JP3043076B2 - Low fluorescent glass - Google Patents
Low fluorescent glassInfo
- Publication number
- JP3043076B2 JP3043076B2 JP2402946A JP40294690A JP3043076B2 JP 3043076 B2 JP3043076 B2 JP 3043076B2 JP 2402946 A JP2402946 A JP 2402946A JP 40294690 A JP40294690 A JP 40294690A JP 3043076 B2 JP3043076 B2 JP 3043076B2
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- Prior art keywords
- less
- glass
- ppm
- fluorescence
- low
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- Solid State Image Pick-Up Elements (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は蛍光測定に使用される試
料セルや、固体撮像素子を保護するカバーガラスに使用
される低蛍光性ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample cell used for fluorescence measurement and a low-fluorescence glass used for a cover glass for protecting a solid-state imaging device.
【０００２】[0002]
【従来の技術】一般に有機化合物は、大部分が大なり小
なり特定の光を出す蛍光性を持っているため、その蛍光
の強度と波長を測定することにより、蛍光物質の同定や
濃度の定量分析が広く行われている。その際、使用され
る溶液セルの材質としては、水晶や通常のガラスではそ
れ自身が蛍光を発するために使用できないことから、特
殊な蛍光の少ない石英ガラスが使われているが、高価で
あると言う欠点を有している。又、近年、カメラ一体型
ＶＴＲなどに多用される固体撮像素子は受光素子である
ＬＳＩチップをアルミナセラミック製のパッケージ内に
納め、エポキシ樹脂などを用いて、受光部をカバーガラ
スで封止した構造になっているが、従来、このカバーガ
ラスとして白板ガラスや無アルカリバリウムシリケート
ガラスが用いられていた。しかし、それらのカバーガラ
スから発生する蛍光が固体撮像素子に入り、ノイズとな
って、素子の性能を劣化させることが問題視されてい
る。2. Description of the Related Art Generally, most of organic compounds have a fluorescent property that emits specific light to a greater or lesser degree. Therefore, by measuring the intensity and wavelength of the fluorescent light, identification and quantification of a fluorescent substance are performed. Analysis is widely performed. At that time, as the material of the solution cell used, quartz glass or ordinary glass cannot be used because it emits fluorescence itself, so quartz glass with little special fluorescence is used, but it is expensive. It has the drawbacks to say. In recent years, solid-state imaging devices frequently used in camera-integrated VTRs and the like have a structure in which an LSI chip, which is a light receiving element, is housed in an alumina ceramic package, and the light receiving portion is sealed with a cover glass using epoxy resin or the like. Conventionally, white glass and alkali-free barium silicate glass have been used as the cover glass. However, it has been considered that the fluorescence generated from the cover glass enters the solid-state imaging device, becomes noise, and deteriorates the performance of the device.
【０００３】[0003]
【発明が解決しようとする課題】上述のように従来、蛍
光測定用溶液セルに用いられていた低蛍光性石英ガラス
は高価であった。また、従来、固体撮像素子のカバーガ
ラス等に用いられていた白板ガラスや無アルカリバリウ
ムシリケートガラスは素子の性能を劣化させるという問
題があった。As described above, conventionally, low-fluorescence quartz glass used in a solution cell for fluorescence measurement was expensive. Further, conventionally, white plate glass or alkali-free barium silicate glass used as a cover glass of a solid-state imaging device has a problem that the performance of the device is deteriorated.
【０００４】従って、本発明は、蛍光測定用溶液セル
や、固体撮像素子のカバーガラス等に好適な、安価で、
蛍光の少ない低蛍光性ガラスを提供することを目的とす
る。Accordingly, the present invention provides an inexpensive, low-cost solution cell for fluorescence measurement and a cover glass for a solid-state image sensor.
It is an object of the present invention to provide a low-fluorescence glass with low fluorescence.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するべく
鋭意研究の結果、本発明者は、 (1) 白板ガラスや無アルカリバリウムシリケートガラス
を始めとする通常のガラスの蛍光発生の主因は、脱泡剤
であるＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3 および使用原料等からの
不純物、特にＶ2 Ｏ5 、ＣｕＯ、ＣｅＯ2 にあること (2) 脱泡剤であるＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3 による蛍光強
度は、ガラス組成の影響を受け、二価金属酸化物（Ｒ
Ｏ）を含有する場合には、含有しない場合よりも蛍光強
度が高くなるので、蛍光強度を低く抑えるために、前者
の場合には後者の場合よりもＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3 の
量を少なくする必要があること (3) Ａｓ2 Ｏ3 、Ｓｂ2 Ｏ3 以外の脱泡剤として使用さ
れる塩化物、弗化物、硫酸塩は蛍光強度に影響しないこ
とを見い出した。本発明は上記の発見に基づき成された
ものであり、二価金属酸化物（ＲＯ）を含まない第１発
明の蛍光性ガラスは、重量基準で ＳｉＯ2 ４５〜８０％ Ｂ2 Ｏ3 ０〜２５％ Ａｌ2 Ｏ3 ０〜３０％ アルカリ金属酸化物（Ｒ2 Ｏ） ２〜２０％ を含み、これらの成分の合量が９０％以上である基礎ガ
ラス組成物に、この基礎ガラス組成物１００％に対し
て、 Ａｓ2 Ｏ3 ４％以下 Ｓｂ2 Ｏ3 ４％以下 Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０．０５〜４％ Ｖ2 Ｏ5 １０ｐｐｍ以下 ＣｕＯ １０ｐｐｍ以下 ＣｅＯ2 １ｐｐｍ以下 を含有すること特徴とする。Means for Solving the Problems As a result of earnest studies to achieve the above object, the present inventor has found that (1) the main causes of fluorescence generation of ordinary glass such as white plate glass and alkali-free barium silicate glass are as follows: as 2 O 3 is a defoamer, Sb 2 O 3 and impurities from the raw materials used or the like, particularly V 2 O 5, CuO, as 2 O 3 is that in the CeO 2 (2) defoamers, Sb 2 The fluorescence intensity due to O 3 is affected by the glass composition, and the divalent metal oxide (R
When O) is contained, the fluorescence intensity is higher than when it is not contained. Therefore, in order to keep the fluorescence intensity low, the amount of As 2 O 3 and Sb 2 O 3 is higher in the former case than in the latter case. (3) It has been found that chlorides, fluorides and sulfates used as defoaming agents other than As 2 O 3 and Sb 2 O 3 do not affect the fluorescence intensity. The present invention has been made based on the above-mentioned discovery, and the fluorescent glass of the first invention containing no divalent metal oxide (RO) has a SiO 2 of 45 to 80% B 2 O 30 by weight. 25% Al 2 O 3 0-30% Alkali metal oxide (R 2 O) 2-20%, and the total amount of these components is 90% or more. % relative, As 2 O 3 4% or less Sb 2 O 3 4% or less As 2 O 3 + Sb 2 O 3 0.05~4% V 2 O 5 10ppm by containing CeO 2 1 ppm or less or less CuO 10 ppm or less Features.
【０００６】また、二価金属酸化物（ＲＯ）を含む第２
発明の低蛍光性ガラスは、重量基準で ＳｉＯ2 ４５〜８０％ Ｂ2 Ｏ3 ０〜２５％ Ａｌ2 Ｏ3 ０〜３０％ アルカリ金属酸化物（Ｒ2 Ｏ） ０〜２０％ 二価金属酸化物（ＲＯ） ４０％以下 Ｒ2 Ｏ＋ＲＯ ２〜４０％ を含み、これらの成分の合量が９０％以上である基礎ガ
ラス組成物に、この基礎ガラス組成物に対して、 Ａｓ2 Ｏ3 ０．０５％以下 Ｓｂ2 Ｏ3 ０．０５％以下 Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０．００００１〜０．０５％ Ｖ2 Ｏ5 １０ｐｐｍ以下 ＣｕＯ １０ｐｐｍ以下 ＣｅＯ2 １ｐｐｍ以下 を含有すること特徴とする。Further, a second material containing a divalent metal oxide (RO) is used.
Low fluorescent glass of the invention, SiO 2 45~80% B 2 O 3 0~25% Al 2 O 3 0~30% alkali metal oxides by weight (R 2 O) 0~20% divalent metal oxide objects (RO) 40% or less R 2 O + RO comprises from 2 to 40% in the total amount of these components base glass composition is 90% or more, relative to the base glass composition, as 2 O 3 0. 0.05% or less Sb 2 O 3 0.05% or less as 2 O 3 + Sb 2 O 3 and 0.00001~0.05% V 2 O 5 10ppm characterized by containing CeO 2 1 ppm or less or less CuO 10 ppm or less.
【０００７】なお第１発明および第２発明の低蛍光性ガ
ラスは、脱泡剤として、塩化物、弗化物、硫酸塩を含有
することができる。The low-fluorescent glasses of the first and second inventions can contain chlorides, fluorides and sulfates as defoaming agents.
【０００８】以下、本発明を詳細に説明する。まず基礎
ガラス組成物における各成分の量的限定理由について述
べる。ＳｉＯ2 、Ｂ2 Ｏ3 及びＡｌ2 Ｏ3 は、第１発明
のガラス及び第２発明のガラスにおいて量的範囲は同じ
である。ＳｉＯ2 を４５〜８０％に限定した理由は、４
５％未満では化学的耐久性が劣化し、８０％を超えると
熔融が困難になるからである。Ｂ2 Ｏ3 を０〜２５％に
限定した理由は、Ｂ2 Ｏ3 は、熔融性と耐失透性を向上
させるが、２５％を超えると化学的耐久性を劣化させる
からである。Ａｌ2 Ｏ3 を０〜３０％に限定した理由
は、Ａｌ2 Ｏ3 は化学的耐久性を良化させるが、３０％
を超えると熔融が困難になるからである。Hereinafter, the present invention will be described in detail. First, the reasons for the quantitative limitation of each component in the basic glass composition will be described. SiO 2 , B 2 O 3 and Al 2 O 3 have the same quantitative range in the glass of the first invention and the glass of the second invention. The reason for limiting SiO 2 to 45 to 80% is that
If it is less than 5%, the chemical durability deteriorates, and if it exceeds 80%, melting becomes difficult. The reason for limiting the B 2 O 3 0 to 25 percent, B 2 O 3 is to improve the meltability and devitrification resistance, because degrade the chemical durability exceeds 25%. The reason for limiting Al 2 O 3 to 0 to 30% is that Al 2 O 3 improves the chemical durability, but 30%
This is because if the ratio exceeds the above range, melting becomes difficult.
【０００９】アルカリ金属酸化物（Ｒ2 Ｏ）と二価金属
酸化物（ＲＯ＝ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、Ｚｎ
Ｏ）の量的範囲は第１発明のガラスと第２発明のガラス
において異なり、第１発明のガラスにおいては、二価金
属酸化物（ＲＯ）を含まず、アルカリ金属酸化物（Ｒ2
Ｏ）が２〜２０％である。その理由は、アルカリ金属酸
化物（Ｒ2 Ｏ）が２％未満では、熔融が困難になり、２
０％を超えると化学的耐久性が悪くなるからである。一
方、第２発明のガラスは、二価金属酸化物（ＲＯ）を４
０％以下含み、アルカリ金属酸化物（Ｒ2 Ｏ）が０〜２
０％である。二価金属酸化物（ＲＯ）を４０％以下に限
定した理由は４０％を超えると化学的耐久性が悪くなる
からである。またアルカリ金属酸化物（Ｒ2 Ｏ）を０〜
２０％に限定した理由は２０％を超えると化学的耐久性
が悪くなるからである。なおＲ2 ＯとＲＯの合量は２〜
４０％である。Alkali metal oxide (R 2 O) and divalent metal oxide (RO = MgO, CaO, SrO, BaO, Zn
The quantitative range of O) is different between the glass of the first invention and the glass of the second invention. In the glass of the first invention, the divalent metal oxide (RO) is not contained and the alkali metal oxide (R 2
O) is 2 to 20%. The reason is that if the alkali metal oxide (R 2 O) is less than 2%, melting becomes difficult and 2
If it exceeds 0%, the chemical durability deteriorates. On the other hand, the glass of the second invention has a divalent metal oxide (RO) of 4%.
Includes 0% or less, alkali metal oxides (R 2 O) 0-2
0%. The reason why the divalent metal oxide (RO) is limited to 40% or less is that if it exceeds 40%, the chemical durability deteriorates. In addition, the alkali metal oxide (R 2 O)
The reason for limiting to 20% is that if it exceeds 20%, the chemical durability deteriorates. The total amount of R 2 O and RO is 2 to
40%.
【００１０】第１発明の低蛍光性ガラスおよび第２発明
の低蛍光性ガラスにおいて、基礎ガラス組成物は、上述
の成分の合量が９０％以上である。従って、上述の成分
以外に合量で１０％未満のＴｉＯ2 、ＺｒＯ2 、Ｌａ2
Ｏ3 、Ｎｂ2 Ｏ5 、ＷＯ3、Ｐ2 Ｏ5 、Ｔａ2 Ｏ5 等を
添加できるが、これらの成分は二価金属酸化物ほど蛍光
に対する影響は大きくないが、大量の添加は悪影響を及
ぼすので避けなければならない。In the low-fluorescence glass of the first invention and the low-fluorescence glass of the second invention, the base glass composition has a total content of the above components of 90% or more. Therefore, in addition to the above components, TiO 2 , ZrO 2 , and La 2 in a total amount of less than 10% are used.
O 3 , Nb 2 O 5 , WO 3 , P 2 O 5 , Ta 2 O 5, etc. can be added, but these components do not have as great an effect on fluorescence as divalent metal oxides, but large amounts do not. Must be avoided.
【００１１】第１発明のガラスおよび第２発明のガラス
は、上述の基礎ガラス組成物に所定量以下のＡｓ
2 Ｏ3 、Ｓｂ2 Ｏ3 、Ｖ2 Ｏ5 、ＣｕＯおよびＣｅＯ2
を含有することにより、低蛍光性を有し、例えば、蛍光
測定用試料セルや、固体撮像素子保護用カバーガラスと
して好適に使用される。[0011] The glass of the first invention and the glass of the second invention can be obtained by adding As to the above-mentioned base glass composition in a predetermined amount or less.
2 O 3 , Sb 2 O 3 , V 2 O 5 , CuO and CeO 2
By containing the compound, it has low fluorescence, and is suitably used, for example, as a sample cell for fluorescence measurement or a cover glass for protecting a solid-state imaging device.
【００１２】含有し得る上記成分の量は第１発明のガラ
スと第２発明のガラスとでは異なり、第１発明のガラス
では、上述の基礎ガラス組成物１００％に対して、 Ａｓ2 Ｏ3 ４％以下 Ｓｂ2 Ｏ3 ４％以下 Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０．０５〜４％ Ｖ2 Ｏ5 １０ｐｐｍ以下 ＣｕＯ １０ｐｐｍ以下 ＣｅＯ2 １ｐｐｍ以下 であり、第２発明のガラスでは、上述の基礎ガラス組成
物１００％に対して、 Ａｓ2 Ｏ3 ０．０５％以下 Ｓｂ2 Ｏ3 ０．０５％以下 Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ０．００００１〜０．０５％ Ｖ2 Ｏ5 １０ｐｐｍ以下 ＣｕＯ １０ｐｐｍ以下 ＣｅＯ2 １ｐｐｍ以下 である。The amount of the above components that can be contained is different between the glass of the first invention and the glass of the second invention. In the glass of the first invention, As 2 O 3 4 % Or less Sb 2 O 3 4% or less As 2 O 3 + Sb 2 O 3 0.05 to 4% V 2 O 5 10 ppm or less CuO 10 ppm or less CeO 2 1 ppm or less, and in the glass of the second invention, As 2 O 3 0.05% or less Sb 2 O 3 0.05% or less As 2 O 3 + Sb 2 O 3 0.00001 to 0.05% V 2 O 5 10 ppm or less CuO 10 ppm with respect to 100% of the composition The CeO 2 content is 1 ppm or less.
【００１３】上記の成分が上記の範囲を超えると、低蛍
光性ガラスが得られず、本発明の目的を達成できない。
なお、第１発明のガラスおよび第２発明のガラスにおい
て、Ｖ2 Ｏ5 、ＣｕＯおよびＣｅＯ2 は合量で０．０５
〜１０ｐｐｍであるのが特に低蛍光性にすぐれたガラス
を得るために好ましい。そのほかの不純物であるＦｅ2
Ｏ3 、Ｃｒ2 Ｏ3 、Ｃｏ2 Ｏ3 、ＮｉＯ、ＭｎＯ2 等
は、数１０ｐｐｍ程度の混入は差し支えない。またＰｂ
Ｏはそれ自体が蛍光を出すため好ましくない成分である
が、１００ｐｐｍ以下の不純物オーダーなら問題ない。When the above components exceed the above ranges, a low-fluorescent glass cannot be obtained, and the object of the present invention cannot be achieved.
Incidentally, in the glass of the first invention and the glass of the second invention, V 2 O 5 , CuO and CeO 2 are 0.05% in total.
It is preferably from 10 to 10 ppm in order to obtain a glass having particularly low fluorescence. Fe 2 which is another impurity
O 3 , Cr 2 O 3 , Co 2 O 3 , NiO, MnO 2 and the like may be mixed at about several tens ppm. Also Pb
O is an undesirable component because it emits fluorescence by itself, but there is no problem if impurities are on the order of 100 ppm or less.
【００１４】[0014]
【実施例】ガラス原料として、還移金属不純物およびＣ
ｅＯ2 が１ｐｐｍ以下の超高純度原料を用い、これらの
混合物を白金製ルツボまたはアルミナ製ルツボで１４０
０〜１６００℃、２〜５時間熔融し、徐冷して得られた
ガラスを１０×１０×３０ｍｍの角柱に研摩して、合計
１５種の本発明の低蛍光性ガラス試料（表１中の試料Ｎ
ｏ．１〜１５に相当）を得た。EXAMPLES As glass raw materials, metal impurities and C
Using ultra-high-purity raw materials having eO 2 of 1 ppm or less, these mixtures were mixed with a platinum crucible or an alumina crucible for 140 minutes.
The glass obtained by melting at 0 to 1600 ° C. for 2 to 5 hours and slowly cooling was polished into 10 × 10 × 30 mm prisms, and a total of 15 low-fluorescent glass samples of the present invention (Table 1) Sample N
o. 1-15).
【００１５】次にこれらのガラス試料について島津製作
所製蛍光分光光度計ＲＦ−５０００を用いて蛍光強度を
測定した結果を表１に示す。なお、蛍光強度は、試料に
波長３００ｎｍまたは３５０ｎｍの光を照射したときの
入射光から７００ｎｍまでの範囲で発生した蛍光の最大
出力の相対値で示してある。Next, the results of measuring the fluorescence intensity of these glass samples using a fluorescence spectrophotometer RF-5000 manufactured by Shimadzu Corporation are shown in Table 1. The fluorescence intensity is shown as a relative value of the maximum output of the fluorescence generated in the range from the incident light to 700 nm when the sample is irradiated with light having a wavelength of 300 nm or 350 nm.
【００１６】比較のため、固体撮像素子のカバーガラス
としてしばしば使用されている無アルカリバリウムシリ
ケートガラスである市販ガラスＡ（組成は表１に明記）
および代表的な光学ガラスである市販ガラスＢ（組成は
表１に明記）についても同様に蛍光強度を測定した結果
を表１に示す。For comparison, commercially available glass A, which is an alkali-free barium silicate glass often used as a cover glass for a solid-state imaging device (the composition is specified in Table 1)
Table 1 shows the results of the same measurement of the fluorescence intensity of commercially available glass B (the composition is specified in Table 1), which is a typical optical glass.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【表３】 [Table 3]
【００２０】[0020]
【表４】 [Table 4]
【００２１】表１より明らかなように、本発明のガラス
試料Ｎｏ．１〜１５は、波長３００ｎｍの光を照射した
ときの３００〜７００ｎｍ間の最大蛍光強度が１．２６
以下であり、また波長３５０ｎｍの光を照射したときの
３５０〜７００ｎｍ間の最大蛍光強度が０．３８以下で
あり、いずれも市販のガラスＡおよびＢに比べ、著しく
小さいことが確認された。As is clear from Table 1, the glass sample No. of the present invention. Nos. 1 to 15 have a maximum fluorescence intensity between 300 and 700 nm when irradiated with light having a wavelength of 300 nm of 1.26.
And the maximum fluorescence intensity between 350 and 700 nm when irradiated with light having a wavelength of 350 nm is 0.38 or less.
It was confirmed that both were significantly smaller than commercially available glasses A and B.
【００２２】また表１の試料Ｎｏ．１の基礎ガラス組成
物（但し、Ａｓ2 Ｏ3 およびＳｂ2 Ｏ3 を除いたもの）
および表１の試料Ｎｏ．４の基礎ガラス組成物につい
て、脱泡剤であるＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3 、ＮａＣｌ、
ＫＦ、Ｎａ2 ＳＯ4 を添加し、それらの影響を調べた。
その結果を表２に示す。Further, the sample Nos. 1. Basic glass composition (excluding As 2 O 3 and Sb 2 O 3 )
And the sample Nos. Regarding the base glass composition of No. 4, As 2 O 3 , Sb 2 O 3 , NaCl
KF and Na 2 SO 4 were added and their effects were examined.
Table 2 shows the results.
【００２３】[0023]
【表５】 [Table 5]
【００２４】表２より、脱泡剤のうち、ＮａＣｌ、ＫＦ
およびＮａ2 ＳＯ4 はガラスベース組成により蛍光は影
響されないが、Ａｓ2Ｏ3 およびＳｂ2 Ｏ3 はガラスベ
ース組成により蛍光が大きく影響されることが判る。Table 2 shows that among the defoaming agents, NaCl, KF
It can be seen that the fluorescence of As 2 O 3 and Na 2 SO 4 is not affected by the glass base composition, whereas the fluorescence of As 2 O 3 and Sb 2 O 3 is greatly affected by the glass base composition.
【００２５】また表１の試料Ｎｏ．１の基礎ガラス組成
物および表１の試料Ｎｏ．４の基礎ガラス組成物につい
て、各種の成分を添加し、それらの影響を調べた。その
結果を表３に示す。Sample No. 1 in Table 1 1 and the sample No. 1 in Table 1. Various components were added to the base glass composition of No. 4, and their effects were examined. Table 3 shows the results.
【００２６】[0026]
【表６】 [Table 6]
【００２７】表３より、Ｖ2 Ｏ5 、ＣｕＯ、ＣｅＯ2は
蛍光を出すが、Ｃｒ2 Ｏ3 、ＭｎＯ2 、Ｆｅ2 Ｏ3 、Ｃ
ｏ2 Ｏ3 、ＮｉＯは蛍光を出していない。なお、Ｖ2 Ｏ
5 、ＣｕＯ、ＣｅＯ2 の蛍光ピーク波長はそれぞれ５０
０ｎｍ、４６５ｎｍ、３４０ｎｍ付近にあり、Ａｓ2 Ｏ
3 、Ｓｂ2 Ｏ3 の蛍光ピーク波長（それぞれ４５０ｎ
ｍ、３７０ｎｍ付近）とは明らかに異なる。一方、試料
Ｎｏ．１の組成物にＢａＯを２％、２０％と添加した時
の蛍光ピーク波長はＡｓ2 Ｏ3 、Ｓｂ2 Ｏ3 の波長と変
らず、ＢａＯ量の多い方が螢光が増大しているため、新
たな蛍光が発生したのではなく、Ａｓ2 Ｏ3 、Ｓｂ2 Ｏ
3の蛍光が増大したものと解釈される。From Table 3, V 2 O 5 , CuO and CeO 2 emit fluorescence, but Cr 2 O 3 , MnO 2 , Fe 2 O 3 and C 2
o 2 O 3 and NiO do not emit fluorescence. Note that V 2 O
5 , the fluorescent peak wavelengths of CuO and CeO 2 are 50
0 nm, 465 nm, 340 nm, and As 2 O
3 , the fluorescence peak wavelength of Sb 2 O 3 (450 n
m, around 370 nm). On the other hand, sample No. The fluorescence peak wavelength when adding BaO to 2% or 20% to the composition No. 1 is the same as the wavelength of As 2 O 3 or Sb 2 O 3 , and the fluorescence increases as the amount of BaO increases. No new fluorescence was generated, but As 2 O 3 , Sb 2 O
3 is interpreted as an increase in fluorescence.
【００２８】[0028]
【発明の効果】以上説明したように、本発明によれば、
蛍光が少なく、蛍光測定用溶液セルや、固体撮像素子の
カバーガラス等に好適に使用することができる低蛍光性
ガラスが提供された。As described above, according to the present invention,
There has been provided a low-fluorescence glass that has low fluorescence and can be suitably used for a solution cell for fluorescence measurement, a cover glass of a solid-state imaging device, and the like.
Claims (6)
ラス組成物に、この基礎ガラス組成物１００％に対し
て、 Ａｓ2Ｏ3 ４％以下 Ｓｂ2Ｏ3 ４％以下 Ａｓ2Ｏ3＋Ｓｂ2Ｏ3 ０．０５〜４％ Ｖ2Ｏ5 １０ｐｐｍ以下 ＣｕＯ １０ｐｐｍ以下 ＣｅＯ2 １ｐｐｍ以下 を含有すること特徴とする低蛍光性ガラス。1. The method of claim 1, wherein the weight of SiOTwo 45-80% BTwoOThree 0-25% AlTwoOThree 0 to 30% alkali metal oxide (RTwoO) 2-20%, and the total amount of these components is 90% or more.
In the glass composition, 100% of the base glass composition
And AsTwoOThree 4% or less SbTwoOThree 4% or less AsTwoOThree+ SbTwoOThree 0.05-4% VTwoOFive 10 ppm or less CuO 10 ppm or less CeOTwo A low-fluorescent glass containing 1 ppm or less.
ラス組成物に、この基礎ガラス組成物１００％に対し
て、 Ａｓ2Ｏ3 ０．０５％以下 Ｓｂ2Ｏ3 ０．０５％以下 Ａｓ2Ｏ3＋Ｓｂ2Ｏ3 ０．００００１〜０．０５％ Ｖ2Ｏ5 １０ｐｐｍ以下 ＣｕＯ １０ｐｐｍ以下 ＣｅＯ2 １ｐｐｍ以下 を含有すること特徴とする低蛍光性ガラス。2. An SiO 2 content of 45 to 80% B 2 O 3 0 to 25% Al 2 O 3 0 to 30% Alkali metal oxide (R 2 O) 0 to 20% Divalent metal oxide (RO) ) comprising 40% or less R 2 O + RO 2~40%, the basic glass composition total amount is 90% or more of these components, relative to the base glass composition 100%, as 2 O 3 0.05 % Or less Sb 2 O 3 0.05% or less As 2 O 3 + Sb 2 O 3 0.00001 to 0.05% V 2 O 5 10 ppm or less CuO 10 ppm or less CeO 2 1 ppm or less Low fluorescence Glass.
酸塩から選ばれる少なくとも１種を添加してなることを
特徴とする、請求項１または２に記載の低蛍光性ガラ
ス。3. The low-fluorescent glass according to claim 1, wherein at least one selected from chloride, fluoride and sulfate is added as a defoaming agent.
性ガラスを用いたことを特徴とする固体撮像素子保護用For protection of solid-state imaging devices characterized by the use of conductive glass
カバーガラス。cover glass.
００〜７００ｎｍ間の最大蛍光強度が１．２６以下で、The maximum fluorescence intensity between 00 and 700 nm is 1.26 or less,
かつ３５０ｎｍの光を照射したときの３５０〜７００ｎAnd 350 to 700 n when irradiated with 350 nm light
ｍ間の最大蛍光強度が０．３８以下となるように、蛍光m so that the maximum fluorescence intensity between m is 0.38 or less.
強度の高い成分の含有を防止したことを特徴とする固体A solid characterized by preventing the inclusion of high-strength components
撮像素子保護用カバーガラス。Cover glass for image sensor protection.
保護用カバーガラスにより、受光部を封止したことを特The fact that the light-receiving part is sealed with a protective cover glass
徴とする固体撮像素子。A solid-state image sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2402946A JP3043076B2 (en) | 1990-12-17 | 1990-12-17 | Low fluorescent glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2402946A JP3043076B2 (en) | 1990-12-17 | 1990-12-17 | Low fluorescent glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04219342A JPH04219342A (en) | 1992-08-10 |
| JP3043076B2 true JP3043076B2 (en) | 2000-05-22 |
Family
ID=18512710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2402946A Expired - Lifetime JP3043076B2 (en) | 1990-12-17 | 1990-12-17 | Low fluorescent glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3043076B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106233A (en) * | 1997-10-03 | 1999-04-20 | Nikon Corp | Low fluorescent optical glass and its production |
| JP4806157B2 (en) * | 2000-08-15 | 2011-11-02 | 株式会社オハラ | Low fluorescent optical glass |
| JP4628667B2 (en) * | 2002-11-15 | 2011-02-09 | 日本電気硝子株式会社 | Cover glass for solid-state image sensor |
| WO2007094373A1 (en) * | 2006-02-14 | 2007-08-23 | Nippon Sheet Glass Company, Limited | Glass composition |
| JP2008280235A (en) | 2007-04-09 | 2008-11-20 | Olympus Corp | Optical glass and optical device using the same |
| WO2009044873A1 (en) | 2007-10-05 | 2009-04-09 | Olympus Corporation | Optical glass, and optical device having the optical glass |
| WO2009044874A1 (en) | 2007-10-05 | 2009-04-09 | Olympus Corporation | Optical glass, and optical device having the optical glass |
| CN101896437A (en) | 2007-12-11 | 2010-11-24 | 奥林巴斯株式会社 | Optical glass and optical device using the same |
| TWI692459B (en) * | 2015-05-29 | 2020-05-01 | 日商Ａｇｃ股份有限公司 | UV transmission glass |
| US10710925B2 (en) * | 2015-07-17 | 2020-07-14 | Nippon Electric Glass Co., Ltd. | Borosilicate glass for pharmaceutical container |
| JP2017137213A (en) * | 2016-02-03 | 2017-08-10 | 日本電気硝子株式会社 | Glassware for raman spectroscopy |
| CN112811812A (en) * | 2021-01-12 | 2021-05-18 | 成都光明光电股份有限公司 | Low-fluorescence optical glass |
| CN112794643A (en) * | 2021-01-12 | 2021-05-14 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
-
1990
- 1990-12-17 JP JP2402946A patent/JP3043076B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04219342A (en) | 1992-08-10 |
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