CN102741185B - Semi-conductor covering glass and the semi-conductor covering material using this glass to be formed - Google Patents

Semi-conductor covering glass and the semi-conductor covering material using this glass to be formed Download PDF

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CN102741185B
CN102741185B CN201180007607.7A CN201180007607A CN102741185B CN 102741185 B CN102741185 B CN 102741185B CN 201180007607 A CN201180007607 A CN 201180007607A CN 102741185 B CN102741185 B CN 102741185B
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glass
semi
conductor covering
content
composition
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CN102741185A (en
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西川欣克
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority claimed from JP2010016552A external-priority patent/JP5565747B2/en
Priority claimed from JP2010195611A external-priority patent/JP5773327B2/en
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to CN201510366918.2A priority Critical patent/CN105152532A/en
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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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds

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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)

Abstract

The object of the invention is to, provide a kind of carrying capacity of environment little and semiconductor surface cover after the large semi-conductor covering glass of surface charge density.The feature of semi-conductor covering glass of the present invention is, is any one in following (1) or (2).The semi-conductor covering glass of following (2), carrying capacity of environment is little and surface charge density after semiconductor surface covering is large, and chemical durability is excellent.(1) in mass %, containing ZnO? 50 ~ 65%, B 2o 319 ~ 28%, SiO 27 ~ 15%, Al 2o 33 ~ 12%, Bi 2o 3the composition of 0.1 ~ 5%, in fact not containing the semi-conductor covering glass of lead composition; (2) in mass %, containing ZnO? 40 ~ 60%, B 2o 35 ~ 25%, SiO 215 ~ 35%, Al 2o 3the composition of 3 ~ 12%, in fact not containing the semi-conductor covering glass of lead composition.

Description

Semi-conductor covering glass and the semi-conductor covering material using this glass to be formed
Technical field
The present invention relates to the glass of the covering of the semiconductor device be used as containing P-N junction and use the semi-conductor covering material of this glass.
Background technology
Usually, in the semiconductor device such as silicon diode and transistor, the pollution caused for preventing extraneous gas, the surface containing P-N junction of semiconductor element is covered by the material containing glass.Thereby, it is possible to make semiconductor component surfaces stablize, suppress the deterioration in characteristics of passing in time.
As the characteristic required by the glass as semi-conductor covering material, can enumerate: (1) thermal expansivity is corresponding to the thermal expansivity of semi-conductor, make to cause crackle etc. because of the difference of the thermal expansivity with semiconductor element when covering; (2) in order to prevent the deterioration in characteristics of semiconductor element, can cover with low temperature (such as less than 900 DEG C); (3) not containing causing the impurity such as dysgenic alkaline constituents to semiconductor component surfaces; (4) electrical property after covering as semiconductor component surfaces, has the high reliability such as breakdown reverse voltage is high, stray current is few.
In the past, as semi-conductor covering glass, there will be a known ZnO-B 2o 3-SiO 2system waits zinc system glass, PbO-SiO 2-Al 2o 3system or PbO-SiO 2-Al 2o 3-B 2o 3the lead system glass such as system.Wherein, from the aspect of operability, PbO-SiO 2-Al 2o 3system and PbO-SiO 2-Al 2o 3-B 2o 3the lead system glass such as system become main flow (for example, referring to patent documentation 1 ~ 4).
At first technical literature
Patent documentation
Patent documentation 1: Japan JP 1-49653 publication
Patent documentation 2: the clear 50-129181 publication of Japanese Laid-Open
Patent documentation 3: the clear 48-43275 publication of Japanese Laid-Open
Patent documentation 4: Japanese Laid-Open 2008-162881 publication
Summary of the invention
The problem that invention will solve
Because the lead compositions such as PbO are environmentally harmful compositions, therefore, in recent years, along with its disabled in electric installation and electronics, the unleaded of various material is also developed.Due to above-mentioned ZnO-B 2o 3-SiO 2system waits in zinc system glass also contains a small amount of lead composition, therefore, from the viewpoint of environment, can not adopt.In addition, even unleaded composition, the material low due to the surface charge density after semiconductor surface covering is main flow, therefore, is difficult in response to the withstand voltage semiconductor element of height.
Therefore, the first problem of the present invention is, even if provide a kind of not containing lead composition, the semi-conductor covering glass that the surface charge density after semiconductor surface covers is also very large.
And, zinc system glass and lead system glassy phase ratio, chemical durability is poor, glass fire after use side operation in more weak to the tolerance of acid.Therefore, be necessary that forming protective membrane further in cover glass surface implements to use side operation.
Therefore, the second problem of the present invention is, even if provide a kind of not containing lead composition, the surface charge density after semiconductor surface covers is also very large, and the semi-conductor covering glass of chemical durability excellence.
Solve the means of problem
The present inventor after extensive studies it, found that: the ZnO-B with specific composition 2o 3-SiO 2be that glass can solve above-mentioned first problem and the second problem, propose the present invention thus.
That is, the feature solving the semi-conductor covering glass of the present invention of the first problem is, in mass %, containing ZnO50 ~ 65%, B 2o 319 ~ 28%, SiO 27 ~ 15%, Al 2o 33 ~ 12%, Bi 2o 3the composition of 0.1 ~ 5%, and in fact not containing lead composition.
Solve the semi-conductor covering glass of the present invention of the first problem, due to relative to ZnO-B 2o 3-SiO 2be glass, the Al containing specified quantitative 2o 3and Bi 2o 3, therefore, be applicable to the covering of the large withstand voltage semiconductor element of height of the surface charge density after semiconductor surface covering.In addition, owing to not containing lead composition in fact, therefore carrying capacity of environment is little.
It should be noted that, in the semi-conductor covering glass of the present invention of solution first problem, " in fact not containing lead composition " means and not has a mind to add as glass ingredient, but and does not mean that the impurity got rid of unavoidably be mixed into completely.Objective, what mean impure lead composition contains quantity not sufficient 0.1 quality %.
In addition, the feature solving the preferred implementation of the semi-conductor covering glass of the present invention of the first problem is, also containing MnO 20 ~ 5%, Nb 2o 50 ~ 5%, CeO 2the composition of 0 ~ 3%.
In addition, the present invention relates to the semi-conductor covering glass of the present invention using and solve above-mentioned first problem and the semi-conductor covering glass powder that formed and semi-conductor covering material.
The feature of the semi-conductor covering glass powder of the present invention of above-mentioned formation is, is formed by any one semi-conductor covering glass above-mentioned.
By making semi-conductor covering glass be Powdered, the covering realizing semiconductor surface can be easy to.
In addition, the feature of the semi-conductor covering material of the present invention of above-mentioned formation is, containing above-mentioned semi-conductor covering glass powder.
In addition, the feature of the preferred implementation of the semi-conductor covering material of the invention described above is, relative to the above-mentioned semi-conductor covering glass powder of 100 mass parts, is selected from TiO containing 0.01 ~ 5 mass parts 2, ZrO 2, ZnO, ZnOB 2o 3and 2ZnOSiO 2in at least one inorganic powder.
Particularly in the very large situation of contact area of the semiconductor elements such as Si and glass, the thermal expansivity being preferably glass and Si is close.The thermal expansivity of glass can crystallize into adjustment of assigning to contained by glass, but the crystallization content that moderate control is separated out from glass is very difficult.For this reason, when suitably adding above-mentioned inorganic powder in semi-conductor covering glass, these inorganic powders play the effect of nucleator, can than the crystallization content being easier to control to separate out.As a result, the thermal expansivity of expectation can be easily adjusted to.
In addition, the feature of other preferred implementation of the semi-conductor covering material of the invention described above is, surface charge density is 7 × 10 11/ cm 2above.
And the feature solving the semi-conductor covering glass of the present invention of the second problem is, in mass %, containing ZnO40 ~ 60%, B 2o 35 ~ 25%, SiO 215 ~ 35%, Al 2o 3the composition of 3 ~ 12%, and in fact not containing lead composition.
Solve the semi-conductor covering glass of the present invention second problem, relative to ZnO-B 2o 3-SiO 2be glass, the Al containing specified quantitative 2o 3, by strictly limiting the content of each composition, the surface charge density that can realize after semiconductor surface covering is large, is applicable to the covering of high withstand voltage semiconductor element, and the feature that chemical durability is high.In addition, owing to not containing lead composition in fact, therefore, the load caused to environment is little.
It should be noted that, in the semi-conductor covering glass solving the present invention second problem, " in fact not containing lead composition " means and not has a mind to add as glass ingredient, and does not mean that the impurity got rid of unavoidably be mixed into completely.Objective, what mean impure lead composition contains quantity not sufficient 0.1 quality %.
In addition, the feature solving the preferred implementation of the semi-conductor covering glass of the present invention of the second problem is, also containing Bi 2o 30 ~ 5%, MnO 20 ~ 5%, Nb 2o 50 ~ 5%, CeO 2the composition of 0 ~ 3%.
In addition, the present invention relates to the semi-conductor covering glass using and solve above-mentioned second problem and the semi-conductor covering material that formed.
The feature of the semi-conductor covering material of the present invention of above-mentioned formation is, containing the glass powder that above-mentioned semi-conductor covering glass is formed.
By using this semi-conductor covering material, the covering of semiconductor surface can be realized easily.
In addition, the feature of the preferred implementation of the semi-conductor covering material of the invention described above is, relative to above-mentioned glass powder 100 mass parts, is selected from TiO containing 0.01 ~ 5 mass parts 2, ZrO 2, ZnO, ZnOB 2o 3and 2ZnOSiO 2in at least one inorganic powder.
Particularly in the very large situation of contact area of the semiconductor elements such as Si and glass, be preferably the similar thermal expansion coefficient of glass and Si.The thermal expansivity of glass can crystallize into adjustment of assigning to contained by glass, but the crystallization content that moderate control is separated out from glass is very difficult.For this reason, when suitably adding above-mentioned inorganic powder in semi-conductor covering glass, these inorganic powders play the effect of nucleator, can than the crystallization content being easier to control to separate out.As a result, the thermal expansivity of expectation can be easily adjusted to.
Embodiment
Below, in semi-conductor covering glass of the present invention, illustrate that each composition carries out the reason specified as mentioned above.It should be noted that, in the following description, unless otherwise stated, " % " means " quality % ".
Below, the semi-conductor cover glass of solution first problem and the semi-conductor covering glass powder using this glass to be formed and semi-conductor covering material are described as the first embodiment, the semi-conductor cover glass of solution second problem and the semi-conductor covering material that uses this glass to be formed are described as the second embodiment.
First embodiment
The semi-conductor covering glass of the first embodiment of the present invention, is characterized in that, in mass %, containing ZnO50 ~ 65%, B 2o 319 ~ 28%, SiO 27 ~ 15%, Al 2o 33 ~ 12%, Bi 2o 3the composition of 0.1 ~ 5%, and in fact not containing lead composition.
ZnO is the composition making stabilization.The content of ZnO is preferably 50 ~ 65%, is particularly preferably 55 ~ 63%.When the content of ZnO is less than 50%, the thermal expansivity of glass will become greatly, when sealing semiconductor element, likely cause crackle because of the thermal expansion difference with semiconductor element.On the other hand, the content of ZnO more than 65% time, crystallization can be carried out rapidly, therefore, can make to cover semiconductor component surfaces become difficulty because of the illiquidity of glass.
B2O3 is the reticulated structure forming component of glass, is also the composition improving mobility.B 2o 3content be preferably 19 ~ 28%, be particularly preferably 20 ~ 25%.Work as B 2o 3content when being less than 19%, crystallinity strengthens, and mobility is impaired, can make to cover semiconductor component surfaces and become difficulty.On the other hand, B is worked as 2o 3content more than 28% time, the thermal expansivity of glass becomes large, when sealing semiconductor element, likely causes crackle because of the thermal expansion difference with semiconductor element.
SiO 2for the reticulated structure forming component of glass, be also improve acid proof composition.SiO 2content be preferably 7 ~ 15%, be particularly preferably 9 ~ 14%.Work as SiO 2content when being less than 7%, the thermal expansivity of glass becomes large, when sealing semiconductor element, likely causes crackle because of the thermal expansion difference with semiconductor element.In addition, be also easy to make the chemical durability of glass to reduce.Work as SiO 2content more than 15% time, be difficult to the glass realizing homogeneous.
Al 2o 3for improving the composition of the surface charge density of glass.Al 2o 3content be preferably 3 ~ 12%, be particularly preferably 5 ~ 10%.Work as Al 2o 3content when being less than 3%, be difficult to realize above-mentioned effect.On the other hand, Al is worked as 2o 3content when being greater than 12%, easily there is devitrification in glass.
Bi 2o 3also be the composition of the surface charge density improving glass.Bi 2o 3content be preferably 0.1 ~ 5%, be particularly preferably 0.5 ~ 3%.Work as Bi 2o 3content when being less than 0.1%, be difficult to realize above-mentioned effect.On the other hand, Bi is worked as 2o 3content more than 5% time, easily there is devitrification in glass.
Except mentioned component, semi-conductor covering glass of the present invention also can contain MnO 2, Nb 2o 5, CeO 2.These compositions have the effect of the stray current reducing semiconductor element.
MnO 2content be preferably 0 ~ 5%, be particularly preferably 0.1 ~ 3%.Work as MnO 2content more than 5% time, the meltbility of glass likely reduces.
Nb 2o 5content be preferably 0 ~ 5%, be particularly preferably 0.1 ~ 3%.Work as Nb 2o 5content more than 5% time, the meltbility of glass likely reduces.
CeO 2content be preferably 0 ~ 3%, be particularly preferably 0.1 ~ 2%.Work as CeO 2more than 3% time, the crystallinity of glass likely become too strong, and the mobility of glass likely reduces.
And from the viewpoint of environment, semi-conductor covering glass of the present invention is not in fact containing lead composition (PbO etc.).
From the viewpoint of the covering being easy to carry out semiconductor component surfaces, semi-conductor covering glass of the present invention is preferably Powdered.The median size D of semi-conductor covering glass powder 50be preferably less than 25 μm, be particularly preferably less than 15 μm.As the median size D of semi-conductor covering glass powder 50when being greater than 25 μm, not easily form cream, be difficult to uniform fold at semiconductor surface.In addition, be also difficult to utilize electrophoresis to cover.And lower limit is not particularly limited, in reality, be more than 0.1 μm.
Semi-conductor covering material of the present invention contains above-mentioned semi-conductor covering glass powder.And semi-conductor covering material of the present invention, also can be selected from TiO for containing relative to above-mentioned semi-conductor covering glass powder 2, ZrO 2, ZnO, ZnOB 2o 3and 2ZnOSiO 2in at least one inorganic powder as the material of nucleator.Relative to the semi-conductor covering glass powder of 100 mass parts, the content of these inorganic powders is preferably 0.01 ~ 5 mass parts, is particularly preferably 0.1 ~ 3 mass parts.When the content of inorganic powder is less than 0.01 mass parts, the crystallization content of precipitation is few, is likely difficult to the thermal expansivity realizing expecting.When the content of inorganic powder is more than 5 mass parts, the crystallization content of precipitation is too much, likely makes mobility impaired, is difficult to cover semiconductor component surfaces.
And the granularity of above-mentioned inorganic powder is less, less from the particle diameter of the crystallization of glass precipitation, physical strength is likely larger.Therefore, the median size D of inorganic powder 50preferably below 5 μm, particularly preferably in less than 3 μm.Lower limit is not particularly limited, and is more than 0.1 μm in reality.
The surface charge density of semi-conductor covering material of the present invention, is preferably 7 × 10 in the semiconductor device of voltage 1000V 11/ cm 2above, in the semiconductor device of more than 1500V, 10 × 10 are preferably 11/ cm 2above.
According to the thermal expansivity of semiconductor element, the thermal expansivity (30 ~ 300 DEG C) of semi-conductor covering material of the present invention is such as adapted at 20 ~ 60 × 10 -7/ DEG C scope in regulate, be more suitable for 30 ~ 50 × 10 -7/ DEG C scope in regulate.
Semi-conductor covering glass of the present invention is by being in harmonious proportion the raw material powder of each oxide components as masterbatch (batch), and at the temperature of about 1400 DEG C, about melting 1 hour is to carry out vitrifying process, then, by shaping, pulverize, classification and obtaining.
Second embodiment
The feature of the semi-conductor covering glass of the second embodiment of the present invention is, as composition, in mass %, containing ZnO40 ~ 60%, B 2o 35 ~ 25%, SiO 215 ~ 35%, Al 2o 33 ~ 12%, and in fact not containing lead composition.
ZnO is the composition making stabilization.The content of ZnO is preferably 40 ~ 60%, is particularly preferably 47 ~ 55%.When the content of ZnO is less than 40%, increased devitrification resistance during glass melting strengthens, and melting becomes difficulty.On the other hand, when ZnO content more than 60% time, acid resistance likely weakens.
B 2o 3for the reticulated structure forming component of glass, it is also the composition improving mobility.B 2o 3content be preferably 5 ~ 25%, be particularly preferably 7 ~ 18%.Work as B 2o 3content when being less than 5%, crystallinity strengthens, and mobility is impaired, can make to cover semiconductor component surfaces and become difficulty.On the other hand, B is worked as 2o 3content more than 25% time, thermal expansivity likely becomes large.In addition, chemical durability likely reduces.
SiO 2for the reticulated structure forming component of glass, be also improve acid proof composition.SiO 2content be preferably 15 ~ 35%, be particularly preferably 20 ~ 33%.Work as SiO 2content when being less than 15%, chemical durability is likely deteriorated.On the other hand, SiO is worked as 2content more than 35% time, increased devitrification resistance during melting strengthens, and is difficult to the glass realizing homogeneous.
Al 2o 3for improving the composition of the surface charge density of glass.Al 2o 3content be preferably 3 ~ 12%, be particularly preferably 5 ~ 10%.Work as Al 2o 3content when being less than 3%, be difficult to realize above-mentioned effect.On the other hand, Al is worked as 2o 3content more than 12% time, easily there is devitrification in glass.
And as composition, semi-conductor covering glass of the present invention is preferably containing Bi 2o 30 ~ 5%, MnO 20 ~ 5%, Nb 2o 50 ~ 5%, CeO 20 ~ 3%.
Bi 2o 3for improving the composition of the surface charge density of glass.Bi 2o 3content be preferably 0 ~ 5%, be particularly preferably 0.1 ~ 3%.Work as Bi 2o 3content more than 5% time, easily there is devitrification in glass.
MnO 2, Nb 2o 5, CeO 2for the composition making the stray current of semiconductor element reduce.
MnO 2content be preferably 0 ~ 5%, be particularly preferably 0.1 ~ 3%.Work as MnO 2content more than 5% time, the meltbility of glass likely reduces.
Nb 2o 5content be preferably 0 ~ 5%, be particularly preferably 0.1 ~ 3%.Work as Nb 2o 5content more than 5% time, the meltbility of glass likely reduces.
CeO 2content be preferably 0 ~ 3%, be particularly preferably 0.1 ~ 2%.Work as CeO 2more than 3% time, the crystallinity of glass likely become too strong, and the mobility of glass likely reduces.
From the viewpoint of environment, semi-conductor covering glass of the present invention is not in fact containing lead composition (PbO).In addition, be preferably not containing having dysgenic alkali composition (Li to semiconductor component surfaces 2o, Na 2o, K 2o).
From the viewpoint of the covering being easy to carry out semiconductor component surfaces, semi-conductor covering glass of the present invention is preferably Powdered.In this case, the median size D of glass powder 50be preferably less than 25 μm, be particularly preferably less than 15 μm.As the median size D of glass powder 50when being greater than 25 μm, be difficult to form the cream for vitreous coating.In addition, electrophoretic coating also becomes difficulty.And lower limit is not particularly limited, in reality, be more than 0.1 μm.
Semi-conductor covering material of the present invention contains above-mentioned semi-conductor covering glass powder.And semi-conductor covering material of the present invention, also can be selected from TiO for containing relative to above-mentioned semi-conductor covering glass powder 2, ZrO 2, ZnO, ZnOB 2o 3and 2ZnOSiO 2in at least one inorganic powder as the material of nucleator.Relative to the semi-conductor covering glass powder of 100 mass parts, the content of these inorganic powders is preferably 0.01 ~ 5 mass parts, is particularly preferably 0.1 ~ 3 mass parts.When the content of inorganic powder is less than 0.01 mass parts, the crystallization content of precipitation is few, is likely difficult to the thermal expansivity realizing expecting.When the content of inorganic powder is more than 5 mass parts, the crystallization content of precipitation is too much, likely makes mobility impaired, is difficult to cover semiconductor component surfaces.
And the granularity of above-mentioned inorganic powder is less, less from the particle diameter of the crystallization of glass precipitation, physical strength is likely larger.Therefore, the median size D of inorganic powder 50preferably below 5 μm, particularly preferably in less than 3 μm.Lower limit is not particularly limited, and is more than 0.1 μm in reality.
According to the thermal expansivity of semiconductor element, the thermal expansivity (30 ~ 300 DEG C) of semi-conductor covering glass of the present invention is such as adapted at 20 ~ 60 × 10 -7/ DEG C scope in regulate, be more suitable for 30 ~ 50 × 10 -7/ DEG C scope in regulate.
The surface charge density of semi-conductor covering material of the present invention, is preferably 7 × 10 in the semiconductor device of voltage 1000V 11/ cm 2above, in the semiconductor device of more than 1500V, 10 × 10 are preferably 11/ cm 2above.It should be noted that, surface charge density refers to the value utilizing method described in embodiment to measure.
Semi-conductor covering glass of the present invention is by being in harmonious proportion the raw material powder of each oxide components as masterbatch, and at the temperature of about 1500 DEG C, about melting 1 hour is to carry out vitrifying, then, is obtained by shaping (thereafter, pulverize as required, classification).
Embodiment
Below, based on embodiment, the present invention is described, but the invention is not restricted to these embodiments.
First embodiment
Table 1 represents embodiment and the comparative example of first embodiment of the invention.
Table 1
The each sample of making as described below.First, the raw material powder that is in harmonious proportion forms the glass composition in table, and make masterbatch, at the temperature of 1400 DEG C, melting 1 hour is to carry out vitrifying.Then, this melten glass is shaped to membranaceous, afterwards, is pulverized by ball mill, use 350 object sieves to carry out classification, obtain semi-conductor covering glass powder (semi-conductor covering material, median size D 50: 12 μm).
Measure thermal expansivity and the surface charge density of gained semi-conductor covering glass powder.It should be noted that, in embodiment 6, be that the material being added with the ZnO powder of 1 mass parts measures to the semi-conductor covering glass powder relative to 100 mass parts.Result is shown in table 1.
Thermal expansivity represents with the value using dilatometer and measure in the temperature range of 30 ~ 300 DEG C.
Surface charge density is as described below to be measured.First, discrete nucleation covering glass powder in organic solvent, forms certain thickness by electrophoresis in silicon substrate attachment, then fires, form glass coating.Form aluminium electrode on glass coating after, use C-V measurement to determine the change of the electrical capacity in glass, calculate surface charge density.
As shown in Table 1, the surface charge density of the sample of embodiment 1 ~ 6 is up to 8 ~ 18.This is and PbO-SiO 2-Al 2o 3system or PbO-SiO 2-Al 2o 3-B 2o 3the surface charge density that the lead system glass being is almost equal.Therefore, the semi-conductor covering material of embodiment 1 ~ 6 is applicable to the covering of high withstand voltage semiconductor element.
On the other hand, the surface charge density of the sample of known comparative example 1 and comparative example 2 is low, is not suitable for the covering of high withstand voltage semiconductor element.
Second embodiment
Table 2 represents embodiment and the comparative example of second embodiment of the invention.
Table 2
The each sample of making as described below.First, the raw material powder that is in harmonious proportion forms glass composition in table as masterbatch, and at the temperature of 1500 DEG C, melting 1 hour is to carry out vitrifying.Then, this melten glass is shaped to membranaceous, afterwards, is pulverized by ball mill, use 350 object sieves to carry out classification, obtain semi-conductor covering glass powder (median size D 50: 12 μm).
Measure the thermal expansivity of gained semi-conductor covering glass powder, surface charge density and acid resistance.Result is shown in table 2.
Thermal expansivity represents with the value using dilatometer and measure in the temperature range of 30 ~ 300 DEG C.
Surface charge density is as described below to be measured.First, dispersing glass powder in organic solvent, forms certain thickness by electrophoresis in silicon substrate attachment, then fires, form glass coating.Form aluminium electrode on glass coating after, use C-V measurement to determine the change of the electrical capacity in glass, calculate surface charge density.
Acid resistance is as described below to be evaluated.First, be the size of diameter 20mm, thickness about 4mm by glass powder compression moulding, fire and make particulate state sample, this sample to be immersed at 25 DEG C in 30% nitric acid 1 minute, then calculate the quality change of per unit area according to Mass lost, evaluate acid resistance.
As shown in Table 1, the specimen surface electric density of embodiment 1 ~ 6 is up to 14 ~ 18.This is and PbO-SiO 2-Al 2o 3system or PbO-SiO 2-Al 2o 3-B 2o 3the lead system glassy phase of system is than equal and even higher surface charge density.In addition, the Mass lost that causes of acid resisting test is at 0.6mg/cm 2below, it can thus be appreciated that its acid resistance is excellent.Therefore, the semi-conductor covering material of embodiment 1 ~ 6 is applicable to the covering of high withstand voltage semiconductor element.
On the other hand, the surface charge density of the sample of comparative example 1 and comparative example 2 is low reaches less than 6, and known its is not suitable for the covering of high withstand voltage semiconductor element.In addition, the Mass lost that causes of acid resisting test is at 3.5mg/cm 2above, acid resistance is poor.
The present invention has been described in detail with reference to particular implementation, but it will be appreciated by those skilled in the art that only otherwise disengaging the spirit and scope of the present invention, can carry out various change and correction.
It should be noted that, the Japanese patent application (Patent 2010-195611) that the application proposes based on the Japanese patent application (Patent 2010-016552) proposed on January 28th, 2010 and on September 1st, 2010, its full content is as being incorporated herein by reference.In addition, all references of quoting at this are cited as a whole.

Claims (6)

1. a semi-conductor covering glass, is characterized in that, in mass %, containing ZnO50 ~ 65%, B 2o 319 ~ 23%, SiO 27 ~ 15%, Al 2o 33 ~ 12%, Bi 2o 3the composition of 0.1 ~ 2%, and in fact not containing lead composition.
2. semi-conductor covering glass as claimed in claim 1, is characterized in that, also containing MnO 20 ~ 5%, Nb 2o 50 ~ 5%, CeO 2the composition of 0 ~ 3%.
3. a semi-conductor covering glass powder, is characterized in that, is formed by the semi-conductor covering glass described in claim 1 or 2.
4. a semi-conductor covering material, is characterized in that, containing semi-conductor covering glass powder according to claim 3.
5. a semi-conductor covering material, is characterized in that, relative to 100 mass parts semi-conductor covering according to claim 3 glass powder, is selected from TiO containing 0.01 ~ 5 mass parts 2, ZrO 2, ZnO, ZnOB 2o 3and 2ZnOSiO 2in at least one inorganic powder.
6. the semi-conductor covering material as described in claim 4 or 5, is characterized in that, surface charge density is 7 × 10 11/ cm 2above.
CN201180007607.7A 2010-01-28 2011-01-19 Semi-conductor covering glass and the semi-conductor covering material using this glass to be formed Active CN102741185B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510366918.2A CN105152532A (en) 2010-01-28 2011-01-19 Glass for semiconductor coating and material for semiconductor coating using the same

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2010-016552 2010-01-28
JP2010016552A JP5565747B2 (en) 2010-01-28 2010-01-28 Semiconductor coating glass and semiconductor coating material using the same
JP2010-195611 2010-09-01
JP2010195611A JP5773327B2 (en) 2010-09-01 2010-09-01 Glass for semiconductor coating
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US9159549B2 (en) * 2011-05-26 2015-10-13 Shindengen Electric Manufacturing Co., Ltd. Glass composition for protecting semiconductor junction, method of manufacturing semiconductor device and semiconductor device
JP6064298B2 (en) * 2011-08-25 2017-01-25 日本電気硝子株式会社 Glass for semiconductor element coating
JP5548276B2 (en) * 2011-08-29 2014-07-16 新電元工業株式会社 Semiconductor junction protecting glass composition, semiconductor device manufacturing method, and semiconductor device
CN104254907B (en) * 2013-03-29 2016-07-06 新电元工业株式会社 Semiconductor bond protection glass composite, the manufacture method of semiconductor device and semiconductor device
JP6410089B2 (en) * 2014-09-09 2018-10-24 日本電気硝子株式会社 Glass for semiconductor element coating
JP6852961B2 (en) * 2015-06-01 2021-03-31 日本電気硝子株式会社 Glass for coating semiconductor devices
WO2017134808A1 (en) * 2016-02-05 2017-08-10 新電元工業株式会社 Method for producing semiconductor device

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