JPH05279074A - Window glass for solid-state image pickup element package - Google Patents
Window glass for solid-state image pickup element packageInfo
- Publication number
- JPH05279074A JPH05279074A JP4322753A JP32275392A JPH05279074A JP H05279074 A JPH05279074 A JP H05279074A JP 4322753 A JP4322753 A JP 4322753A JP 32275392 A JP32275392 A JP 32275392A JP H05279074 A JPH05279074 A JP H05279074A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- solid
- state image
- image pickup
- window glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005357 flat glass Substances 0.000 title claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 39
- 230000005260 alpha ray Effects 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 238000003384 imaging method Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000002285 radioactive effect Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052776 Thorium Inorganic materials 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052705 radium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910007541 Zn O Inorganic materials 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Transforming Light Signals Into Electric Signals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ビデオカメラ等に使用
される固体撮像素子のパッケージ窓用として用いられる
ガラスに関し、特に固体撮像素子のノイズ発生を低減さ
せた固体撮像素子パッケージ用窓ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass used for a package window of a solid-state image pickup device used in a video camera or the like, and more particularly to a window glass for a solid-state image pickup device package in which noise generation of the solid-state image pickup device is reduced. ..
【０００２】[0002]
【従来の技術】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パッケージ内に納め、その
受光面に色分解モザイクフィルターを重ねてワイヤボン
ディングし、さらにその上にカバーガラスをエポキシ樹
脂または、ガラスフリットを用いて封着した構造となっ
ている。ここで用いられるカバーガラスは、アルミナセ
ラミックパッケージとの気密封着によりＬＳＩチップを
保護するだけではなく受光面へ効率的に光を導入するた
め、内部欠陥の少ない光学的に均質な材料特性、高い透
過率特性が要求される。また、このような用途に使用さ
れるガラスは、アルミナセラミックパッケージと封着さ
れた時に割れや歪みが発生してはならない。すなわち、
ガラスとアルミナセラミックパッケージの熱膨張係数を
適合させる必要がある。このため従来、この種のガラス
には、硼珪酸系のガラスが使用されてきた。2. Description of the Related Art A solid-state image sensor is an LSI that is a light-receiving element
The chip is housed in an alumina ceramic package, a color separation mosaic filter is overlaid on the light-receiving surface of the chip, wire bonding is performed, and a cover glass is sealed on the chip with epoxy resin or glass frit. The cover glass used here not only protects the LSI chip by hermetically sealing with the alumina ceramic package but also efficiently introduces light to the light-receiving surface, so that it has optically uniform material characteristics with few internal defects and high characteristics. Transmittance characteristics are required. Also, the glass used for such applications should not crack or distort when sealed with an alumina ceramic package. That is,
It is necessary to match the coefficient of thermal expansion of the glass and the alumina ceramic package. For this reason, borosilicate glass has been conventionally used for this type of glass.
【０００３】一方、通常のＩＣはもちろん、大容量メモ
リー素子など各種超ＬＳＩチップ半導体装置において、
アッセンブリに使用される気密封着用低融点ガラスある
いはその充填剤（フィラー）がα線粒子を放出し、ソフ
トエラーを発生することが知られている。これは、主と
して低融点ガラスの線膨脹係数の調整および強度向上を
目的として使用される充填剤（例えば、ジルコン Ｚｒ
ＳｉＯ4 など）が原因であり、放射性元素の分離が困難
である封着物質が使用された結果、α線放射率が著しく
増大し、高集積ＩＣの封止材料として用いることは適当
でないことが判明している。On the other hand, in addition to ordinary ICs, in various ultra-LSI chip semiconductor devices such as large-capacity memory devices,
It is known that the low melting point glass for airtightness or the filler thereof used in the assembly emits α-ray particles and causes a soft error. This is a filler mainly used for the purpose of adjusting the linear expansion coefficient of low melting glass and improving the strength (for example, zircon Zr.
Etc. SiO 4) is caused, as a result of the sealing material is difficult to separate the radioactive element is used, increased α-ray radiation rate significantly, it is not appropriate to use as a sealing material for highly integrated IC It's known.
【０００４】[0004]
【発明が解決しようとする課題】テレビカメラなどに応
用されるイメージセンサとしての固体撮像素子は、高解
像度化の要請からしだいに画素数を増加させる方向にあ
る。同時にカメラ一体型ＶＴＲの小型，軽量化の進展と
ともに、光学系は、１／２インチ系から１／３インチ系
への縮小化が進んでいる。したがって画素面積が全体的
に縮小化され更に画素数が増加するため、一画素当たり
の信号レベルは相対的に低下し、従来問題にならなかっ
た微小ノイズが画質向上の大きな妨げとなってきてい
る。固体撮像素子の高解像度化を達成するためには、一
画素当りの感度を上げるとともにできるだけノイズを減
らす必要がある。In the solid-state image pickup device as an image sensor applied to a television camera or the like, the number of pixels is gradually increasing due to the demand for higher resolution. At the same time, with the progress of miniaturization and weight reduction of the camera-integrated VTR, the optical system is being reduced from 1/2 inch system to 1/3 inch system. Therefore, the pixel area is reduced as a whole and the number of pixels is further increased, so that the signal level per pixel is relatively lowered, and minute noise which has not been a problem in the past has become a major obstacle to the improvement of image quality. .. In order to achieve high resolution of the solid-state image sensor, it is necessary to increase sensitivity per pixel and reduce noise as much as possible.
【０００５】本発明者らは、ＣＣＤなど固体撮像素子の
窓ガラスがα線放出性元素を大量に含有しα線粒子を放
出する場合、固体撮像素子に一過性の誤動作を引き起こ
しノイズとなることを見出した。α線粒子は、天然に存
在するウラン（Ｕ），トリウム（Ｔｈ），ラジウム（Ｒ
ａ）など放射性同位元素がα崩壊する際に放出される荷
電粒子である。α線粒子に起因するノイズをなくすため
には、ガラス中に不純物として含まれる放射性同位元素
を除去すればよい。このためにはできるだけ高純度に精
製された原料を使用し、溶融工程における不純物の混入
を防止してガラスを製造する必要がある。原料精製には
物理的・化学的各種方法があるが、技術的・経済的に限
界があり、特に放射性同位元素の分離が容易な原料と困
難な原料が存在するため、α線源となる放射性同位元素
を含まないガラスを容易に得ることは難しかった。When the window glass of a solid-state image pickup device such as a CCD contains a large amount of α-ray emitting elements and emits α-ray particles, the present inventors cause a transient malfunction of the solid-state image pickup device and cause noise. I found that. α-ray particles are naturally occurring uranium (U), thorium (Th), and radium (R).
It is a charged particle that is released when a radioactive isotope such as a) is α-decayed. In order to eliminate the noise caused by the α-ray particles, the radioactive isotope contained as an impurity in the glass may be removed. For this purpose, it is necessary to use raw materials that have been purified to the highest possible purity and prevent the mixing of impurities in the melting process to produce glass. Although there are various physical and chemical methods for refining raw materials, there are technical and economic limits, and there are raw materials in which radioactive isotopes can be easily separated and difficult ones exist. It was difficult to easily obtain isotope-free glass.
【０００６】本発明は、これらの事情を考慮してなされ
たもので、実質的にガラス、特にガラス中のα線放出性
元素に起因する固体撮像素子のノイズ発生がない固体撮
像素子パッケージ用窓ガラスを提供することを目的とす
る。The present invention has been made in consideration of these circumstances, and a window for a solid-state image pickup device package in which noise of the solid-state image pickup device caused by glass, particularly an α-ray emitting element in the glass is substantially not generated. Intended to provide glass.
【０００７】[0007]
【課題を解決するための手段】本発明は、上記目的を達
成するために、ガラス中の放射性同位元素の含有量の合
計を１００ｐｐｂ以下としたことを特徴とする固体撮像
素子パッケージ用窓ガラスである。In order to achieve the above object, the present invention provides a window glass for a solid-state imaging device package, wherein the total content of radioisotopes in the glass is 100 ppb or less. is there.
【０００８】また、ガラスからのα線放出量が０．０５
ｃ／ｃｍ2 ・ｈ以下としたものである。The amount of α rays emitted from glass is 0.05
c / cm 2 · h or less.
【０００９】さらに、これらいずれかのの要件を満足
し、本発明の用途に適合するガラス組成としては、重量
百分率でＳｉＯ2 ５０〜７５％，Ａｌ2 Ｏ3 ０．２
〜５．０％，Ｂ2 Ｏ3 ５〜２０％，Ｌｉ2 Ｏ ０〜１
％，Ｎａ2 Ｏ ０．５〜９．５％，Ｋ2 Ｏ ０．２〜６
％，Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ５〜１２％，ＭｇＯ
０〜３％，ＣａＯ ０〜５％，ＢａＯ ０〜６％，Ｚｎ
Ｏ ０〜５％，ＭｇＯ＋ＣａＯ＋ＢａＯ＋ ０〜１２
％，Ａｓ2 Ｏ3 ０〜１％，Ｓｂ2 Ｏ3 ０〜１％，Ｃ
ｌ- ０〜０．２％，Ｆ- ０〜０．５％，Ａｓ2 Ｏ3 ＋Ｓ
ｂ2 Ｏ3 ＋Ｃｌ-＋Ｆ- ０．０２〜１．５％の基本組
成を有し、熱膨張係数が４８〜７５×１０-7Ｋ-1である
ものが好適する。Further, as a glass composition satisfying any of these requirements and adapted to the use of the present invention, SiO 2 50 to 75% by weight percentage, Al 2 O 3 0.2
~5.0%, B 2 O 3 5~20 %, Li 2 O 0~1
%, Na 2 O 0.5 to 9.5%, K 2 O 0.2 to 6
%, Li 2 O + Na 2 O + K 2 O 5-12%, MgO
0-3%, CaO 0-5%, BaO 0-6%, Zn
O 0-5%, MgO + CaO + BaO + 0-12
%, As 2 O 3 0 to 1%, Sb 2 O 3 0 to 1%, C
l - 0~0.2%, F - 0~0.5 %, As 2 O 3 + S
b 2 O 3 + Cl − + F − having a basic composition of 0.02 to 1.5% and a coefficient of thermal expansion of 48 to 75 × 10 −7 K −1 is preferable.
【００１０】[0010]
【作用】次に本発明のガラスを構成する成分の作用と、
その含有量を上記のように限定した理由を説明する。Next, the action of the components constituting the glass of the present invention,
The reason for limiting the content as described above will be described.
【００１１】ＳｉＯ2 が５０％未満では、熱膨脹係数が
大きくなりアルミナセラミックパッケージとの気密封着
に支障をきたし、７５％を越えるとガラスの溶融性が悪
化する。Ｂ2 Ｏ3 は、５％未満では溶融性が悪くなり、
２０％を越えると化学耐久性が悪化し長期間使用時に表
面にウェザリングを生じ画像を不鮮明にする。Ａｌ2Ｏ
3 は０．２％未満では、ガラスの分相が生じ成形が困難
になり、５％を越えると脈理が発生して均質なガラスが
得られなくなる。Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏは、融剤
として作用しガラスの溶融性を改良するが、同時にガラ
スの熱膨脹係数を調整する効果があり、その合量が５％
以下では粘度が高くなり溶融性が悪化すると共に熱膨脹
係数も低くなり過ぎる。また、１２％を越える場合は耐
風化性が悪くなるとともに、熱膨脹係数が高くなり過ぎ
るため不適となる。ＺｎＯは、Ｂ2 Ｏ3 やアルカリ成分
の溶融時の揮発を抑える効果があるが、５％を越えると
失透性が増す。ＢａＯやＭｇＯ，ＣａＯは、５〜６％以
下の使用で化学耐久性を向上させる効果がある。ＺｎＯ
も同様な効果をもつが、その合量が１２％をこえると失
透性が増大する。また、上記ガラスの清澄剤としては、
Ａｓ2 Ｏ3 ，Ｓｂ2Ｏ3 ，Ｆ- ，Ｃｌ- が各々１％未満
で使用されるが、その合量が０．０２％未満では十分な
清澄効果が得られず、１．５％以上では再発泡を生ずる
ため望ましくない。If the SiO 2 content is less than 50%, the coefficient of thermal expansion becomes large, which hinders the airtight adhesion to the alumina ceramic package, and if it exceeds 75%, the meltability of the glass deteriorates. When B 2 O 3 is less than 5%, the meltability becomes poor,
If it exceeds 20%, the chemical durability is deteriorated and weathering occurs on the surface during long-term use to make the image unclear. Al 2 O
If the content of 3 is less than 0.2%, phase separation of the glass occurs and molding becomes difficult, and if it exceeds 5%, striae occur and uniform glass cannot be obtained. Li 2 O + Na 2 O + K 2 O acts as a flux and improves the meltability of the glass, but at the same time it has the effect of adjusting the coefficient of thermal expansion of the glass, and the total amount is 5%.
Below, the viscosity becomes high, the meltability deteriorates, and the thermal expansion coefficient becomes too low. On the other hand, if it exceeds 12%, the weather resistance becomes poor and the coefficient of thermal expansion becomes too high, which is not suitable. ZnO has an effect of suppressing volatilization of B 2 O 3 and an alkali component at the time of melting, but if it exceeds 5%, devitrification increases. BaO, MgO, and CaO have the effect of improving chemical durability when used in an amount of 5 to 6% or less. ZnO
Also has a similar effect, but if the total amount exceeds 12%, devitrification increases. Further, as the glass fining agent,
As 2 O 3 , Sb 2 O 3 , F − , and Cl − are used in an amount of less than 1% each, but if the total amount is less than 0.02%, a sufficient refining effect cannot be obtained and 1.5% or more. Is not desirable because it causes re-foaming.
【００１２】上記ガラスは、その有効組成を形成するた
め原料を精製することができ、含有されるα放射性元素
（Ｕ，Ｔｈ，Ｒａなど）を１００ｐｐｂ以内に抑えるこ
とが可能である。また、α放射性元素の濃度が１００ｐ
ｐｂを越えると、α線放出量が０．０５ｃ／ｃｍ2 ・ｈ
以上に増大し、固体撮像素子のノイズ発生の原因とな
る。したがって固体撮像素子パッケージ用窓ガラスから
のα線放出率を０．０５ｃ／ｃｍ2 ・ｈ以下に抑えるこ
とが好ましい。In order to form the effective composition of the above-mentioned glass, the raw material can be refined and the contained α-radioactive elements (U, Th, Ra, etc.) can be suppressed within 100 ppb. In addition, the concentration of α radioactive element is 100p
When it exceeds pb, the amount of α-ray emission is 0.05 c / cm 2 · h
It increases above, and causes noise in the solid-state image sensor. Therefore, it is preferable to suppress the α-ray emission rate from the window glass for a solid-state imaging device package to 0.05 c / cm 2 · h or less.
【００１３】また、α放射性元素の精製分離が困難なＦ
ｅ2 Ｏ3 ，ＴｉＯ2 ，ＰｂＯ，ＺｒＯ2 等については、
原料や溶融工程からの混入を防止する必要がある。たと
えガラス中にこれらが混入した場合でも、各々１００ｐ
ｐｍ以下に抑えることが望ましい。これらの成分が各々
１００ｐｐｍを越えて含有されるとα放射性元素の濃度
が１００ｐｐｂを越え、α線放出量が急激に増大するか
らである。Further, it is difficult to purify and separate α-radioactive elements from F.
For e 2 O 3 , TiO 2 , PbO, ZrO 2, etc.,
It is necessary to prevent contamination from the raw materials and the melting process. Even if these are mixed in the glass, each 100p
It is desirable to suppress it to pm or less. This is because if each of these components exceeds 100 ppm, the concentration of the α-radioactive element exceeds 100 ppb, and the amount of α-ray emission sharply increases.
【００１４】平均熱膨張係数（０〜３００℃）を４８〜
７５×１０-7℃-1に限定した理由は、パッケージ材料が
主としてアルミナ（Ａｌ2 Ｏ3 ）セラミックとなるた
め、エポキシ系樹脂封着あるいはフリットガラス封着い
ずれの場合も、熱膨張係数をアルミナと同一、または低
めに保持し封着強度の向上、そりなどの変形を防止する
ためである。The average coefficient of thermal expansion (0 to 300 ° C.) is 48 to
The reason for limiting the temperature to 75 × 10 -7 ° C -1 is that the packaging material is mainly alumina (Al 2 O 3 ) ceramic, and therefore the thermal expansion coefficient is set to alumina in both epoxy resin sealing and frit glass sealing. This is for keeping the same as or lower than the above to improve the sealing strength and prevent deformation such as warpage.
【００１５】[0015]
【実施例】以下、本発明の実施例について説明する。本
発明の実施例を表１に示す。表１中試料No.1ないしNo.6
は本発明の実施例を示し、No.7は従来例である。また表
中の組成は重量比で示してある。EXAMPLES Examples of the present invention will be described below. Examples of the present invention are shown in Table 1. Sample No.1 to No.6 in Table 1
Shows an example of the present invention, and No. 7 is a conventional example. The compositions in the table are shown by weight ratio.
【００１６】表１に示した組成に従い、各種高純度に精
製された原料を使用し最終ガラス組成として１０００ｇ
となるよう調合し混合した後、１４８０℃の電気炉中で
５時間白金ルツボを使用して溶融した。その後炉内より
取り出し、鉄板上に成形したブロックを６００℃の温度
の電気炉に移し室温まで徐冷し、得られたガラスを所定
の寸法に光学研磨加工した。これらガラス板より放出さ
れるα線量の測定は、２πガスフロー式比例計数管を用
いた超低レベルα線測定装置で行ない、同時に遷移元素
とα線放射元素の化学分析をＩＣＰ−ＭＡＳＳにより測
定し、ＴＭＡ分析装置により平均熱膨張係数を測定し
た。そして、これらのガラスを実際に有効画素数３８万
画素のＣＣＤチップを内臓したアルミナパッケージに封
着して、固体撮像素子に使用した場合のノイズの有無を
調査した。また比較例としてα線放射元素を含有したガ
ラスを調整し、同様の試験に供した。According to the composition shown in Table 1, various high-purity raw materials were used and the final glass composition was 1000 g.
After being mixed and mixed so as to be, the mixture was melted in a platinum crucible for 5 hours in an electric furnace at 1480 ° C. After that, it was taken out of the furnace, the block formed on the iron plate was transferred to an electric furnace at a temperature of 600 ° C. and gradually cooled to room temperature, and the obtained glass was optically polished to a predetermined size. The α dose emitted from these glass plates is measured by an ultra low level α ray measuring device using a 2π gas flow type proportional counter, and at the same time, chemical analysis of transition elements and α ray emitting elements is measured by ICP-MASS. Then, the average thermal expansion coefficient was measured by a TMA analyzer. Then, these glasses were actually sealed in an alumina package containing a CCD chip having an effective pixel number of 380,000 pixels, and the presence or absence of noise when used in a solid-state imaging device was investigated. As a comparative example, a glass containing an α-ray emitting element was prepared and subjected to the same test.
【００１７】[0017]
【表１】 [Table 1]
【００１８】表１の結果より、Ｕ，Ｔｈ，Ｒａのα放射
性元素の含有量の合量が１００ｐｐｂ以下である１〜６
のサンプルでは、α線放出量は０．０５ｃ／ｃｍ2 ・ｈ
以下であって固体撮像素子におけるノイズもみられな
い。これに対して、上記含有量が本発明の範囲より外れ
ている従来例では、α線放出量は０．０５ｃ／ｃｍ2 ・
ｈ以上に高くなり固体撮像素子におけるノイズが発生し
ている。From the results shown in Table 1, the total content of α-radioactive elements of U, Th, and Ra is 100 ppb or less, and 1 to 6
Sample, the amount of α-ray emission is 0.05 c / cm 2 · h
It is below, and no noise is observed in the solid-state image sensor. On the other hand, in the conventional example in which the above content is out of the range of the present invention, the α-ray emission amount is 0.05 c / cm 2 ·
It becomes higher than h and noise is generated in the solid-state image sensor.
【００１９】[0019]
【発明の効果】以上のように本発明のガラスは、α線放
出量が低く、固体撮像素子のパッケージ用窓ガラスとし
て使用した場合、ガラスからのα線に起因するノイズの
発生を著しく低減することができる。また光学的、熱的
特性にも優れているため、アルミナセラミックパッケー
ジと封着した際に歪みの発生がなく、固体撮像素子上の
結像に歪みを生じない。したがって、本発明のガラス
は、固体撮像素子のパッケージ用窓ガラスとして極めて
好適し、固体撮像素子の高解像度化に貢献することがで
きる。As described above, the glass of the present invention has a low α-ray emission amount, and when used as a window glass for a package of a solid-state image pickup element, the generation of noise due to α-ray from the glass is remarkably reduced. be able to. Further, since it has excellent optical and thermal characteristics, no distortion occurs when it is sealed with the alumina ceramic package, and no distortion occurs in the image formation on the solid-state imaging device. Therefore, the glass of the present invention is extremely suitable as a window glass for a package of a solid-state image sensor, and can contribute to high resolution of a solid-state image sensor.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年３月２５日[Submission date] March 25, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Name of item to be corrected] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】さらに、これらいずれかのの要件を満足
し、本発明の用途に適合するガラス組成としては、重量
百分率でＳｉＯ2 ５０〜７５％，Ａｌ2 Ｏ3 ０．２
〜５．０％，Ｂ2 Ｏ3 ５〜２０％，Ｌｉ2 Ｏ ０〜１
％，Ｎａ2 Ｏ ０．５〜９．５％，Ｋ2 Ｏ ０．２〜６
％，Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ５〜１２％，ＭｇＯ
０〜３％，ＣａＯ ０〜５％，ＢａＯ ０〜６％，Ｚｎ
Ｏ ０〜５％，ＭｇＯ＋ＣａＯ＋ＢａＯ＋ＺｎＯ ０〜
１２％，Ａｓ2 Ｏ3 ０〜１％，Ｓｂ2 Ｏ3 ０〜１％，
Ｃｌ- ０〜０．２％，Ｆ- ０〜０．５％，Ａｓ2 Ｏ3 ＋
Ｓｂ2 Ｏ3 ＋Ｃｌ- ＋Ｆ- ０．０２〜１．５％の基本
組成を有し、熱膨張係数が４８〜７５×１０-7Ｋ-1であ
るものが好適する。Further, as a glass composition satisfying any of these requirements and adapted to the use of the present invention, SiO 2 50 to 75% by weight percentage, Al 2 O 3 0.2
~5.0%, B 2 O 3 5~20 %, Li 2 O 0~1
%, Na 2 O 0.5 to 9.5%, K 2 O 0.2 to 6
%, Li 2 O + Na 2 O + K 2 O 5-12%, MgO
0-3%, CaO 0-5%, BaO 0-6%, Zn
O 0-5%, MgO + CaO + BaO + ZnO 0-
12%, As 2 O 3 0 to 1%, Sb 2 O 3 0 to 1%,
Cl - 0~0.2%, F - 0~0.5 %, As 2 O 3 +
Sb 2 O 3 + Cl − + F − having a basic composition of 0.02 to 1.5% and a coefficient of thermal expansion of 48 to 75 × 10 −7 K −1 is preferable.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１７】[0017]
【表１】 [Table 1]
Claims (3)
計が１００ｐｐｂ以下であることを特徴とする固体撮像
素子パッケージ用窓ガラス。1. A window glass for a solid-state imaging device package, wherein the total content of radioisotopes in the glass is 100 ppb or less.
ｃｍ2 ・ｈ以下であることを特徴とする固体撮像素子パ
ッケージ用窓ガラス。2. The amount of α-ray emission from glass is 0.05 c /
A window glass for a solid-state imaging device package, which is characterized by having a cm 2 · h or less.
Ａｌ2 Ｏ3 ０．２〜５．０％，Ｂ2 Ｏ3 ５〜２０
％，Ｌｉ2 Ｏ ０〜１％，Ｎａ2 Ｏ ０．５〜９．５
％，Ｋ2 Ｏ ０．２〜６％，Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2
Ｏ ５〜１２％，ＭｇＯ ０〜３％，ＣａＯ ０〜５
％，ＢａＯ ０〜６％，ＺｎＯ ０〜５％，ＭｇＯ＋Ｃ
ａＯ＋ＢａＯ＋ ０〜１２％，Ａｓ2 Ｏ3 ０〜１％，
Ｓｂ2 Ｏ3 ０〜１％，Ｃｌ- ０〜０．２％，Ｆ- ０〜
０．５％，Ａｓ2 Ｏ3 ＋Ｓｂ2 Ｏ3 ＋Ｃｌ- ＋Ｆ-
０．０２〜１．５％の基本組成を有し、熱膨張係数が４
８〜７５×１０-7Ｋ-1であることを特徴とする請求項１
または２のいずれかに記載の固体撮像素子パッケージ用
窓ガラス。3. SiO 2 50-75% by weight,
Al 2 O 3 0.2-5.0%, B 2 O 3 5-20
%, Li 2 O 0 to 1%, Na 2 O 0.5 to 9.5
%, K 2 O 0.2 to 6%, Li 2 O + Na 2 O + K 2
O 5-12%, MgO 0-3%, CaO 0-5
%, BaO 0-6%, ZnO 0-5%, MgO + C
aO + BaO + 0 to 12%, As 2 O 3 0 to 1%,
Sb 2 O 3 0~1%, Cl - 0~0.2%, F - 0~
0.5%, As 2 O 3 + Sb 2 O 3 + Cl − + F −
It has a basic composition of 0.02 to 1.5% and a thermal expansion coefficient of 4
It is 8 to 75 × 10 -7 K -1.
Or the window glass for a solid-state image sensor package as described in any one of 2 above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-19524 | 1992-01-08 | ||
| JP1952492 | 1992-01-08 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06548497A Division JP3206804B2 (en) | 1997-03-03 | 1997-03-03 | Window glass for solid-state imaging device package |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05279074A true JPH05279074A (en) | 1993-10-26 |
| JP2660891B2 JP2660891B2 (en) | 1997-10-08 |
Family
ID=12001732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4322753A Expired - Lifetime JP2660891B2 (en) | 1992-01-08 | 1992-11-06 | Window glass for solid-state image sensor package |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2660891B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011168455A (en) * | 2010-02-19 | 2011-09-01 | Asahi Glass Co Ltd | Near-infrared light cutting filter glass |
| JP2012049400A (en) * | 2010-08-27 | 2012-03-08 | Canon Inc | Optical sensor manufacturing method, optical sensor, and camera |
| JP2012094904A (en) * | 2005-05-10 | 2012-05-17 | Nippon Electric Glass Co Ltd | Glass substrate for semiconductor element and chip scale package using the same |
| JP2013235933A (en) * | 2012-05-08 | 2013-11-21 | Nikon Corp | Imaging element and manufacturing method of the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5378158B2 (en) * | 2003-02-19 | 2013-12-25 | 日本電気硝子株式会社 | Cover glass for semiconductor packages |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62176940A (en) * | 1987-01-24 | 1987-08-03 | Mitsubishi Metal Corp | Lead borate for low-melting point glass for sealing semiconductor device and its production |
| JPS6398660U (en) * | 1986-12-18 | 1988-06-25 | ||
| JPH01173639A (en) * | 1987-12-26 | 1989-07-10 | Sony Corp | Solid-state image sensing device |
-
1992
- 1992-11-06 JP JP4322753A patent/JP2660891B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6398660U (en) * | 1986-12-18 | 1988-06-25 | ||
| JPS62176940A (en) * | 1987-01-24 | 1987-08-03 | Mitsubishi Metal Corp | Lead borate for low-melting point glass for sealing semiconductor device and its production |
| JPH01173639A (en) * | 1987-12-26 | 1989-07-10 | Sony Corp | Solid-state image sensing device |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012094904A (en) * | 2005-05-10 | 2012-05-17 | Nippon Electric Glass Co Ltd | Glass substrate for semiconductor element and chip scale package using the same |
| JP2011168455A (en) * | 2010-02-19 | 2011-09-01 | Asahi Glass Co Ltd | Near-infrared light cutting filter glass |
| JP2012049400A (en) * | 2010-08-27 | 2012-03-08 | Canon Inc | Optical sensor manufacturing method, optical sensor, and camera |
| US8790950B2 (en) | 2010-08-27 | 2014-07-29 | Canon Kabushiki Kaisha | Method of manufacturing optical sensor, optical sensor, and camera including optical sensor |
| JP2013235933A (en) * | 2012-05-08 | 2013-11-21 | Nikon Corp | Imaging element and manufacturing method of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2660891B2 (en) | 1997-10-08 |
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