CN119200067A - A near infrared absorption filter - Google Patents
A near infrared absorption filter Download PDFInfo
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- CN119200067A CN119200067A CN202411697949.1A CN202411697949A CN119200067A CN 119200067 A CN119200067 A CN 119200067A CN 202411697949 A CN202411697949 A CN 202411697949A CN 119200067 A CN119200067 A CN 119200067A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
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Abstract
本发明涉及一种近红外吸收滤光片，其包括15~35%重量的铁、5~20%重量的铝、1~10%重量的硅、40~75%的磷、0.2~10%重量的钙、0.2~10%重量的镁、1~10%重量的锌以及0.1~1%的硫，所述近红外吸收滤光片对波长介于930~950nm的光的平均穿透率小于15%，所述近红外吸收滤光片的厚度小于0.7mm。
The present invention relates to a near-infrared absorption filter, which comprises 15-35% by weight of iron, 5-20% by weight of aluminum, 1-10% by weight of silicon, 40-75% by weight of phosphorus, 0.2-10% by weight of calcium, 0.2-10% by weight of magnesium, 1-10% by weight of zinc and 0.1-1% by weight of sulfur. The near-infrared absorption filter has an average transmittance of less than 15% for light with a wavelength between 930 and 950 nm, and a thickness of less than 0.7 mm.
Description
Technical Field
The present invention relates to an optical element, and more particularly, to a near infrared absorption filter.
Background
With the advancement of technology, many products provided with a biometric module capable of recognizing a face, a fingerprint, an iris, a vein, or the like have appeared in the market, which uses infrared rays having a wavelength of 940nm as a light source, but the infrared rays affect the imaging quality of the sensing module, especially, devices provided with the biometric module and the camera module at the same time, and the closer the distance from each other, the more serious the interference, so there is a demand for an optical filter having an excellent absorption effect for the infrared rays having a wavelength of 940nm in the market.
Disclosure of Invention
The invention aims to solve the technical problem of providing a near infrared absorption filter which overcomes the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
A near infrared absorption filter comprises 15-35% by weight of iron, 5-20% by weight of aluminum, 1-10% by weight of silicon, 40-75% by weight of phosphorus, 0.2-10% by weight of calcium, 0.2-10% by weight of magnesium, 1-10% by weight of zinc and 0.1-1% by weight of sulfur, wherein the average transmittance of the near infrared absorption filter to light with the wavelength of 930-950 nm is less than 15%, and the thickness of the near infrared absorption filter is less than 0.7mm.
In one embodiment, the average transmittance of light having a wavelength of 420-650 nm is greater than 80%.
In one embodiment, it further comprises 0 to 10% by weight of an alkali metal.
In one embodiment, the alkali metal is one or more of lithium, sodium, and potassium.
In one embodiment, it further comprises 0 to 10% by weight of boron.
In one embodiment, the device further comprises 0.5-5% by weight of a sulfur-free reducing agent, wherein the sulfur-free reducing agent is one or more of glucose, carbon and metal powder.
In one embodiment, the thickness is between 0.25 mm and 0.6 mm.
In one embodiment, the average transmittance of light with the wavelength of 930-950 nm is less than 13%.
In one embodiment, the half-transmission wavelength is between 700 and 800 nm.
In one embodiment, the half-transmission wavelength is 715-785 nm.
In one embodiment, it has one or more of elemental sulfur, sodium sulfide, iron sulfide.
In one embodiment, the transmittance of light having a wavelength of 940nm is less than 12%.
In one embodiment, the transmittance of light with a wavelength of 650nm is greater than 82%.
In one embodiment, the thickness is less than 0.3mm.
In one embodiment, the half-transmission wavelength is 760-785 nm
In summary, the near infrared absorption filter has excellent near infrared ray filtering performance on the premise of smaller thickness by setting the component proportion, and the near infrared absorption filter comprises sulfur, so that the stability of a product can be improved, the yield can be improved, the production cost can be reduced, and the benefit can be improved.
Drawings
For a further understanding of the features and technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are included to illustrate and not to limit the scope of the invention.
FIG. 1 is a spectrum showing the transmittance of the near infrared absorption filters prepared in comparative examples 1 to 5 to light having a wavelength of 350 to 1100 nm;
FIG. 2 is a spectrum showing the transmittance of the near infrared absorption filter prepared in comparative examples 6 to 10 to light having a wavelength of 350 to 1100 nm;
FIG. 3 is a transmittance spectrum of the near infrared absorption filter of examples 1 to 5 for light with a wavelength of 350 to 1100 nm;
FIG. 4 is a transmittance spectrum of the near infrared absorption filter of examples 6 to 10 for light with a wavelength of 350 to 1100 nm;
Fig. 5 is a transmittance spectrum of the near infrared absorption filter of example 11 and comparative example 11 to light having a wavelength of 350 to 1100 nm.
Detailed Description
The following description of the embodiments of the invention is provided with reference to specific embodiments, and it is intended that the spirit, advantages and efficacy of the invention be apparent to those skilled in the art from the description of the invention.
Where the terms "comprises," "comprising," or "having" are used in this specification, unless stated otherwise, they include, but do not exclude other elements, components, structures, regions, portions, devices, systems, steps, or connections.
The near infrared absorbing filter of the present invention comprises 15-35 wt% iron, 5-20 wt% aluminum, 1-10 wt% silicon, 40-75 wt% phosphorus, 0.2-10 wt% calcium, 0.2-10 wt% magnesium, 1-10 wt% zinc and 0.1-1 wt% sulfur, in some embodiments, the iron content may be 15%, 20%, 25%, 30%, or 35 wt%, the aluminum content may be 5%, 10%, 15%, or 20 wt%, the silicon content may be 1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%、 or 10wt%, the phosphorus content may be 40%, 45%, 50%, 55%, 60%, 65%, 70%, or 75 wt%, the calcium content may be 0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%、 or 10wt%, the magnesium content may be 0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%、0.9%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%、 or 10wt%, the zinc content may be 1%、1.1%、1.2%、1.3%、1.4%、1.5%、1.6%、1.7%、1.8%、1.9%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%、 or 10wt%, the sulfur content may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% but not limited thereto.
In some embodiments, the near infrared absorbing filter of the present invention further includes 0 to 10% by weight of boron, and in some embodiments, the content of boron may be 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% by weight, but is not limited thereto. In one embodiment, the near infrared absorbing filter of the present invention includes substantially no boron.
In some embodiments, the near infrared absorbing filter of the present invention further comprises 0-10% by weight of an alkali metal, wherein the alkali metal is one or more of lithium, sodium and potassium. In some embodiments, the alkali metal content may be 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% by weight, but is not limited thereto. In one embodiment, the near infrared absorbing filter of the present invention includes substantially no alkali metal.
In order to make the thickness of the filter thin, the iron content in the filter must be increased, but in this case, the iron content in the filter is high, a reducing agent needs to be added to help the reduction of iron ions, so that ferric iron is avoided being formed, ferric iron absorbs the visible light region near the ultraviolet region, the glass is made to be brown yellow, and ferrous iron absorbs the visible light region near the near infrared region, so that the glass is made to be blue-green, therefore, the formation of ferric iron needs to be avoided as much as possible, the use amount of the reducing agent also increases along with the increase of the iron content in the filter, and the proportion of each component needs to be adjusted by matching with the reducing agent, but the use amount of the reducing agent has the upper limit, and excessive addition or crystallization of the glass is caused. In order to achieve a sufficient reduction effect, the process may be further modified, for example, by additionally supplying a reducing gas reducing agent such as nitrogen, argon, or hydrogen and a mixture thereof, to ensure that the ferrous iron is obtained. Moreover, the glass process requiring a high temperature (e.g., 1300 °) is performed in the case of a high iron content, and further, when the iron content in the filter increases, the glass is easily crystallized, is difficult to form, and does not provide a sufficient reducing force even with a reducing agent, so that a large amount of undesirable trivalent iron is obtained.
The near infrared filter of the present invention can finally obtain divalent iron stably by adding sulfur as a reducing agent and controlling the ratio of each component in the filter, and specifically, for forming the near infrared absorbing filter of the present invention, metaphosphates such as aluminum metaphosphate, lithium metaphosphate, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, zinc metaphosphate and calcium metaphosphate, carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate, metal oxides such as iron oxide, aluminum oxide, zinc oxide, magnesium oxide, boron oxide and silicon oxide, elemental sulfur or sulfides such as sodium sulfide, iron sulfide and the like can be used.
The near infrared absorption filter can be manufactured by using glass raw materials in the prior art, for example, each glass raw material is placed in a crucible, the crucible is placed in a reducing atmosphere furnace, the temperature is controlled to be 1200-1500 ℃, and then the glass in a molten state is stirred, clarified, flows out of a casting mould and is annealed and molded, so that homogenized glass is finally obtained. The reducing gas in the reducing atmosphere furnace can be nitrogen, argon or hydrogen and the mixed gas thereof.
The near infrared absorbing filter of the present invention includes sulfur as a reducing agent, and on the premise of sulfur, an organic substance such as glucose, carbon, metal powder, etc. may be added as a reducing agent. If the content of the sulfur-free reducing agent is 0.5 to 5% by weight, the reducing effect may be insufficient if the content is less than 0.5% by weight, and if it exceeds 5% by weight, crystallization may occur and glass formation is difficult. The metal powder can be tin, zinc or aluminum.
In the present invention, the thickness of the near infrared absorption filter is thinner than 0.7mm, and in some embodiments, the thickness may be 0.25mm, 0.3mm, 0.4: 0.4 mm, 0.5:0.5 mm, or 0.6: 0.6 mm, but not limited thereto, and in general, the thinner the near infrared absorption filter, the worse the near infrared absorption effect, so the near infrared absorption filter in the market usually has a thicker filter thickness in order to achieve a better near infrared absorption effect, while the near infrared absorption filter in the present invention can still achieve excellent optical performance on the premise of thinner thickness.
The near infrared absorption filter of the present invention has excellent optical performance, specifically, the average transmittance of the near infrared absorption filter for light with the wavelength of 930-950 nm is less than 15%, and in some embodiments, the average transmittance of the near infrared absorption filter for light with the wavelength of 930-950 nm is 14.5%、14%、13.5%、13%、12.5%、12%、11.5%、11%、10.5%、10%、9.5%、9%、8.5%、8%、7.5%、7%、6.5%、6%、5.5%、5%、4.5%、4%、3.5%、3%、2.5%、2%、1.5%、1%、0.5%, but not limited thereto.
In some embodiments, the near infrared absorbing filter of the present invention has a transmittance of less than 12% for light having a wavelength of 940nm, such as 11.9%、11.8%、11.7%、11.6%、11.5%、11.4%、11.3%、11.2%、11.1%、11%、10.5%、10%、9.5%、9%、8.5%、8%、7.5%、7%、6.5%、6%、5.5%、5%、4.5%、4%、3.5%、3%、2.5%、2%、1.5%、1%、0.5%, but not limited thereto.
The near infrared absorption filter of the present invention has excellent optical performance, specifically, the half-transmission wavelength (t50%) is at least 700nm and above, for example, the half-transmission wavelength is between 700 and 800nm, or the half-transmission wavelength is between 715 and 785nm, or between 760 and 785nm, and in some embodiments, the half-transmission wavelength may be 715nm, 720nm, 725nm, 730nm, 735nm, 740nm, 745nm, 750nm, 755nm, 760nm, 765nm, 770nm, 775nm, 780nm, 785nm, but is not limited thereto. Therefore, the visible light region is maintained at a high transmittance, and the high transmittance specifically refers to the average transmittance of the near infrared absorption filter of the present invention for light with a wavelength of 420-650 nm being greater than 80%, and in some embodiments, the average transmittance is 81%, 82.5%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, but not limited thereto.
Referring to tables 1 and 2, table 1 is the proportion of the main element oxide or the main element in comparative examples 1 to 10 and examples 1 to 11, expressed as mole% and wt%, table 2 is the proportion of the main element in comparative examples 1 to 10 and examples 1 to 11, expressed as wt%, raw materials of various components are weighed 100 to 300g according to the proportions in table 1 and table 2, and are thoroughly mixed to obtain a raw material composition, the raw material composition is placed in a crucible, the crucible is placed in a reducing atmosphere furnace, the temperature of the reducing atmosphere furnace is controlled to be between 1200 ° and 1500 °, and then glass in a molten state is stirred, clarified, flowed out of a mold and annealed to be molded, finally the near infrared absorption filters of comparative examples 1 to 10 and examples 1 to 11 are obtained, wherein no reducing agent is added in comparative examples 1 to 10, 0.85% by weight of tin is added in comparative examples 6 to 10, and 0.23% by weight of sulfur is added in examples 1 to 11.
As shown in fig. 1, for the transmittance spectra of the near infrared absorption filters of comparative examples 1 to 5 to light having a wavelength of 350 to 1100nm, table 3 shows that the thicknesses and the spectral data of the near infrared absorption filters of comparative examples 1 to 5 are 0.25mm, and as can be seen from fig. 1 and table 3, the average transmittance of the comparative examples 1 to 5 without reducing agent to the visible light region having a wavelength of 420 to 650nm is extremely unstable, only the average transmittance of the comparative example 1 reaches 80% or more, only 26.31% of the comparative example 5 is a defective filter, and the average transmittance of the comparative examples 1 to 5 to the near infrared region having a wavelength of 930 to 950 nm is also extremely unstable, wherein the average transmittance of the comparative examples 4 and 5 is more than 24% as a defective filter.
As shown in fig. 2, the near infrared absorption filters of comparative examples 6 to 10 have transmittance spectra for light having a wavelength of 350 to 1100nm, the near infrared absorption filters of comparative examples 6 to 10 have thicknesses of 0.25mm and spectral data, and as shown in fig. 2 and 4, the comparative examples 6 to 10 having a reducing agent tin have average transmittance in the visible light range of 420 to 650nm which is not stable, and only comparative examples 6, 7 and 9 have a transmittance of 80% or more, and both comparative examples 8 and 10 have a transmittance of less than 70% and are defective filters.
As shown in fig. 3, for the transmittance spectra of the near infrared absorption filters of examples 1 to 5 for light with a wavelength of 350 to 1100nm, table 4 shows the thickness and the spectral data of the near infrared absorption filters of examples 1 to 5, wherein the thickness is 0.25mm, and as can be seen from fig. 3 and table 5, the average transmittance of the examples 1 to 5 with the reducing agent sulfur for the visible light region with a wavelength of 420 to 650nm is more than 87%, and the average transmittance of the examples 1 to 5 for the near infrared region with a wavelength of 930 to 950 nm is also more stable and is less than 12.1%.
As shown in fig. 4, for the transmittance spectra of the near infrared absorption filters of examples 6 to 10 for light having a wavelength of 350 to 1100nm, table 5 shows the thicknesses and the spectral data of the near infrared absorption filters of examples 6 to 10, wherein the thicknesses are 0.25mm, 0.3mm, 0.4mm, 0.5mm, and 0.6mm, respectively, as shown in fig. 5 and table 6, the average transmittance of the near infrared absorption filters for the visible light region having a wavelength of 420 to 650nm is very stable and is 84.4% or more, and the average transmittance of the near infrared absorption filters for examples 6 to 10 for the near infrared region having a wavelength of 930 to 950 nm is also very stable and is less than 11%.
As shown in fig. 5, the transmittance spectra of the near infrared absorption filters of comparative example 11 and example 11 for light having a wavelength of 350 to 1100nm are shown, and table 5 shows the thickness and spectral data of the near infrared absorption filters of comparative example 11 and example 11, wherein the thickness of example 11 is 0.25mm, the thickness of comparative example 11 is a commercially available near infrared absorption filter, the thickness is 0.7mm, and the spectral patterns of the two are relatively close, but the thickness of comparative example 11 is much larger than that of example 11.
The foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention, so that all changes which come within the meaning and range of equivalency of the description and drawings are intended to be embraced therein.
Claims (12)
1. A near infrared absorption filter is characterized by comprising 15-35% by weight of iron, 5-20% by weight of aluminum, 1-10% by weight of silicon, 40-75% by weight of phosphorus, 0.2-10% by weight of calcium, 0.2-10% by weight of magnesium, 1-10% by weight of zinc and 0.1-1% by weight of sulfur, wherein the average transmittance of the near infrared absorption filter to light with the wavelength of 930-950 nm is less than 15%, and the thickness of the near infrared absorption filter is less than 0.7mm.
2. The near infrared absorbing filter of claim 1, wherein the average transmittance of light having a wavelength of 420-650 nm is more than 80%.
3. The near infrared absorbing filter of claim 1, further comprising 0.5-5 wt% of a sulfur-free reducing agent, wherein the sulfur-free reducing agent is one or more of glucose, carbon, and metal powder.
4. The near infrared absorbing filter of claim 1, wherein the thickness is 0.25-0.6 mm.
5. The near infrared absorbing filter of claim 1, wherein the average transmittance of light having a wavelength of 930-950 nm is less than 13%.
6. The near infrared absorbing filter of claim 1, wherein the semi-transmission wavelength is 700-800 nm.
7. The near infrared absorbing filter of claim 6, wherein the semi-transmission wavelength is 715-785 nm.
8. The near infrared absorbing filter of claim 1, wherein the filter has one or more of elemental sulfur, sodium sulfide, and iron sulfide.
9. The near infrared absorbing filter of claim 1, wherein the transmittance of light having a wavelength of 940nm is less than 12%.
10. The near infrared absorbing filter of claim 1, wherein the transmittance of light with a wavelength of 650nm is more than 82%.
11. The near infrared absorbing filter of claim 1, wherein the thickness is less than 0.3mm.
12. The near infrared absorbing filter of claim 11, wherein the half-transmission wavelength is 760-785 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202411697949.1A CN119200067A (en) | 2024-11-26 | 2024-11-26 | A near infrared absorption filter |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202411697949.1A CN119200067A (en) | 2024-11-26 | 2024-11-26 | A near infrared absorption filter |
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| CN119200067A true CN119200067A (en) | 2024-12-27 |
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|---|---|---|---|---|
| US3652303A (en) * | 1970-01-26 | 1972-03-28 | Ppg Industries Inc | Heat absorbing blue soda-lime-silica glass |
| US3723142A (en) * | 1969-12-11 | 1973-03-27 | Asahi Glass Co Ltd | Neutral gray glass |
| US5013487A (en) * | 1989-08-18 | 1991-05-07 | Libbey-Owens-Ford Co. | Infrared radiation absorbing glue glass composition |
| CN103483391A (en) * | 2013-09-25 | 2014-01-01 | 中国科学院长春应用化学研究所 | Strong near-infrared absorption polysulfide metal complex as well as preparation method and application thereof |
| CN104136386A (en) * | 2012-02-24 | 2014-11-05 | Ppg工业俄亥俄公司 | Lithium containing glass with high oxidized iron content and method of making same |
| CN115716706A (en) * | 2021-08-24 | 2023-02-28 | 白金科技股份有限公司 | Near Infrared Absorbing Glass and Near Infrared Cut Filter |
-
2024
- 2024-11-26 CN CN202411697949.1A patent/CN119200067A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723142A (en) * | 1969-12-11 | 1973-03-27 | Asahi Glass Co Ltd | Neutral gray glass |
| US3652303A (en) * | 1970-01-26 | 1972-03-28 | Ppg Industries Inc | Heat absorbing blue soda-lime-silica glass |
| US5013487A (en) * | 1989-08-18 | 1991-05-07 | Libbey-Owens-Ford Co. | Infrared radiation absorbing glue glass composition |
| CN104136386A (en) * | 2012-02-24 | 2014-11-05 | Ppg工业俄亥俄公司 | Lithium containing glass with high oxidized iron content and method of making same |
| CN103483391A (en) * | 2013-09-25 | 2014-01-01 | 中国科学院长春应用化学研究所 | Strong near-infrared absorption polysulfide metal complex as well as preparation method and application thereof |
| CN115716706A (en) * | 2021-08-24 | 2023-02-28 | 白金科技股份有限公司 | Near Infrared Absorbing Glass and Near Infrared Cut Filter |
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