 174, 116.8,3.8, 167.4, 66.9, 32.5, 74.3, 173.6, 49.3, 68.5, 50.6, 157.6, 35.6, 82.6, 82.5 in nm, in the second main film system, the 1, 3, 7, 10, 14, 16, 20, 23, 27, 31 layers are high refractive index films Ti 3 O 5 The 5 th, 9 th, 12 th, 15 th, 18 th, 21 st, 25 th, 29 th and 32 th layers are low refractive index films SiO 2 The balance being intermediate refractive index film HfO 2 。
7. A method for preparing the dual-channel filter according to any one of claims 1 to 6 by spin-coating blue dye, comprising the following steps:
1) A blue dye layer is coated on a glass substrate by adopting a spin coating method;
2) Adopting a vacuum plating method and combining low-energy ions to assist in depositing an adhesive layer;
the low-energy ion auxiliary deposition condition is 350-500V beam voltage and 300-500 mA beam current;
3) The ultra-wideband antireflection film and the double-channel optical filter are deposited by adopting a vacuum coating method and combining high-energy ions in an auxiliary way;
the conditions of the high-energy ion-assisted deposition are as follows: the beam pressure is 700V-900V, and the beam current is 700 mA-900 mA.
8. The method according to claim 7, wherein in step 1), the spin coating method employs a diamine water blue dye or a diamine Ha Wasu blue jade dye.
9. The method of claim 7, wherein in step 2), the conditions for the low energy ion assisted deposition are: the beam voltage is 350V-450V, and the beam current is 350 mA-450 mA;
in the step 3), the conditions of the high-energy ion-assisted deposition are as follows: the beam pressure is 750V-850V, and the beam current is 750 MA-850 MA.
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| CN110412674B (en) * | 2019-08-19 | 2024-02-27 | 苏州微纳激光光子技术有限公司 | Full-day blind ultraviolet filter |
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| CN102759768A (en) * | 2012-07-31 | 2012-10-31 | 杭州科汀光学技术有限公司 | Optical filter |
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