CN103359936A - Near-infrared light absorbing glass, element and filter - Google Patents
Near-infrared light absorbing glass, element and filter Download PDFInfo
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- CN103359936A CN103359936A CN2012101041245A CN201210104124A CN103359936A CN 103359936 A CN103359936 A CN 103359936A CN 2012101041245 A CN2012101041245 A CN 2012101041245A CN 201210104124 A CN201210104124 A CN 201210104124A CN 103359936 A CN103359936 A CN 103359936A
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Abstract
The invention provides an environment-friendly near-infrared light absorbing glass, element and filter with high chemical stability and excellent permeation characteristic in the visible range. When the thickness of the near-infrared light absorbing glass is 0.4 mm, the transmittance at the wavelength of 400 nm is greater than 80%, and the transmittance at the wavelength of 500 nm is greater than 83%; and in the spectral transmittance within the wavelength range of 500 nm to 700 nm, the wavelength range is 605-630 nm when the transmittance is 50%. The near-infrared light absorbing glass contains Al(PO3)3, AlF3, R'F2, ZnO and CuO, wherein the R'F2 represents the sum of MgF2, CaF2, SrF2 and BaF2.
Description
Technical field
The present invention relates to a kind of near-infrared absorption glass, near-infrared absorption element and near-infrared absorption spectral filter.Particularly, the near-infrared absorption spectral filter that the present invention relates to a kind of suitable chromatic sensitivity correction is with, near-infrared absorption glass that chemical stability is good, and the near-infrared absorption element and the spectral filter that are made of this glass.
Background technology
In recent years, the spectrum sensitivity that is used for the semiconductor camera elements such as CCD, CMOS of digital camera and VTR photographic camera, spread near the near infrared field that begins from visual field the 1100nm, use the spectral filter that absorbs near infrared field light can obtain being similar to people's visual sense degree.Therefore, the chromatic sensitivity correction is increasing with the demand of spectral filter, and this just has higher requirement to the near-infrared absorption functional glass for the manufacture of this type of spectral filter, namely require this type of glass have the visible range excellence through characteristic.
In the prior art, near-infrared ray absorption glass is by add Cu in phosphate glass or fluorphosphate glass
2+Make near-infrared absorption glass.But relative fluorphosphate glass, the phosphate glass chemical stability is relatively poor, if glass is exposed under the hot and humid environment for a long time, glass surface can produce the defective of be full of cracks and gonorrhoea.Prior art is also by introducing Sb
3+Eliminate the Cu in the glass solution
2+Be reduced to Cu
+, solve the technical problem that near the transmitance the glass wavelength 400nm reduces with this, but Sb
2O
3Introducing environment is affected.
In addition, the miniaturization of photoelectricity end product, lightweight promote the thin plate of near-infrared absorption filter glass.But if directly with the glass attenuation, then near-infrared absorption also diminishes, and can't obtain required dichroism, so often by increasing coloring components Cu
2+Content reduce and near-infrared absorption filter glass Cu with the absorption that remedies thin plate and cause
2+The concentration height is Cu then
2+Valence mumber change, near the transmitance the 400nm reduces and becomes blue-greenish colour.In addition, if increase Cu
2+Amount, then the glass devitrification resistance worsens, crystal is easily separated out in the glass.
Summary of the invention
That technical problem to be solved by this invention provides a kind of environmental protection and have superior chemical stability and have excellent near-infrared absorption glass, element and the spectral filter that sees through characteristic at visible range.
The present invention solves the problems of the technologies described above the technical scheme that adopts: near-infrared absorption glass, when described near-infrared absorption thickness of glass is 0.4mm, show greater than 80% in wavelength 400nm transmitance, show greater than 83% in wavelength 500nm transmitance, in the spectral transmittance in the wavelength region of 500nm to 700nm, corresponding wavelength region was the scope of 605-630nm when transmitance was 50%, and described near-infrared absorption glass contains Al (PO
3)
3, AlF
3, R ' F
2, ZnO and CuO, described R ' F
2Represent MgF
2, CaF
2, SrF
2And BaF
2Total amount, the stable D of the water-fast effect of glass
WReach 1 grade, the stable D of acidproof effect
AReach or be better than 4 grades.
Further, when described near-infrared absorption thickness of glass is 0.4mm, show greater than 88% in wavelength 400nm transmitance, show greater than 90% in wavelength 500nm transmitance.
Further, the Al (PO that contains 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; The CuO of 3-10%.
Further, the Al (PO that contains 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 3-7%.
Further, the Al (PO that contains 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 3-5.5%.
Further, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; Greater than 0.1% but less than 3% CuO; The RF of 0-15%, described RF represents the total amount of LiF, NaF and KF; It is 0-1% that finings adds up to amount; The SiO of 0-5%
2
Further, its weight percent consists of: the Al (PO of 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 0.5-2.9%; The RF of 3-10%; It is 0.005-0.5% that finings adds up to amount; The SiO of 0-2%
2
Further, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 1-2.6%; The RF of 3-10%; It is 0.01-0.07% that finings adds up to amount; The SiO of 0.1-1.5%
2
Further, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; The CuO of 3-10%; The RF of 0-15%, described RF represents the total amount of LiF, NaF and KF; The BaCl of 0-1%; The SiO of 0-5%
2
Further, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 3-7%; The RF of 3-10%, described RF represents the total amount of LiF, NaF and KF; The BaCl of 0.005-0.5%; The SiO of 0-2%
2
Further, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3The MgF of 1-5%
2The CaF of 5-8%
2The BaF of 20-25%
2The SrF of 0-2%
2The ZnO of 2-10%; The CuO of 3-5.5%; The NaF of 3-7%; The Li of 2-8%
2O; The BaCl of 0.01-0.07%; The SiO of 0.1-1.5%
2
Near-infrared absorption glass contains the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2, described R ' F
2Represent MgF
2, CaF
2, SrF
2And BaF
2Total amount; The ZnO of 1-20%; The CuO of 3-10%.
Further, the Al (PO that contains 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 3-7%.
Further, the Al (PO that contains 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 3-5.5%.
Further, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; Greater than 0.1% but less than 3% CuO; The RF of 0-15%, described RF represents the total amount of LiF, NaF and KF; It is 0-1% that finings adds up to amount; The SiO of 0-5%
2
Further, its weight percent consists of: the Al (PO of 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 0.5-2.9%; The RF of 3-10%; It is 0.005-0.5% that finings adds up to amount; The SiO of 0-2%
2
Further, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 1-2.6%; The RF of 3-10%; It is 0.01-0.07% that finings adds up to amount; The SiO of 0.1-1.5%
2
Further, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3The MgF of 0-8%
2The CaF of 0-10%
2The BaF of 15-35%
2The SrF of 0-5%
2The ZnO of 1-20%; Greater than 0.1% but less than 3% CuO; The NaF of 0-15%; The Li of 0-15%
2O; The BaCl of 0-1%; The SiO of 0-5%
2
Further, its weight percent consists of: the Al (PO of 38-50%
3)
3The AlF of 5-12%
3The MgF of 1-5%
2The CaF of 1-8%
2The BaF of 18-30%
2The SrF of 0-3%
2The ZnO of 1-15%; The CuO of 0.5-2.9%; The NaF of 1-8%; The Li of 1-10%
2O; The BaCl of 0.005-0.5%; The SiO of 0-2%
2
Further, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3The MgF of 1-5%
2The CaF of 5-8%
2The BaF of 20-25%
2The SrF of 0-2%
2The ZnO of 2-10%; The CuO of 1-2.6%; The NaF of 3-7%; The Li of 2-8%
2O; The BaCl of 0.01-0.07%; The SiO of 0.1-1.5%
2
Further, in wavelength 400-700nm spectral transmittance, transmitance shows that 50% wavelength is that the thickness of 615nm is between 0.3-0.6mm.
The near-infrared absorption element is made of above-mentioned near-infrared absorption glass.
The near-infrared absorption spectral filter is made of above-mentioned near-infrared absorption glass.
The invention has the beneficial effects as follows: the present invention with fluophosphate glass as host glass, by introducing an amount of ZnO, the 400nm transmitance of having improved the one-tenth glass of glass and having improved glass, and ZnO and P
2O
5Improved effect the chemical stability of glass, the stable D of the water-fast effect of glass
W(powder method) reaches 1 grade, the stable D of acidproof effect
A(powder method) reaches or is better than 4 grades; The present invention has introduced an amount of NaF, effectively reduce the temperature of fusion of glass, so that glass Near-infrared Spectral Absorption excellent performance of the present invention: when thickness of glass is 0.4mm, wavelength 400nm transmitance shows greater than 80%, show greater than 83% in wavelength 500nm transmitance, in the spectral transmittance in the wavelength region of 500nm to 700nm, corresponding wavelength (λ when transmitance is 50%
50Corresponding wavelength value) scope is 605-630nm.
Description of drawings
Fig. 1 is the spectral transmittance graphic representation of the near-infrared absorption glass of embodiments of the invention 1.
Embodiment
Near-infrared absorption glass of the present invention be with fluophosphate glass as the basis, the CuO that is added with the near-infrared absorption effect obtains.Be weight %, the restriction reason of each component concentration of formation glass of the present invention is described as follows.
Al (PO
3)
3The main component that forms glass network structure of the present invention, if content less than 30%, stability, glass can variation, hot swollen Zhang coefficient can become greatly, resistance to sudden heating is understood step-down.If content surpasses 55%, it is bad that chemical durability can become.Therefore, Al (PO
3)
3Content range be 30-55%, be preferably 38-50%, more preferably 40-45%.
AlF
3Can improve the chemical durability of glass, if its content less than 1%, just can not get above-mentioned effect, if surpass 15%, glass becomes the glass properties variation.Therefore, AlF
3Content range be 1-15%, be preferably 5-12%, more preferably 7-10%.
RF can improve the one-tenth glass of glass.Here RF represents LiF, NaF, KF, if RF surpasses 15%, the chemical durability of glass can obviously reduce.Therefore, it is 0-15% that RF adds up to content range, and preferably adding up to content is 3-10%.
Only introduce NaF among the preferred RF of the present invention, NaF can improve the alkalescence of glass metal, is conducive to cupric ion and is present in the glass with high valence state, can effectively reduce the melt temperature of glass simultaneously.When the glass melting temperature raises, Cu
2+Be reduced to Cu
+Trend strengthens, and consequently cause near the transmitance the wavelength 400nm to reduce, thereby the color of glass becomes blue-greenish colour from blueness, has damaged colour sensitivity correct application necessary characteristic to the semi-conductor image-forming component.Therefore, NaF content is preferably 0-15%, more preferably 1-8%, more preferably 3-7%.
In addition, the present invention preferably introduces Li
2O, to increase oxygen atmosphere in the glass metal, the Cu ion that is conducive in the glass metal exists with the state of divalence, thereby reaches the goal of the invention of glass Near-infrared Spectral Absorption excellent performance of the present invention.Therefore, Li
2The content range of O is 0-15%, is preferably 1-10%, more preferably 2-8%.
R ' F
2The component of one-tenth glass, devitrification resistance and the workability of Effective Raise glass, here R ' F
2Represent MgF
2, CaF
2, SrF
2And BaF
2R ' F
2If the total amount less than 15%, the light transmission rate of glass is significantly the trend that reduces, if surpass 53%, glass has the tendency that worsens devitrification resistance.Therefore, R ' F
2The total amount is 15-53%, and preferably adding up to amount is 20-45%, and more preferably adding up to amount is 25-35%.
Wherein, MgF
2And CaF
2Be improved the effect of glass devitrification resistance, chemical stability, processibility.MgF
2Amount is that 0-8% is more satisfactory, more preferably 1-5%.CaF
2Content is preferably 0-10%, more preferably 1-8%, more preferably 5-8%.
BaF
2And SrF
2Has the effect that improves into glass, glass devitrification resistance, meltbility.Wherein, BaF
2Content is preferably 15-35%, more preferably 18-30%, more preferably 20-25%.SrF
2Content is preferably 0-5%, more preferably 0-3%, more preferably 0-2%.
BaF
2Relative SrF
2The effect that increases glass metal alkalescence is better, and SrF
2As the fluorochemical of high price, the present invention does not preferably introduce.Glass of the present invention strengthens BaF in forming
2Content, do not introduce SrF
2, also effectively improved the chemical stability of glass.
If CuO content is too much, the obvious variation of one-tenth stability, glass of glass, and also the 400nm transmitance of glass reduces; The present invention introduces an amount of ZnO, can effectively reduce the introducing amount of CuO in the glass, can reach the goal of the invention of glass spectrum property of the present invention; Simultaneously, an amount of ZnO and P
2O
5Acting in conjunction has not only improved the stability that becomes glass, but also Effective Raise the chemical stability of glass, particularly improve the glass water resistance.Therefore, the content of ZnO is 1-20%, is preferably 1-15%, more preferably 2-10%.
CuO is the necessary component of glass near-infrared absorption characteristic of the present invention, when its content is lower than 3%, can not get the desirable characteristic that sees through of the present invention, if opposite its content surpasses 10%, and then stability, glass variation, easily devitrification.Therefore, the content range of CuO is 3-10%, and preferable range is 3-7%, more preferably 3-5.5%.
When CuO content was higher in the glass, the present invention is a small amount of SiO of preferred introducing also
2, with the stability of raising glass, if but its content is too much, can reduce the melting of glass, thereby necessary rising melt temperature can reduce the colour sensitivity correct functioning.Therefore, SiO
2Content range is 0-5%, preferred 0-2%, more preferably 0.1-1.5%.SiO
2Preferably with NaSi
2F
6Or KSi
2F
6Arbitrary form is introduced, more preferably with NaSi
2F
6Form introduce.
In addition, in order to remove the bubble that produces in the glass melting process, the present invention preferably introduces and contains Cl
-, Br
-And I
-In one or more finings.If the total amount of described finings surpasses 1%, the Cu in the glass metal
2+Easily be reduced into Cu
+, near the transmitance the wavelength 400nm worsens.Therefore, it is 0-1% that the finings that the present invention introduces adds up to amount, and preferred content is 0.005-0.5%, and more preferably content is 0.009-0.1%, and most preferred content is 0.01-0.07%.
Above-mentioned finings is preferably introduced BaCl, and content range is 0-1%, and preferred content is 0.005-0.5%, and more preferably content is 0.009-0.1%, and most preferred content is 0.01-0.07%.
The below is explained the characteristic of glass of the present invention.
The transmitance of glass is along with variation in thickness, if know thickness of glass and the transmitance of light transmission direction, then by calculating the transmitance that can obtain specific thickness.
When thickness of glass of the present invention is 0.4mm, the characteristic that shows below the spectral transmittance in 400 to 1200nm wavelength region has.
The spectral transmittance of the wavelength of 400nm more than or equal to 80%, preferably greater than or equal to 85%, more preferably greater than or equal 88%.
The spectral transmittance of the wavelength of 500nm more than or equal to 83%, preferably greater than or equal to 88%, more preferably greater than or equal 90%.
The spectral transmittance of the wavelength of 600nm more than or equal to 50%, preferably greater than or equal to 55%, more preferably greater than or equal 60%.
Be less than or equal to 15% at the spectral transmittance of the wavelength of 700nm, preferably be less than or equal to 10%, be more preferably less than or equal 8%.
Be less than or equal to 8% at the spectral transmittance of the wavelength of 800nm, preferably be less than or equal to 5%, be more preferably less than or equal 3%, also be more preferably less than or equal 2%.
Be less than or equal to 10% at the spectral transmittance of the wavelength of 900nm, preferably be less than or equal to 5%, be more preferably less than or equal 2.8%.
Be less than or equal to 10% at the spectral transmittance of the wavelength of 1000nm, preferably be less than or equal to 7%, be more preferably less than or equal 5.8%.
Be less than or equal to 15% at the spectral transmittance of the wavelength of 1100nm, preferably be less than or equal to 13%, be more preferably less than or equal 12.5%.
Be less than or equal to 28% at the spectral transmittance of the wavelength of 1200nm, preferably be less than or equal to 26%, be more preferably less than or equal 23.5%.
That is, when thickness of glass of the present invention was 0.4mm, the absorption in the near infrared region wavelength region of 700nm to 1200nm was large, and the absorption in the wavelength region of the visible region of 400nm to 600nm is little.In the spectral transmittance in 500 to 700nm wavelength region, corresponding wavelength (λ when transmitance is 50%
50Corresponding wavelength value) scope is 605-630nm, and preferable range is 610-625nm, more preferably 612-620nm.
And in wavelength 400-700nm spectral transmittance, transmitance shows that 50% wavelength is that the thickness of 615nm is between 0.1-0.8mm, preferably between 0.2-0.6mm, more preferably between 0.3-0.6mm.Preferably the transmitance of the wavelength 400nm under described thickness is more than 80%.
Thickness of the present invention is that the transmitance of 0.4mm glass refers to that its wavelength of glass of measuring with spectrophotometer is the transmitance of 400-1200nm.Transmitance is measured the value that obtains in this way: the supposition glass sample has two planes of parallel to each other and optical polish, light vertical incidence from the parallel planes, from the outgoing of another one parallel planes, this outgoing light intensity is exactly transmitance divided by the incident light intensity, and this transmitance is also referred to as outer transmitance.
According to the above-mentioned characteristic of glass of the present invention, can realize admirably the color correction of semi-conductor image-forming component such as CCD or CMOS.
The characteristic of the chemical stability aspect of glass is as follows: the stable D of water-fast effect
WCan reach 1 grade; The stable D of acidproof effect
AReach 4 grades, preferably reach 3 grades, more preferably reach 2 grades.
The stable D of above-mentioned water-fast effect
W(powder method) presses the testing method of GB/T17129, calculates according to following formula:
D
W＝(B-C)/(B-A)*100
In the formula: D
W-glass leaches percentage ratio (%)
The quality of B-strainer and sample (g)
The quality (g) of sample after C-strainer and the erosion
A-filter quality (g)
By the leaching percentage ratio that calculates, D is stablized in the water-fast effect of opticglass
WBeing divided into 6 classes sees the following form.
The stable D of above-mentioned acidproof effect
A(powder method) presses the testing method of GB/T17129, calculates according to following formula:
D
A＝(B-C)/(B-A)*100
In the formula: D
A-glass leaches percentage ratio (%)
The quality of B-strainer and sample (g)
The quality (g) of sample after C-strainer and the erosion
A-filter quality (g)
By the leaching percentage ratio that calculates, D is stablized in the acidproof effect of opticglass
ABeing divided into 6 classes sees the following form.
Involved in the present invention to the near-infrared absorption element consisted of by described near-infrared absorption glass, can exemplify out for the laminal glass elements of near-infrared absorption spectral filter or lens etc., be applicable to the colour correction purposes of solid-state imager, possess good through performance and chemical stability.And the thickness of near-infrared absorption element (seeing through the plane of incidence of light and the interval of outgoing plane) is determined by the light transmission rate of this element, preferably between about 0.1-0.8mm, more preferably between 0.3-0.6mm, determine, and preferred λ
50Between 605-630nm, particularly preferably 615nm. adjusts the composition of near-infrared absorption glass in order to obtain such near-infrared absorption element, is processed into the element with above-mentioned spectral response curve thickness.
Involved in the present invention to the near infrared filter device formed by the near-infrared absorption element that near-infrared absorption glass consists of, possesses the two sides by near-infrared absorption element optical grinding, that near-infrared absorption glass consists of, colour correction function by this element is given spectral filter also possesses good chemical stability simultaneously.
Embodiment
Hereinafter, reference example will be described the present invention in more detail.Yet, the invention is not restricted to described embodiment.
At first; with fluorochemical, metaphosphate, oxide compound, nitrate and carbonate as frit; raw material weighed be the glass with the composition that shows among the 1-3 at table; after mixing fully; mixing raw material is put into in the platinum crucible of sealing of lid, and heating and melting under 700-900 ℃ temperature is after oxygen protection while homogenizing is adopted in clarification; melten glass is flowed out continuously with constant flow rate from the temperature control pipeline, obtain opticglass of the present invention after the moulding.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Al(PO 3) 3 | 42.9 | 37.1 | 38 | 39.7 | 40 | 44.2 | 45.6 | 50.5 | 51.4 | 51.2 |
| AlF 3 | 8.9 | 4.2 | 5 | 7 | 8.9 | 10 | 11.8 | 12 | 13.9 | 14.5 |
| MgF 2 | 3.4 | 1 | 2 | 2.7 | 3.5 | 4 | 4.7 | 5 | 6.6 | 7.9 |
| CaF 2 | 6.8 | 9.1 | 8 | 7.3 | 6.7 | 5 | 4.8 | 3.2 | 1 | 0 |
| BaF 2 | 22.3 | 30 | 29.1 | 25 | 23.4 | 20 | 19.7 | 18 | 16.3 | 15.3 |
| NaF | 5.8 | 1 | 2.3 | 3 | 4.1 | 5.4 | 6.8 | 6.1 | 7.6 | 7.6 |
| |
0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.9 | 0.5 | 1.2 |
| Li 2O | 5.3 | 9.6 | 8 | 8.3 | 7 | 6.4 | 3.3 | 2 | 1.7 | 1 |
| ZnO | 4.6 | 8 | 7.6 | 7 | 6.4 | 5 | 3.3 | 2.3 | 1 | 1.3 |
| BaCl | 0.03 | 0.04 | 0.02 | 0.03 | 0.05 | 0.01 | 0.06 | 0.07 | 0.05 | 1 |
| CuO | 3.4 | 3.7 | 3.9 | 3.2 | 3.7 | 3.6 | 4 | 4.8 | 4.3 | 4.5 |
| D W | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| D A | 3 | 3 | 3 | 3 | 3 | 3 | 4 | 3 | 4 | 4 |
Table 2
| Embodiment | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| Al(PO 3) 3 | 41.5 | 31.4 | 41.8 | 41.2 | 50.2 | 45.2 | 39.8 | 42.3 | 43.2 | 44.1 |
| AlF 3 | 9.1 | 1.9 | 9.2 | 9.8 | 3.4 | 12.3 | 10.9 | 7.4 | 8.3 | 9.2 |
| MgF 2 | 3.7 | 0.9 | 3.5 | 3.6 | 1.1 | 2.4 | 3.2 | 2.7 | 3.1 | 2.8 |
| CaF 2 | 6.3 | 10 | 6.4 | 6.2 | 2.3 | 3.5 | 6.7 | 7.5 | 7.3 | 5.4 |
| BaF 2 | 22.5 | 34 | 22.7 | 22.9 | 20.3 | 18.9 | 21.1 | 22.8 | 21.8 | 24.2 |
| NaF | 5.7 | 0.8 | 4.0 | 5.9 | 4.2 | 7.2 | 6.3 | 5.3 | 5.7 | 6.1 |
| |
0 | 1 | 1.2 | 0 | 0 | 0 | 0.3 | 1 | 0 | 1.5 |
| Li 2O | 5.4 | 10 | 5.5 | 4.9 | 8.9 | 4.7 | 7.8 | 6.2 | 6.1 | 3.7 |
| ZnO | 5.8 | 10 | 5.7 | 5.5 | 9.6 | 5.8 | 3.9 | 4.8 | 4.5 | 3 |
| BaCl | 0.04 | 0 | 0.05 | 0.04 | 0 | 0.02 | 0.1 | 0.03 | 0 | 0 |
| CuO | 3.1 | 5.5 | 3.7 | 3.3 | 5.7 | 3.8 | 4.7 | 5.4 | 4.4 | 6.0 |
| D W | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| D A | 3 | 2 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 4 |
Table 3
| Embodiment | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 |
| Al(PO 3) 3 | 42.2 | 42.5 | 42.3 | 41.8 | 54.1 | 34.3 | 48.5 | 39.9 | 44.9 | 40.6 |
| AlF 3 | 9.4 | 9.1 | 9.2 | 9.4 | 1.1 | 14.8 | 5.1 | 11.9 | 7.8 | 9.9 |
| MgF 2 | 3.2 | 3.2 | 3.2 | 3.6 | 0.2 | 7.9 | 4.9 | 2.1 | 3.9 | 3.4 |
| CaF 2 | 6.3 | 6.3 | 6.7 | 6.3 | 0.2 | 9.8 | 1.2 | 7.8 | 5.3 | 7.9 |
| BaF 2 | 22.8 | 22.7 | 22.4 | 22.7 | 34.2 | 15.3 | 29.8 | 19.2 | 24.8 | 21.3 |
| NaF | 5.2 | 5.4 | 5.3 | 5.7 | 0.3 | 7.1 | 1.4 | 7.9 | 3.2 | 6.8 |
| |
0 | 0 | 0 | 0 | 0 | 0.7 | 0 | 0 | 0 | 0 |
| Li 2O | 5.5 | 5.6 | 5.4 | 5.3 | 8.7 | 0.2 | 7.9 | 3.4 | 6.9 | 3.2 |
| ZnO | 5.4 | 5.2 | 5.5 | 5.2 | 1.2 | 9.9 | 1.2 | 7.8 | 3.2 | 6.9 |
| BaCl | 0.031 | 0.05 | 0.04 | 0.05 | 0.05 | 0.9 | 0.03 | 0.4 | 0.05 | 0.08 |
| CuO | 3.85 | 3.1 | 3.5 | 3.5 | 5.5 | 4.4 | 6.0 | 3.8 | 3.3 | 3.8 |
| D W | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| D A | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
Above-mentioned glass processing is become tabular, and optical polish is carried out with the sample for the preparation of the measurement transmitance in two sides respect to one another, use spectrum to see through the spectral transmittance that instrument is measured each sample, obtain the transmitance of typical wavelengths of each sample of 0.4mm thickness.
Shown described glass when 0.4mm thickness among the table 4-6, the transmitance value of glass of the present invention can confirm that described glass all has the excellent properties of proofreading and correct glass as the colour sensitivity that is used for the semi-conductor image-forming component.
Table 4
Table 5
Table 6
Table 7-9 has illustrated the glass of embodiment 1-30, is the thickness of glass of 50% correspondence in the transmitance of wavelength 615nm, and wavelength is respectively the spectral transmittance of 400nm, 500nm, 600nm, 800nm, 1000nm, 1200nm under this thickness.
Table 7
Table 8
Table 9
Fig. 1 is that thickness is the spectral transmittance graphic representation of 0.4mm embodiment 1 glass.As can be seen from the figure, be in the situation of 0.4mm at thickness of glass, the transmitance of optimal wavelength 400nm is more than 80%.In the spectral transmittance in 500 to 700nm wavelength region, corresponding wavelength (λ when transmitance is 50%
50Corresponding wavelength value) scope is 605-630nm.In the spectral transmittance of wavelength 400-1200nm, the transmitance of the wavelength zone of wavelength 800-1000nm is minimum.Because this zone is near-infrared region, semiconductor camera element is not very low at this regional susceptibility, therefore must suppress colour correction with the transmitance of spectral filter, makes it reach fully low degree.And when wavelength during at 1000-1200nm regional, the susceptibility relative reduce of semi-conductor image-forming component, therefore the transmitance of glass of the present invention increases to some extent.
Claims (23)
1. near-infrared absorption glass, it is characterized in that, when described near-infrared absorption thickness of glass is 0.4mm, show greater than 80% in wavelength 400nm transmitance, show greater than 83% in wavelength 500nm transmitance, in the spectral transmittance in the wavelength region of 500nm to 700nm, corresponding wavelength region was the scope of 605-630nm when transmitance was 50%, and described near-infrared absorption glass contains Al (PO
3)
3, AlF
3, R ' F
2, ZnO and CuO, described R ' F
2Represent MgF
2, CaF
2, SrF
2And BaF
2Total amount, the stable D of the water-fast effect of glass
WReach 1 grade, the stable D of acidproof effect
AReach or be better than 4 grades.
2. near-infrared absorption glass as claimed in claim 1 is characterized in that, when described near-infrared absorption thickness of glass is 0.4mm, shows greater than 88% in wavelength 400nm transmitance, shows greater than 90% in wavelength 500nm transmitance.
3. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, contains the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; The CuO of 3-10%.
4. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, contains the Al (PO of 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 3-7%.
5. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, contains the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 3-5.5%.
6. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; Greater than 0.1% but less than 3% CuO; The RF of 0-15%, described RF represents the total amount of LiF, NaF and KF; It is 0-1% that finings adds up to amount; The SiO of 0-5%
2
7. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, its weight percent consists of: the Al (PO of 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 0.5-2.9%; The RF of 3-10%; It is 0.005-0.5% that finings adds up to amount; The SiO of 0-2%
2
8. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 1-2.6%; The RF of 3-10%; It is 0.01-0.07% that finings adds up to amount; The SiO of 0.1-1.5%
2
9. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; The CuO of 3-10%; The RF of 0-15%, described RF represents the total amount of LiF, NaF and KF; The BaCl of 0-1%; The SiO of 0-5%
2
10. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 3-7%; The RF of 3-10%, described RF represents the total amount of LiF, NaF and KF; The BaCl of 0.005-0.5%; The SiO of 0-2%
2
11. near-infrared absorption glass as claimed in claim 1 or 2 is characterized in that, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3The MgF of 1-5%
2The CaF of 5-8%
2The BaF of 20-25%
2The SrF of 0-2%
2The ZnO of 2-10%; The CuO of 3-5.5%; The NaF of 3-7%; The Li of 2-8%
2O; The BaCl of 0.01-0.07%; The SiO of 0.1-1.5%
2
12. near-infrared absorption glass is characterized in that, contains the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2, described R ' F
2Represent MgF
2, CaF
2, SrF
2And BaF
2Total amount; The ZnO of 1-20%; The CuO of 3-10%.
13. near-infrared absorption glass as claimed in claim 12 is characterized in that, contains the Al (PO of 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 3-7%.
14. near-infrared absorption glass as claimed in claim 12 is characterized in that, contains the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 3-5.5%.
15. near-infrared absorption glass as claimed in claim 12 is characterized in that, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3R ' the F of 15-53%
2The ZnO of 1-20%; Greater than 0.1% but less than 3% CuO; The RF of 0-15%, described RF represents the total amount of LiF, NaF and KF; It is 0-1% that finings adds up to amount; The SiO of 0-5%
2
16. near-infrared absorption glass as claimed in claim 12 is characterized in that, its weight percent consists of: the Al (PO of 38-50%
3)
3The AlF of 5-12%
3R ' the F of 20-45%
2The ZnO of 1-15%; The CuO of 0.5-2.9%; The RF of 3-10%; It is 0.005-0.5% that finings adds up to amount; The SiO of 0-2%
2
17. near-infrared absorption glass as claimed in claim 12 is characterized in that, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3R ' the F of 25-35%
2The ZnO of 2-10%; The CuO of 1-2.6%; The RF of 3-10%; It is 0.01-0.07% that finings adds up to amount; The SiO of 0.1-1.5%
2
18. near-infrared absorption glass as claimed in claim 12 is characterized in that, its weight percent consists of: the Al (PO of 30-55%
3)
3The AlF of 1-15%
3The MgF of 0-8%
2The CaF of 0-10%
2The BaF of 15-35%
2The SrF of 0-5%
2The ZnO of 1-20%; Greater than 0.1% but less than 3% CuO; The NaF of 0-15%; The Li of 0-15%
2O; The BaCl of 0-1%; The SiO of 0-5%
2
19. near-infrared absorption glass as claimed in claim 12 is characterized in that, its weight percent consists of: the Al (PO of 38-50%
3)
3The AlF of 5-12%
3The MgF of 1-5%
2The CaF of 1-8%
2The BaF of 18-30%
2The SrF of 0-3%
2The ZnO of 1-15%; The CuO of 0.5-2.9%; The NaF of 1-8%; The Li of 1-10%
20; The BaCl of 0.005-0.5%; The SiO of 0-2%
2
20. near-infrared absorption glass as claimed in claim 12 is characterized in that, its weight percent consists of: the Al (PO of 40-45%
3)
3The AlF of 7-10%
3The MgF of 1-5%
2The CaF of 5-8%
2The BaF of 20-25%
2The SrF of 0-2%
2The ZnO of 2-10%; The CuO of 1-2.6%; The NaF of 3-7%; The Li of 2-8%
2O; The BaCl of 0.01-0.07%; The SiO of 0.1-1.5%
2
21. near-infrared absorption glass as claimed in claim 12 is characterized in that, in wavelength 400-700nm spectral transmittance, transmitance shows that 50% wavelength is that the thickness of 615nm is between 0.3-0.6mm.
22. the near-infrared absorption element is characterized in that, is made of the described near-infrared absorption glass of arbitrary claim among the claim 1-21.
23. the near-infrared absorption spectral filter is characterized in that, is made of the described near-infrared absorption glass of arbitrary claim among the claim 1-21.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316103A (en) * | 2015-06-30 | 2017-01-11 | Hoya株式会社 | Near infrared ray absorbing glass and filter |
| CN106517773A (en) * | 2016-10-20 | 2017-03-22 | 南通向阳光学元件有限公司 | High-transmissivity cyanine polycrystalline glass |
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|---|---|---|---|---|
| CN1508087A (en) * | 2002-07-05 | 2004-06-30 | Hoya株式会社 | Nearinfrared-ray absorbing galss, element, light filter and their production method and copper-contained glass |
| US20070096067A1 (en) * | 2005-09-29 | 2007-05-03 | Hoya Corporation | Lens, near-infrared ray absorption glass lot and manufacturing method therefore |
| CN101472849A (en) * | 2006-07-03 | 2009-07-01 | Hoya株式会社 | Phosphate glass, fluorophosphate glass, preforms for precision press molding, optical elements, and processes for the production of them |
| CN101591143A (en) * | 2008-05-30 | 2009-12-02 | Hoya株式会社 | Opticglass, glass material for press molding, optical element blank, optical element and manufacture method thereof |
-
2012
- 2012-04-11 CN CN201210104124.5A patent/CN103359936B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508087A (en) * | 2002-07-05 | 2004-06-30 | Hoya株式会社 | Nearinfrared-ray absorbing galss, element, light filter and their production method and copper-contained glass |
| US20070096067A1 (en) * | 2005-09-29 | 2007-05-03 | Hoya Corporation | Lens, near-infrared ray absorption glass lot and manufacturing method therefore |
| CN101472849A (en) * | 2006-07-03 | 2009-07-01 | Hoya株式会社 | Phosphate glass, fluorophosphate glass, preforms for precision press molding, optical elements, and processes for the production of them |
| CN101591143A (en) * | 2008-05-30 | 2009-12-02 | Hoya株式会社 | Opticglass, glass material for press molding, optical element blank, optical element and manufacture method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316103A (en) * | 2015-06-30 | 2017-01-11 | Hoya株式会社 | Near infrared ray absorbing glass and filter |
| CN106517773A (en) * | 2016-10-20 | 2017-03-22 | 南通向阳光学元件有限公司 | High-transmissivity cyanine polycrystalline glass |
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