CN1616364A - Layer coated glass for encapsulating semiconductor - Google Patents

Layer coated glass for encapsulating semiconductor Download PDF

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Publication number
CN1616364A
CN1616364A CN 200410092909 CN200410092909A CN1616364A CN 1616364 A CN1616364 A CN 1616364A CN 200410092909 CN200410092909 CN 200410092909 CN 200410092909 A CN200410092909 A CN 200410092909A CN 1616364 A CN1616364 A CN 1616364A
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glass
layer coated
coated glass
encapsulating semiconductor
content
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CN100418911C (en
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桥本幸市
二上勉
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • 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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • 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
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium

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  • 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)
  • Solid State Image Pick-Up Elements (AREA)

Abstract

The present invention relates to a cover glass plate for a semiconductor package containing no As2O3 as a clarifier and containing fewer bubbles while restricting contents of Sb2O3 or Sb2O5. The glass contains, by mass %, 58-72% SiO2, 0.5-15% Al2O3, 8-18% B2O3, 7.5-20% alkali metal oxide, 0-20% alkaline earth metal oxide, 0-10% ZnO, 0-0.2% Sb2O3+Sb2O5, 0.01-3% F2+Cl2+C+SO3>+SnO2 and does not substantially contain As2O3.

Description

Layer coated glass for encapsulating semiconductor
Technical field
The present invention relates generally to the layer coated glass for encapsulating semiconductor that the protection solid-state imager that is installed in the semiconductor packages front of accommodating solid-state imager uses as light inlet window simultaneously.
Background technology
In the solid-state imager front, in order to protect semiconductor element, be equipped with cladding glasses with tabular transparent surface.This cladding glasses is in the encapsulation that is formed by stupaliths such as aluminum oxide or metallic substance or resin material; the adhesives that adopts various organic resins or low melting glass to constitute seals, and plays a part the light inlet window of visible light etc. in the solid-state imager that accommodate protection packaging inside.
As solid-state imager, using maximum photosemiconductors at present is CCD (charge coupled device, Charge Coupled Device).Because CCD can absorb high-precision image, mainly be used in the pick up camera in the past, in recent years, along with the application of the data processing of image is quickened, the use field just sharply enlarges.Particularly be placed in digital still camera (digital camera) or the mobile telephone, be used for changing high-precision image into the electronic information data, use increasing day by day.In addition, require simultaneously with saving spatial, packaged material has the tendency of attenuation gradually, compares with resin package, progressively adopts the high alumina-ceramic encapsulation of strength reliability.
CCD must correctly change image into electronic information, therefore, at its surperficial employed cladding glasses, adheres to etc. for spot, wound, the foreign matter on surface and to be provided with strict standard, requires to have high-quality cleanliness factor.In addition, except surface cleanliness, also require glass inside should not have bubble, drawing lines (Veins reason), crystallization etc., and prevent that foreign matter such as platinum from sneaking into.Moreover, in order to realize good sealing, require to have proximate thermal linear expansion coefficient with packaged material with various encapsulation.And, the excellent weather resistance that this glass also requires the long-time surface quality of process also not reduce, and can realize light-weighted low density.Moreover if contain radio isotope U (uranium) or Th (thorium), then easily from glass radiation alpha-ray, its radiation quantity is too much, can produce the noise (soft error, soft error) of solid-state imager in the glass, therefore, requires not contain U, Th as far as possible.For this reason, when making glass, the inwall that has adopted the melting furnaces of selecting high-purity raw for use or will fusing raw material is with countermeasures such as the few refractory materials of radio isotope (for example aluminum oxide electrocast refractories, quartzy series refractory material, platinum) formation.For example, the scheme that reduces radio isotope, reduced the solid-state imager layer coated glass for encapsulating of alpha-ray discharging amount has been proposed in the patent documentation 1～3.
No. 2660891 communique of [patent documentation 1] Japanese Patent
[patent documentation 2] spy opens flat 6-211539 communique
[patent documentation 3] spy opens flat 7-215733 communique
Summary of the invention
In the aforesaid solid-state imager layer coated glass for encapsulating, require subsurface defects such as bubble few.This is because the bubble amount is many in the glass, forms optical defect, and noise takes place solid-state imager easily.In order to obtain the few homogeneous glass of bubble, the gas that produces in the time of vitrifying should being reacted is discharged from glass metal with clarification gas, when homogenizing is clarified, residual micro-bubble is produced once more then, makes bubble directly become floating removing on the ambassador by clarification gas.
In the past, as such glass fining agent, widely used was the As that can produce clarification gas in wide temperature range (about 1300～1700 ℃) 2O 3But, As 2O 3In raw material, contain radio isotope easily, have from the many problems of glass radiating alpha-ray discharging amount.
Because this situation, As an alternative 2O 3Finings, progressively used Sb 2O 3Or Sb 2O 5But, Sb 2O 3Or Sb 2O 5Be the material that environment is polluted, wish not contain as far as possible.
In view of the above fact, technical task of the present invention just provides layer coated glass for encapsulating semiconductor, does not contain the As finings 2O 3, and limited Sb 2O 3Or Sb 2O 5Content, simultaneously bubble is few.
For solving above-mentioned technical task, layer coated glass for encapsulating semiconductor of the present invention is characterised in that, in quality %, contains SiO 258～72%, Al 2O 30.5 B～15%, 2O 38～18%, alkalimetal oxide 7.5～20%, alkaline-earth metals oxide 0～20%, ZnO 0～10%, Sb 2O 3+ Sb 2O 50～0.2%, F 2+ Cl 2+ C+SO 3+ SnO 20.01～3%, in fact do not contain As 2O 3
In fact layer coated glass for encapsulating semiconductor of the present invention owing to do not contain As 2O 3, can prevent radioisotopic the sneaking into that cause thus, and to contain total amount be 0.01～3% F 2, Cl 2, C, SO 3, SnO 2, can obtain good clarification, reduce bubble.
Embodiment
Layer coated glass for encapsulating semiconductor of the present invention in quality %, contains SiO 258～72%, Al 2O 30.5 B～15%, 2O 38～18%, the essentially consist of alkalimetal oxide 7.5～20%, alkaline-earth metals oxide 0～20%, ZnO 0～10% is because contain Sb as finings 2O 3+ Sb 2O 50～0.2%, F 2+ Cl 2+ C+SO 3+ SnO 2+ CeO 20.01～3%, even do not contain As 2O 3, also can eliminate the bubble that becomes optical defect.
Glass with above-mentioned composition can easily reduce the U, the Th that sneak into from frit, and for example the U content in the glass is controlled at below the 5ppb, Th content is controlled at below the 10ppb.Its result, the Alpha-ray burst size of being sent by glass can be reduced to 0.005c/cm 2Below the hr, can reduce the noise of the solid-state imager that alpha-ray causes.Further, by make U content below the 4ppb, Th content below 8ppb, the Alpha-ray burst size of being sent by glass can be reduced to 0.003c/cm 2Below the hr.Like this, even be placed in the small-sized solid camera head of high pixel count (for example more than 1,000,000 pixels), also can realize reducing the purpose of the noise that alpha-ray causes.In addition, compare with Th, the easier alpha-ray that sends of U, therefore, the permission content of U allows content to compare and will lack with Th.
In addition, layer coated glass for encapsulating semiconductor of the present invention, in 30～380 ℃ temperature range, mean thermal expansion coefficients can be adjusted into 30～85 * 10 -7/ ℃.Like this, even use the adhesives that adopts organic resin or low melting glass to constitute to carry out aluminum oxide encapsulation (about 70 * 10 -7/ ℃) or various resin package seal, inside does not deform yet, and can keep good sealed state for a long time.The preferred thermal expansivity of cladding glasses is 35～80 * 10 -7/ ℃, more preferably thermal expansivity is 50～75 * 10 -7/ ℃.
In addition, layer coated glass for encapsulating semiconductor of the present invention can be adjusted to 2.45g/cm with the density of glass 3Below, the alkali stripping quantity adjusts to below the 1.0mg purposes of using in the portable electric appts that is particularly suitable for using out of doors.In other words, because pick up camera, digital still camera (digital camera), mobile telephone, PDA (personal digital assistant, Personal DigitalAssistant) etc. equipment also has situation about using out of doors, require in light weight, be suitable for holding usefulness, have high-weatherability.Therefore, the solid-state imager layer coated glass for encapsulating that uses in these purposes except the characteristic of light weight, also should have stable weathering resistance, even harsh and unforgiving environments out of doors uses the characteristic that surface quality does not also reduce down.For this reason, wish to be used for this purposes cladding glasses lightweight by reducing glass density, improve weathering resistance by reducing the alkali stripping quantity.
In addition, layer coated glass for encapsulating semiconductor of the present invention, preferred thickness is 0.05～0.7mm.If it is big that thickness becomes, transmittance reduces, and becomes light-weighted obstruction.In addition, if thickness is thin excessively, or the practical intensity deficiency, or the flexural deformation of massive plate glass (わ body) becomes big, is difficult to handle.More preferably thickness 0.1～0.5mm, preferred thickness is 0.1～0.4mm again.
The reason that each component content that constitutes layer coated glass for encapsulating semiconductor of the present invention is carried out above-mentioned restriction below is described.
SiO 2Be the main component that constitutes the glass skeleton, the effect of the weathering resistance that improves glass is arranged, but content be too much, the high temperature viscosity of glass rises, and meltbility or clarification property have the tendency of deterioration.Therefore, SiO 2Content is 58～72%, and is preferred 60～70%, more preferably 62～68.5%.
Al 2O 3Be the composition that improves the glass weathering resistance, but content is too much, the high temperature viscosity of glass rises, and meltbility or clarification property have the tendency of deterioration.Therefore, Al 2O 3Content is 0.5～15%, preferred 1.1～12%, more preferably 3.5～12%, most preferably 5.5～11%.
B 2O 3Working as fusing assistant, is the composition that reduces glass adhesion, improves meltbility or clarification property.But B 2O 3Content is too much, and the weathering resistance of glass reduces, and volatilization becomes many during fusion, is easy to generate drawing lines.So B 2O 3Content be 8～18%, preferred 9～18%, more preferably 11～18%, most preferably 12～17%.
Alkalimetal oxide (Na 2O, K 2O, Li 2O) be viscosity, raising meltbility and the clarification property that reduces glass, the composition of adjusting thermal expansivity.But these component contents are too much, and thermal expansivity has the tendency that becomes big, and the weathering resistance of glass significantly reduces.Therefore the content of alkalimetal oxide is 7.5～20%, and is preferred 8～20%, more preferably 9～15%.Should illustrate, because Li 2Contain radio isotope in the O raw material easily, its content should be restricted to 0～6%, preferred 0～5.5%, and more preferably 0～5%, preferred again 0～4.5%, most preferably 0～1.0%.
Alkaline-earth metals oxide (MgO, CaO, SrO, BaO) is when improving the weathering resistance of glass, reduce glass viscosity, improve the composition of meltbility, but content is too much, the easy devitrification of glass, density has the tendency of rising simultaneously.Therefore the content of alkaline-earth metals oxide is 0～20%, and is preferred 0.5～18%, more preferably 1.0～18%.
CaO particularly, owing to can obtain high-purity raw with comparalive ease, and it is good to improve the effect of weathering resistance, preferably contains 0.5～10%, preferably contains 1～8% again.Should illustrate, the density because BaO and SrO raise easily, and contain radio isotope in the raw material easily, preferred content is each defined in below 3%, more preferably is each defined in below 1.4%.
It is good that ZnO improves the weathering resistance effect, and have the glass melting of improvement, inhibition B 2O 3Or alkalimetal oxide is from the evaporable effect of melten glass, but content is too much, the easy devitrification of glass, and density rises, so content should be limited in below 10%, and preferred below 9%, more preferably below 6%.Especially, among the present invention, Al 2O 3After reaching below 3%, weathering resistance has significantly reduced tendency.In addition, B 2O 3Reach more than 14%, it is many that volatilization becomes, and is easy to generate drawing lines.For this reason, Al 2O 3Be below 3% or B 2O 3Be under the situation more than 14%, preferably contain more than the ZnO2%, more preferably contain more than 4.5%.
Sb 2O 3And Sb 2O 5Work as finings, should use less as far as possible from environmental.Therefore, Sb 2O 3And Sb 2O 5Total content be 0～0.2%, preferred 0～0.1%, most preferably in fact do not contain.In addition, among the present invention, the meaning of so-called " in fact not containing " is to be reduced to the amount of sneaking into as impurity.
F 2, Cl 2, C, SO 3, SnO 2, CeO 2All are the compositions that work as finings.These finingss and As 2O 3Or Sb 2O 3It is poor to compare clarification, but the cladding glasses viscosity of the present invention with above-mentioned composition is low, and clarification easily is therefore at F 2, Cl 2, C, SO 3, SnO 2, CeO 2As long as in contain more than a kind or 2 kinds and 0.01～3% just can fully outgas.Should illustrate that above-mentioned finings content is many more, clarifying effect is big more, the therefore preferred content 0.02～3%, more preferably 0.05～3%, most preferably 0.2～3% that adds up to.
In addition, glass of the present invention is equivalent to 10 at high temperature viscosity 2.5Temperature during pool is about 1300～1600 ℃.Cl particularly 2And SO 3, be easy to generate clarification gas in such temperature range, its add up to content preferred 0.02～2%, more preferably contain 0.05～2%.But CeO 2Make glass coloring, its content should be controlled at 1%, more preferably below 0.7%.
In addition, among the present invention, except that mentioned component,, can contain P in the scope below 5% in the scope of the characteristic of glass 2O 5, Y 2O 3, Nb 2O 3, La 2O 3Deng composition.
Should illustrate, as mentioned above, if used As 2O 3, sneak into radio isotope easily, should in fact not contain.And PbO, CdO be the composition of strong toxicity, should avoid using.
In addition, Fe 2O 3Use though also can be used as finings, can make glass coloring, its content should be controlled at below the 500ppm, below the preferred 300ppm, more preferably below the 200ppm.
TiO 2Though the weathering resistance of improving glass is arranged, reduce the effect of high temperature viscosity, can promote Fe 2O 3What cause is painted, and preferred content is not too much.Should illustrate, if Fe 2O 3Content is below the 200ppm, and its content can be no more than 5%.
ZrO 2Though be the composition that improves weathering resistance, contain radio isotope in the raw material easily, content should be controlled at 0～2%, preferred 0～0.5%, more preferably below the 500ppm.
Layer coated glass for encapsulating semiconductor of the present invention when having above-mentioned composition, adopts high-purity raw and is adjusted to the fusion environment that is difficult to sneak into impurity, can critically control U, Th, Fe thus 2O 3, PbO, TiO 2, MnO 2, ZrO 2Deng content, particularly dock the influential Fe of transmittance in near-ultraviolet ray zone 2O 3, PbO, TiO 2, MnO 2, can be controlled at the order of magnitude of 1～100ppm respectively, for U, the Th of soft error (soft error) reason that becomes the CCD element that produces because of alpha-ray, can be controlled at the order of magnitude of 0.1～10ppb respectively.
Below narrate the manufacture method of layer coated glass for encapsulating semiconductor of the present invention.
At first prepare the frit mixture according to the glass of desirable composition.Frit uses the few high-purity raws of impurity such as U, Th.The content that uses U and Th specifically is the high-purity raw below 5ppb all.Afterwards the frit that mixes is dropped into melting furnaces and carry out fusion.Though melting furnaces also can use the platinum container, but in glass, sneak into platinum impurity easily, preferably should adopt the poor refractory materials of U, Th make at the inwall (side, bottom surface etc.) of melting furnaces at least.Concrete, alumina refractory (for example aluminum oxide electrocast brick) or quartzy series refractory material (for example silica brick) etc. are difficult to corrosion, and the content of U, Th is dropped to respectively below the 1ppm, and U, Th to lack to melting of glass, thereby preferred.Carry out the homogenizing (outgasing, remove drawing lines) of melten glass afterwards at clarifying tank.This clarifying tank can be made by refractory materials or platinum, and but, zirconia refractory should be avoided using owing to contain more radio isotope.
After inferior, the melten glass of homogenizing injects mould, and casting perhaps pulls straight at Yan Banshang, is configured as predetermined shape.Then,, after it is cut out by certain thickness, attrition process is carried out on its surface, form the massive plate glass of specific thickness, this sheet glass size is according to the rules cut off processing, make cladding glasses glass shaping body (glass ingot) Xu Leng of gained.
In addition, except above-mentioned method, can be tabular with glass tube down-drawing (ダ ウ Application De ロ one) or float forming also with melten glass, after acquisition has the sheet glass of wishing thickness, size is according to the rules cut off processing, and necessity is carried out surface working, makes cladding glasses.Glass tube down-drawing can be used overflow downdraw (オ one バ one Off ロ one ダ ウ Application De ロ one) or groove glass tube down-drawing (ス ロ Star ト ダ ウ Application De ロ one), particularly overflow downdraw shaping sheet glass can improve surface quality, need not attrition process, reduce production costs, thus preferred.
Embodiment
Followingly layer coated glass for encapsulating of the present invention is described according to embodiment.
Table 1 is depicted as the embodiment of the invention (sample No.1～7) and comparative example (sample No.8).
Table 1
Sample No. forms ??1 ??2 ??3 ??4 ??5 ??6 ??7 ????8
??SiO 2 ??69.07 ??67.5 ??66.9 ??65.48 ??67.8 ??68.32 ??68.2 ????68.5
??Al 2O 3 ??7.0 ??8.0 ??7.0 ??8.0 ??2.1 ??5.2 ??8.5 ????5.4
??B 2O 3 ??13.1 ??13.1 ??13.1 ??13.1 ??15.2 ??10.9 ??10.0 ????11.0
??CaO ??2.2 ??0.6 ??2.2 ??0.6 ??- ??3.2 ??- ????2.5
??ZnO ??- ??- ??- ??- ??5.0 ??0.9 ??2.0 ????1.5
??Li 2O ??- ??0.2 ??- ??- ??- ??- ??4.0 ????-
??Na 2O ??6.7 ??8.4 ??8.6 ??8.6 ??6.0 ??11.3 ??7.0 ????8.5
??K 2O ??1.9 ??1.6 ??2.0 ??2.0 ??3.4 ??- ??- ????2.1
??TiO 2 ??- ??- ??- ??1.6 ??- ??- ??- ????-
??Sb 2O 3 ??- ??- ??- ??- ??- ??0.08 ??- ????0.5
??F 2 ??- ??- ??- ??- ??- ??- ??0.1 ????-
??Cl 2 ??- ??0.1 ??＝ ??0.6 ??0.5 ??- ??0.2 ????-
??SO 3 ??0.03 ??- ??- ??0.02 ??- ??- ??- ????-
??SnO 2 ??- ??- ??0..2 ??- ??- ??0.1 ??- ????-
??CeO 2 ??- ??0.5 ??- ??- ??- ??- ??- ????-
??U(ppb) ??4 ??4 ??4 ??4 ??2 ??2 ??4 ????4
??Th(ppb) ??2 ??2 ??2 ??2 ??6 ??2 ??6 ????2
Thermal expansivity (* 10 -7/℃) ??55.8 ??60.1 ??62.8 ??61.4 ??54.1 ??67.6 ??68.3 ????66.9
Density ??2.35 ??2.35 ??2.39 ??2.36 ??2.39 ??2.45 ??2.41 ????2.43
The viscosity deformation point (℃) Xu Lengdian (℃) softening temperature (℃) 10 4(℃) ??10 3(℃) ??10 2.5(℃) ? ??535 ??571 ??765 ??1119 ??1345 ??1500 ? ??520 ??561 ??753 ??1085 ??1326 ??1451 ? ??530 ??568 ??745 ??1059 ??1261 ??1401 ? ??510 ??552 ??744 ??1086 ??1306 ??1461 ? ??492 ??533 ??729 ??1053 ??1245 ??1374 ? ??543 ??576 ??739 ??1029 ??1211 ??1340 ? ??459 ??494. ??655 ??965 ??1162 ??1297 ? ????541 ????579 ????755 ????1055 ????1242 ????1382
Alkali stripping quantity (mg) ??0.06 ??0.06 ??0.06 ??0.06 ??0.06 ??0.07 ??0.04 ????0.06
Alpha-ray discharging amount (c/cm 2·hr) ??0.0020 ??0.0021 ??0.0021 ??0.0021 ??0.0017 ??0.0016 ??0.0030 ????0.0018
The bubble number (individual/100g) ??71 ??85 ??68 ??62 ??87 ??64 ??65 ????80
Each sample in the table prepares as follows.
At first will be according to the glass 500g that forms in can the acquisition table synthetic high purity glass raw material drop into the crucible that platinum rhodium or quartzy series refractory material are made, in having the electric smelter of agitating function,, this melten glass is flowed out on carbon plate with 1570 ℃, 2 hours condition fusion.With this sheet glass Xu Leng, as glass specimen.
Can be clear and definite from table, the thermal expansivity of embodiment glass (sample No.1～7) is 54.1～68.3 * 10 -7/ ℃, density below 2.45, be equivalent to 10 2.5The temperature of dPas viscosity below 1500 ℃, the alkali stripping quantity below 0.07mg, the alpha-ray discharging amount is at 0.0030c/cm 2Below the hr, be suitable for use as the solid-state imager layer coated glass for encapsulating.In addition, the bubble number in the embodiment glass with contain Sb 2O 3The bubble number of 0.5% comparative example glass (sample No.8) is in same grade, and clarification property is good.
In addition, the content of U, Th is measured by ICP-MASS in the table 1.Thermal expansivity is to be determined at the mean thermal expansion coefficients between 30～380 ℃ with Dilight meter (デ イ ラ ト メ one one).Density is tried to achieve according to known Archimedes's method.
In addition, deformation point, Xu Lengdian measure with reference to ASTM C336-71 method, and softening temperature is measured with reference to ASTM C338-93 method.10 4Pas temperature, 10 3Pas temperature and 10 2.5The Pas temperature is tried to achieve by known platinum ball pulling method.10 2.5The Pas temperature is to measure and high temperature viscosity 10 2.5Moor suitable temperature, it is worth, and low melt is good more more.
In addition, the alkali stripping quantity is measured according to JIS R3502.The alpha-ray discharging amount adopts ultra low levels alpha-ray determinator, and (sumitomo chemical company LACS-4000M) is measured.The bubble number is that the number of bubbles more than the 100 μ m in the glass is counted, and is scaled the number of bubbles of every 100g and tries to achieve.
Industrial applicibility
Layer coated glass for encapsulating of the present invention is suitable for use as the solid-state imager layer coated glass for encapsulating, in addition, to accommodate the representative that is encapsulated as of laser diode, can be used as the cladding glasses for various encapsulating semiconductors. And the mean thermal expansion coefficients of this cladding glasses in 30～380 ℃ temperature range can be adjusted into 30～85 * 10-7/ ℃, therefore except alumina packaging, also can in the various encapsulation that resin, tungsten metal, section's watt (kovar) iron cobalt nickel alloy, molybdenum, 36Ni-Fe alloy, 42Ni-Fe alloy, 45Ni-Fe alloy, 46Ni-Fe alloy, 52Ni-Fe alloy etc. are made, use organic resin or low-melting glass to seal.

Claims (7)

1. layer coated glass for encapsulating semiconductor is characterized in that containing SiO in quality % 258～72%, Al 2O 30.5 B～15%, 2O 38～18%, alkalimetal oxide 7.5～20%, alkaline-earth metals oxide 0～20%, ZnO 0～10%, Sb 2O 3+ Sb 2O 50～0.2%, F 2+ Cl 2+ C+SO 3+ SnO 2+ CeO 20.01～3%, in fact do not contain As 2O 3
2. the layer coated glass for encapsulating semiconductor of claim 1 record is characterized in that the mean thermal expansion coefficients in 30～380 ℃ temperature range is 30～85 * 10 -7/ ℃.
3. the layer coated glass for encapsulating semiconductor of claim 1 or 2 records is characterized in that from glass radiating alpha-ray burst size at 0.005c/cm 2Below the hr.
4. the layer coated glass for encapsulating semiconductor of each record of claim 1～3 is characterized in that U content is below 5ppb in the glass, and Th content is below 10ppb.
5. the layer coated glass for encapsulating semiconductor of each record of claim 1～4 is characterized in that density is at 2.45g/cm 3Below.
6. the layer coated glass for encapsulating semiconductor of each record of claim 1～5 is characterized in that the alkali stripping quantity is below 1.0mg.
7. the layer coated glass for encapsulating semiconductor of claim 1～6 record is characterized in that being used to accommodate the encapsulation of solid-state imager.
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JP2003380646 2003-11-11
JP2004283177A JP2005162600A (en) 2003-11-11 2004-09-29 Cover glass plate for semiconductor package
JP2004283177 2004-09-29
JP2004-283177 2004-09-29

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