CN102603189B

CN102603189B - Near-infrared absorption glass, element and filter

Info

Publication number: CN102603189B
Application number: CN201210036873.9A
Authority: CN
Inventors: 孙伟; 匡波; 王东俊
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2012-02-17
Filing date: 2012-02-17
Publication date: 2017-12-29
Anticipated expiration: 2032-02-17
Also published as: CN102603189A

Abstract

The present invention provides a kind of with superior chemical stability and in excellent near-infrared absorption glass, element and the filter through characteristic of visible range.Near-infrared absorption glass, when the near-infrared absorption thickness of glass is 1mm, show more than 80%, shown in wavelength 500nm transmissivities more than 85%, the P that the near-infrared absorption glass shows containing useful cation form in wavelength 400nm transmissivities⁵⁺、Al³⁺、Li⁺、R²⁺And Cu²⁺, the R²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺, while the O represented containing useful anion^2‑And F^‑, and F^‑Content is more than O^2‑Content, the water-fast effect stability D of the near-infrared absorption glass_WReach 1 grade, acidproof effect stability D_AReach more than 4 grades.

Description

Near-infrared absorption glass, element and filter

Technical field

The present invention relates to the optical filtering of a kind of near-infrared absorption glass, near-infrared absorption element and near-infrared absorption Device.In particular it relates to a kind of near-infrared absorption filter of suitable chromatic sensitivity amendment is used, chemical stability is excellent Near-infrared absorption glass, and the near-infrared absorption element and filter being made up of the glass.

Background technology

In recent years, the spectrum sensitivity for semiconductor camera elements such as CCD, CMOS of digital camera and VTR cameras Degree, spreads to since the near-infrared field visual field near 1100nm, can using the filter for absorbing near-infrared field light To obtain the visual sense degree for being similar to people.Therefore, the demand of chromatic sensitivity amendment filter is increasing, and this is just to for manufacturing The near-infrared absorption functional glass of such filter proposes higher requirement, that is, it is excellent in visible range to require that such glass has Different transmission characteristic.

In the prior art, near-infrared ray absorption glass is by adding Cu in phosphate glass or fluorphosphate glass²⁺ To manufacture near-infrared absorption glass.But for relative fluorphosphate glass, phosphate glass chemical stability is poor, glass If the defects of long-time is exposed under hot and humid environment, and glass surface can produce cracking and gonorrhoea.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of with superior chemical stability and excellent in visible range Through near-infrared absorption glass, element and the filter of characteristic.

Technical scheme is used by the present invention solves above-mentioned technical problem：Near-infrared absorption glass, the near-infrared When light absorbs thickness of glass is 1mm, is shown in wavelength 400nm transmissivities more than 80%, show and be more than in wavelength 500nm transmissivities 85%, the P that the near-infrared absorption glass shows containing useful cation form⁵⁺、Al³⁺、Li⁺、R²⁺And Cu²⁺, the R²⁺Represent Mg² ⁺、Ca²⁺、Sr²⁺And Ba²⁺, while the O represented containing useful anion^2-And F^-, and F^-Content is more than O^2-Content, the near infrared light The water-fast effect stability D of heat absorbing glass_WReach 1 grade, acidproof effect stability D_AReach more than 4 grades.

Further, when the near-infrared absorption thickness of glass is 1mm, shows and be more than in wavelength 400nm transmissivities 88%, shown in wavelength 500nm transmissivities more than 90%.

Further, the P containing 15-35%⁵⁺；5-20% Al³⁺；1-30% Li⁺；0-10% Na⁺；R²⁺Content is 30-65%；Cu²⁺Content is 0.1-8%.

Further, the P containing 15-35%⁵⁺；5-20% Al³⁺；1-15% Li⁺；0-10% Na⁺；R²⁺Content is 30-65%；Cu²⁺Content is 0.1-8%.

Further, the P containing 15-35%⁵⁺；5-20% Al³⁺；2-5% Li⁺；0-10% Na⁺；R²⁺Content is 30-65%；Cu²⁺Content is 0.1-8%.

Further, the P containing 20-30%⁵⁺；10-15% Al³⁺；1-15% Li⁺；0-5% Na⁺；R²⁺Content is 40-65%；Cu²⁺Content is 1.2-5%.

Further, the P containing 20-30%⁵⁺；10-15% Al³⁺；1-10% Li⁺；0-5% Na⁺；R²⁺Content is 40-65%；Cu²⁺Content is 1.2-5%.

Further, the P containing 20-30%⁵⁺；10-15% Al³⁺；2-5% Li⁺；0-5% Na⁺；R²⁺Content is 40-65%；Cu²⁺Content is 1.2-5%.

Further, the P containing 21-25%⁵⁺；10-15% Al³⁺；1-15% Li⁺；0.5-3% Na⁺；R²⁺Content For 54-65%；Cu²⁺Content is 1.2-5%.

Further, the P containing 21-25%⁵⁺；10-15% Al³⁺；1-10% Li⁺；0.5-3% Na⁺；R²⁺Content For 54-65%；Cu²⁺Content is 1.2-5%.

Further, the P containing 21-25%⁵⁺；10-15% Al³⁺；2-5% Li⁺；0.5-3% Na⁺；R²⁺Content For 54-65%；Cu²⁺Content is 1.2-5%.

Further, wherein O^2-Content is more than or equal to 40% but is less than 50%, F^-Content is more than 50% but is less than Or equal to 60%.

Further, wherein O^2-Content is more than or equal to 43% but is less than 50%, F^-Content is more than 50% but is less than Or equal to 57%.

Further, wherein O^2-Content is 45-49%, F^-Content is 51-55%.

Further, wherein O^2-Content is 47-49%, F^-Content is 51-53%.

Near-infrared absorption element, it is made up of above-mentioned near-infrared absorption glass.

Near-infrared absorption filter, it is made up of above-mentioned near-infrared absorption glass.

The beneficial effects of the invention are as follows：For the present invention using fluophosphate glass as host glass, fluorophosphate host glass is cloudy F in ion component^-Content is more than O^2-Content, the melting temperature of glass can be effectively reduced, the chemistry of glass can also be made steady It is qualitative excellent, it is mainly shown as water-fast effect stability D_WReach 1 grade, acidproof effect stability D_AReach 4 grades or better than 4 grades；This Invention is by increasing the R in fluorophosphate host glass composition²⁺Content, the alkali content of glass metal is increased, suppress Cu²⁺Reduction Into Cu⁺So that the near-infrared absorption excellent performance of glass.When the thickness of glass of the present invention is 1mm, transmitted in wavelength 400nm Rate is shown more than 80%, is shown in wavelength 500nm transmissivities more than 85%.Meanwhile in 500 to 700nm wave-length coverage In spectral transmittance, corresponding wavelength (λ when transmitance is 50%₅₀Corresponding wavelength value) scope be 615 ± 10nm scope.

Brief description of the drawings

Fig. 1 is the spectral-transmission favtor curve map of the near-infrared absorption glass of embodiments of the invention 1.

Embodiment

The near-infrared absorption glass of the present invention is based on fluophosphate glass, is acted on added with near-infrared absorption Cu²⁺Obtained from.

Hereinafter, cationic componentses content accounts for the degree table of whole cation gross weights with the cation weight Show, the degree that anionic group content accounts for whole anion gross weights with the anion weight represents.

P⁵⁺It is a kind of important component that absorption is produced in region of ultra-red for the basis of fluorphosphate glass.When it contains When amount is less than 15%, glass near-infrared absorption effect reduces, and colour correction function deteriorates and with green；More than 35% glass is resistance to Increased devitrification resistance deteriorates with chemical stability, therefore P⁵⁺Content be defined to 15-35%, preferably 20-30%, more preferably 21- 25%.

Al³⁺Be improve fluorphosphate glass into glassy, chemical stability, a kind of component of resistance to sudden heating.Work as Al³ ⁺When content is less than 5%, the effect above is not reached；Work as Al³⁺When content is more than 20%, near-infrared absorbing characteristic reduces.Therefore, Al³⁺Content is 5-20%, more preferably 10-15%.

Li⁺、Na⁺And K⁺It is meltability, the component into glassy and visible region transmitance for improving glass.Also, phase For adding Na in a manner of being introduced separately into⁺、K⁺For, introduce Li⁺It is more preferable to the chemical stability effect of glass.But work as Li⁺Contain When amount is more than 30%, the chemical stability and processing characteristics of glass deteriorate.Therefore, Li⁺Content is 1-30%, preferably 1- 15%, more preferably 1-10%, most preferably 2-5%.

The present invention more preferably adds a small amount of Na⁺With Li⁺Consolute, the chemical stability of glass can be effectively improved.Na⁺Draw Enter also to be improved the effect of meltbility and devitrification resistance, its content is 0-10%, preferably 0-5%, more preferably 0.5-3%.K⁺Content is 0-3%, if its content is more than 3%, chemical durability of glass and processing characteristics reduce on the contrary.

R²⁺Be effectively improve glass into glassy, devitrification resistance and the component of machinability, R here²⁺Represent Mg²⁺、 Ca²⁺、Sr²⁺And Ba²⁺.As near-infrared absorption filter, the light transmission rate for being contemplated to be visible range is higher.It is visual in order to improve The transmitance in domain, the copper ion introduced in glass is not Cu⁺, it is necessary to it is Cu²⁺.If glass solution is in reducing condition, Cu²⁺Just Become Cu⁺, the result is that the transmitance near wavelength 400nm will reduce.The present invention by increasing Mg in right amount²⁺、Ca²⁺、Sr²⁺With Ba²⁺Total amount, add the alkali content of glass metal, Cu can be suppressed²⁺It is reduced into Cu⁺So that the near infrared light of glass is inhaled Receive excellent performance.Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺If total amount less than 30%, the light transmission rate of glass is in being greatly reduced Trend, if it exceeds 65%, glass has the tendency of to deteriorate devitrification resistance.Therefore, Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount For 30-65%, preferably total amount be 40-65%, and more preferably total amount is more than 50% but is less than or equal to 65%, Further preferably total amount is 54-65%, and most preferably total amount is 54-60%.

Wherein, Mg²⁺And Ca²⁺It is improved the effect of glass devitrification resistance, chemical stability, processability.Mg²⁺Amount is 0.1-10% is more satisfactory, more preferably 2-8%, further preferred 3-7%.Ca²⁺Content is preferably 1-20%, more preferably 5- 15%, it is still more preferably 7-11%.

With respect to Mg²⁺And Ca²⁺For, the present invention has been primarily introduced into the Sr of high content²⁺And Ba²⁺, it is being effectively increased R²⁺Contain Amount, while bringing raising light transmission rate effect, Sr²⁺And Ba²⁺Also have and improve into glassy, glass devitrification resistance, meltbility Effect.Sr²⁺Content is preferably 15-35%, more preferably 21-30%, further preferred 23-28%.The reasons why same, Ba²⁺ Content is preferably 10-30%, more preferably 15-30%, more preferably 21-30%, most preferably 21-25%.

Copper in glass of the present invention is the leading indicator of near-infrared absorbing characteristic, and with Cu²⁺In the presence of.Work as Cu²⁺Content During less than 0.1%, as near-infrared absorption filter, it is impossible to sufficiently achieve necessary near-infrared absorption effect；But work as it When content is more than 8%, the devitrification resistance of glass, reduce into glassy.Therefore, Cu²⁺Content is 0.1-8%, preferably 1.2- 5%, more preferably 1.8-3%.

Contain the O as anion component in glass of the present invention^2-And F^-.It is molten when improving in near-infrared ray absorption glass When melting temperature, Cu²⁺Also easily it is reduced to Cu⁺, the color of glass is changed into green from blueness, so as to compromise colour sensitivity school Just it is being applied to necessary characteristic on semiconductor image-forming component.The present invention by increasing F in right amount^-Content, and F^-Content is more than O^2-Content, can be effectively reduced the melting temperature of glass, and increase F in right amount^-The chemical stability of glass can also be made excellent It is different, F^--O^2-Preferred scope be 0.1-20%, further preferred scope is 0.1-10%, most preferred range 0.1-3%.

F^-It is to reduce the melting temperature of glass and improve the important anionic group of chemical stability.In the present invention, work as F^- When content is equal to or less than 50%, chemical stability reduces；Work as F^-When content is more than 60%, because O^2-Content reduces, Cu²⁺Subtract It cannot suppress less, Cu in glass⁺Content raises, and shortwave partially absorbs increase, and infrared absorption reduces.Therefore, F^-Content be more than 50% but less than or equal to 60%, preferably greater than 50% but being less than or equal to 57%, more preferably 51-55%, it is more excellent Elect 51-53% as.

O^2-It is a kind of important anionic group in glass of the present invention, its content is that total nonionic content subtracts F^-After remain Remaining whole contents.Work as O^2-Content very little when because Cu²⁺It is reduced to Cu⁺, so in short wavelength region, particularly exist Absorption near 400nm is become much larger until shown in green；But work as O^2-Content it is excessive when because the viscosity of glass becomes more Height is so as to cause higher melting temperature, so transmitance reduces.Therefore, O in the present invention^2-Content be more than or equal to 40% But less than 50%, preferably greater than or equal to 43% but less than 50%, more preferably 45-49%, more preferably 47- 49%.

The present invention is designed by specific component, and the characteristic in terms of the chemical stability of glass is as follows：Water-fast effect is stable Property D_W1 grade can be reached；Acidproof effect stability D_AReach 4 grades, preferably reach 3 grades, more preferably up to 2 grades.

Above-mentioned water-fast effect stability D_W(powder method) presses GB/T17129 method of testing, is calculated according to following formula：

D_W=(B-C)/(B-A) * 100

In formula：D_W- glass leaches percentage (%)

The quality (g) of B- filters and sample

The quality (g) of sample after C- filters and erosion

A- filter qualities (g)

By the leaching percentage being calculated, by the stable D of the water-fast effect of optical glass_WIt is divided into 6 classes see the table below.

Classification	1	2	3	4	5	6
							Leach percentage (D_W)	＜ 0.04	0.04-0.10	0.10-0.25	0.25-0.60	0.60-1.10	＞ 1.10

Above-mentioned acidproof effect stability D_A(powder method) presses GB/T17129 method of testing, is calculated according to following formula：

D_A=(B-C)/(B-A) * 100

In formula：D_A- glass leaches percentage (%)

The quality (g) of B- filters and sample

The quality (g) of sample after C- filters and erosion

A- filter qualities (g)

By the leaching percentage being calculated, by the stable D of the acidproof effect of optical glass_AIt is divided into 6 classes see the table below.

Classification	1	2	3	4	5	6
							Leach percentage (D_A)	＜ 0.20	0.20-0.35	0.35-0.65	0.65-1.20	1.20-2.20	＞ 2.20

The preferred light transmission rate of glass of the present invention is as follows：

When thickness of glass is 1mm, the spectral transmittance in 400 to 1200nm wave-length coverage has the spy being illustrated below Property.

400nm wavelength spectral transmittance be more than or equal to 80%, preferably greater than or equal to 85%, more preferably greater than Or equal to 88%.

500nm wavelength spectral transmittance be more than or equal to 85%, preferably greater than or equal to 88%, more preferably greater than Or equal to 90%.

600nm wavelength spectral transmittance be more than or equal to 58%, preferably greater than or equal to 61%, more preferably greater than Or equal to 64%.

700nm wavelength spectral transmittance be less than or equal to 12%, preferably lower than or equal to 10%, more preferably less than Or equal to 9%.

800nm wavelength spectral transmittance be less than or equal to 5%, preferably lower than or equal to 3%, more preferably less than or Equal to 2.5%, even more preferably less than or equal to 2%.

900nm wavelength spectral transmittance be less than or equal to 5%, preferably lower than or equal to 3%, more preferably less than or Equal to 2.5%.

1000nm wavelength spectral transmittance be less than or equal to 7%, preferably lower than or equal to 6%, more preferably less than Or equal to 5%.

1100nm wavelength spectral transmittance be less than or equal to 15%, preferably lower than or equal to 13%, it is more preferably small In or equal to 11%.

1200nm wavelength spectral transmittance be less than or equal to 24%, preferably lower than or equal to 22%, it is more preferably small In or equal to 21%.

That is, the absorption in 700nm to 1200nm near infrared region wave-length coverage is big, in the visible of 400nm to 600nm Absorption in light region wavelength range is small.

In spectral transmittance in 500 to 700nm wave-length coverage, corresponding wavelength (λ when transmitance is 50%₅₀ Corresponding wavelength value) scope is 615 ± 10nm.

The transmitance of glass of the present invention refers to the value obtained in this way by spectrophotometer：It is assumed that glass sample has There are two planes parallel to each other and optical polish, light is from vertical incidence on a parallel plane, from another parallel plane Outgoing, the intensity of the emergent light divided by the intensity of incident light are exactly transmitance, and the transmitance is also referred to as outer transmitance.

According to the above-mentioned characteristic of the glass of the present invention, it can admirably realize semiconductor image-forming component such as CCD or CMOS Color correction.

The near-infrared absorption element that the present invention relates to is made up of the near-infrared absorption glass, can be included For laminal glass elements or lens in near-infrared absorption filter etc., suitable for the colour correction of solid-state imager Purposes, possess good transmission performance and chemical stability.

The near infrared filter device that the present invention relates to is the near-infrared absorption member being made up of near-infrared absorption glass Part, therefore also possess good optical transmittance property and chemical stability.

Embodiment

Hereinafter, the present invention will be described in further detail in reference implementation example.However, the invention is not restricted to the embodiment.

First, using fluoride, metaphosphate, oxide, nitrate and carbonate as frit, raw material, which is weighed, to be made It is the glass with the composition shown in Tables 1 and 2, and after being thoroughly mixed, mixed material is put into what is sealed with lid In platinum crucible, melting is heated at a temperature of 700-900 DEG C, clarification is homogenized using oxygen protection simultaneously after, makes melten glass Flowed continually out from temperature control pipeline with constant flow rate, the optical glass of the present invention is obtained after shaping.

Embodiment 1-15 (the manufacture embodiment of near-infrared ray absorption glass)

Table 1

Table 2

R in table 1-2²⁺For：Mg²⁺、Ca²⁺、Sr²⁺And K²⁺Total content.

By above-mentioned glass processing into tabular, and two sides relative to each other is subjected to optical polish and is used to measure to prepare The sample of rate is crossed, the spectral transmittance of each sample is measured using spectral transmission instrument, obtains the typical case of each sample of 1mm thickness The transmitance of wavelength.

The glass is shown in table 3-4 in 1mm thickness, the transmittance values of glass of the present invention, and λ₅₀Corresponding ripple Long value, it can be verified that the glass all has the superiority as the colour sensitivity correction glass for semiconductor image-forming component Energy.

Table 3

Table 4

Fig. 1 is the spectral-transmission favtor curve map of above-described embodiment 1.It can be seen that in the feelings that thickness of glass is 1mm Under condition, optimal wavelength 400nm transmissivity is more than 80%.In spectral transmittance in 500 to 700nm wave-length coverage, Corresponding wave-length coverage is 615 ± 10nm when transmitance is 50%.In wavelength 400-1200nm spectral-transmission favtor, wavelength The transmissivity of 800-1000nm wavelength zone is minimum.Because this region is near-infrared region, semiconductor camera element is in the region Susceptibility be not very low, it is therefore necessary to suppress the transmissivity of colour correction filter, reach substantially low degree.And work as Wavelength is at 1000-1200nm region, the susceptibility relative reduction of semiconductor image-forming component, therefore the glass of the present invention is saturating The rate of penetrating increased.

Claims

1. near-infrared absorption glass, it is characterised in that when the near-infrared absorption thickness of glass is 1mm, in wavelength 400nm Transmissivity is shown more than 80%, shows that the near-infrared absorption glass contains useful sun more than 85% in wavelength 500nm transmissivities The P that ion represents⁵⁺、Al³⁺、Li⁺、R²⁺And Cu²⁺, the R²⁺Represent Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺,R²⁺Content be more than 50% but Less than or equal to 65%, while the O represented containing useful anion^2-And F^-, and F^-Content is more than O^2-Content, contain 15-24.2% P⁵⁺；The water-fast effect stability D of the near-infrared absorption glass_WReach 1 grade, acidproof effect stability D_AReach 4 grades with On.

2. near-infrared absorption glass as claimed in claim 1, it is characterised in that the near-infrared absorption thickness of glass is During 1mm, show more than 88% in wavelength 400nm transmissivities, shown in wavelength 500nm transmissivities more than 90%.

3. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 15-24.2%⁵⁺；5-20%'s Al³⁺；1-30% Li⁺；0-10% Na⁺；R²⁺Content is more than 50% but less than or equal to 65%；Cu²⁺Content is 0.1- 8%.

4. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 15-24.2%⁵⁺；5-20%'s Al³⁺；1-15% Li⁺；0-10% Na⁺；R²⁺Content is more than 50% but less than or equal to 65%；Cu²⁺Content is 0.1- 8%.

5. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 15-24.2%⁵⁺；5-20%'s Al³⁺；2-5% Li⁺；0-10% Na⁺；R²⁺Content is more than 50% but less than or equal to 65%；Cu²⁺Content is 0.1-8%.

6. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 20-24.2%⁵⁺；10-15% Al³⁺；1-15% Li⁺；0-5% Na⁺；R²⁺Content is more than 50% but less than or equal to 65%；Cu²⁺Content is 1.2- 5%.

7. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 20-24.2%⁵⁺；10-15% Al³⁺；1-10% Li⁺；0-5% Na⁺；R²⁺Content is more than 50% but less than or equal to 65%；Cu²⁺Content is 1.2- 5%.

8. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 20-24.2%⁵⁺；10-15% Al³⁺；2-5% Li⁺；0-5% Na⁺；R²⁺Content is more than 50% but less than or equal to 65%；Cu²⁺Content is 1.2- 5%.

9. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 21-24.2%⁵⁺；10-15% Al³⁺；1-15% Li⁺；0.5-3% Na⁺；R²⁺Content is 54-65%；Cu²⁺Content is 1.2-5%.

10. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 21-24.2%⁵⁺；10-15% Al³⁺；1-10% Li⁺；0.5-3% Na⁺；R²⁺Content is 54-65%；Cu²⁺Content is 1.2-5%.

11. near-infrared absorption glass as claimed in claim 1, it is characterised in that the P containing 21-24.2%⁵⁺；10-15% Al³⁺；2-5% Li⁺；0.5-3% Na⁺；R²⁺Content is 54-65%；Cu²⁺Content is 1.2-5%.

12. the near-infrared absorption glass as described in claim 1-11 any claims, it is characterised in that wherein O^2-Content More than or equal to 40% but to be less than 50%, F^-Content is more than 50% but less than or equal to 60%.

13. the near-infrared absorption glass as described in claim 1-11 any claims, it is characterised in that wherein O^2-Content More than or equal to 43% but to be less than 50%, F^-Content is more than 50% but less than or equal to 57%.

14. the near-infrared absorption glass as described in claim 1-11 any claims, it is characterised in that wherein O^2-Content For 45-49%, F^-Content is 51-55%.

15. the near-infrared absorption glass as described in claim 1-11 any claims, it is characterised in that wherein O^2-Content For 47-49%, F^-Content is 51-53%.

16. near-infrared absorption element, it is characterised in that as the near infrared light described in any claim in claim 1-11 Heat absorbing glass is formed.

17. near-infrared absorption filter, it is characterised in that as the near-infrared described in any claim in claim 1-11 Light absorbs glass is formed.