JPH0476337B2 - - Google Patents

Description

Claim 1: A low melting glass composition containing the following components in weight percent calculated on oxide: (a) Pbo 30-35%, (b) V ₂ O ₅ 30-55%, ( c) Bi ₂ O ₃ 0.1-18%, (d) P ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , or a combination thereof 0.1-10%, (e) ZnO, BaO, SrO, or these Combination 0.1-10%, where the total weight% of (c) + (d) + (e) is 0.3%
and 20%, with the proviso that (a) may be partially replaced by up to 25% by weight of cesium oxide. 2. A low melting glass composition according to claim 1, wherein the composition contains at least one additive selected from the group consisting of: up to 3% by weight of Cu ₂ O 5% by weight. A low-melting glass composition according to claim 1 containing the following components by weight: MoO ₃ up to 3 wt. % Ag ₂ O up to 5 wt. % WO ₃ up to 3 wt. % F 3 Materials: (a) Pbo 35-45%, (b) V ₂ O ₅ 35-45%, (c) Bi ₂ O ₃ 3-8%, (d) ZnO 2-7% (e) P ₂ O ₅ 0-5%, (f) Nb ₂ O ₅ 0-5%, (g) Ta ₂ O ₅ 0-8%, where the total weight % of (e) + (f) + (g) is: 0.1%
Within the range of ~10%. 4. According to claim 1, 2, or 3, the ceramic particulate filler having a low coefficient of thermal expansion is mixed in an amount of about 1 to 50% by weight based on the weight of the mixture. glass composition. 5. The glass composition according to claim 4, wherein the filler is a Group V metal oxide. 6. The glass composition according to claim 4, wherein the filler is a niobium-containing oxide, zirconium phosphate, or tantalum oxide. 7. The glass composition according to claim 4, wherein the filler is niobium pentoxide. 8 Silver or gold powder, based on the mixture,
A glass composition according to claim 1, 2, 3, 4, 5, 6, or 7, mixed up to 90% by weight. 9. An article of manufacture used in melt sealing electronic components, the article of manufacture being coated with a pattern of a low melting glass composition containing the following components in weight percentages calculated on an oxide basis: (a) PbO 30-55%, (b) V ₂ O ₅ 30-55%, (c) Bi ₂ O ₃ 0.1-18%, (d) P ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , or a combination of these 0.1 to 10%, (e) ZnO, BaO, SrO, or a combination of these 0.1 to 10%, where (c) + (d ) + (e) total weight% is 0.3%
and 20%, with the proviso that (a) may be partially replaced by up to 25% by weight of cesium oxide. 10. The article of manufacture of claim 9, wherein the low melting glass composition contains at least one additive selected from the group consisting of: up to 3% Cu ₂ O 5% by weight. MoO ₃ up to 3% Ag ₂ O up to 5% WO ₃ up to 3% F 11 The low melting glass composition contains the following components in weight %: Articles manufactured as described in paragraphs: (a) PbO 35-45%, (b) V ₂ O ₅ 35-45%, (c) Bi ₂ O ₃ 3-8%, (d) ZnO 2-7% (e )P ₂ O ₅ 0-5%, (f) Nb ₂ O ₅ 0-5%, (g) Ta ₂ O ₅ 0-8%, where the sum of (e) + (f) + (g) Weight% is 0.1%
Within the range of ~10%. 12. Claims 9 and 10, wherein the low melting glass composition further contains about 1 to 50% by weight, based on the weight of the mixture, of a ceramic particulate filler having a low coefficient of thermal expansion. or the 11th
Articles of manufacture described in Section. 13. The article of manufacture of claim 12, wherein the filler is a Group V metal oxide. 14. The article of manufacture of claim 12, wherein the filler is a niobium-containing oxide, zirconium phosphate, or tantalum oxide. 15. The article of manufacture of claim 12, wherein the filler is niobium pentoxide. TECHNICAL FIELD The present invention relates to a novel low temperature melting glass. The present invention particularly relates to glasses that melt at very low temperatures. The glass, with or without added ceramic fillers, can hermetically seal electronic ceramic components such as alumina and beryllia in the 300°C range. BACKGROUND OF THE INVENTION The present invention addresses the problem of glass sealing semiconductor devices and hybrid circuits that do not withstand sealing cycles above about 300°C. Such semiconductor devices include, for example, gallium arsenide and many other group-group compounds (ie, compounds of group elements of the periodic table). It is well known in the art that commercially available solder glasses capable of sealing ceramic and glass components such as television picture tubes and semiconductor ceramic packages are useful in the temperature range of 420 to 500 degrees Celsius. . These solder glasses are derived from lead-boron oxide binary systems that in combination with silica and alumina produce extensive glass-forming areas. The lead oxide-boron oxide eutectic contains 13% by weight boron oxide and 87% by weight lead oxide, and is the most fluid glass in such a binary system. It is the starting point from which most commercially available solder glasses are derived. certain metal oxides,
For example, the addition of silica, alumina, tin oxide and barium oxide to the glass melt makes the resulting glass more complex and improves its stability and resistance to chemicals and hot water. Lead borate glass has been developed over the past 20 years by adding fine-particle ceramic filler with a small expansion coefficient to adjust the linear thermal expansion coefficient of the entire fused glass.
It has been very successful in meeting the requirements for mechanical strength and hermeticity in the semiconductor packaging industry. However, when lead borate glass or lead borosilicate glass is used, there is a specific lower temperature limit, which prevents sealing at temperatures lower than 400 to 420°C. With the advent of certain advanced semiconductor devices (e.g., gallium arsenide) and related compound multilayer semiconductor devices (e.g., laser diodes), which can be processed at or below 300°C and Specifications (MIL-SPECS 883)
There is an urgent need for a practical melt-sealed glass that can further satisfy the following requirements. Various attempts have been made to develop low-temperature melting glasses that are practical for melting at temperatures of 300°C or lower, but these attempts have been limited due to the limited selection of possible materials. was severely limited. In particular, what is expected are mixtures of metal oxides with a unique combination of the following properties: low melting points, true solutions, forming glasses (supercooled liquids); A mixture of metal oxides that has a low viscosity in the liquid phase and a small coefficient of linear thermal expansion and is stable in the glass phase. A possible candidate is a lead-vanadium oxide binary system;
Forms a eutectic at a lower temperature than the boron oxide eutectic. This system tends to form a glass during rapid cooling, but upon reheating, it recrystallizes too quickly to be practical. Dumesnil et al., in U.S. Pat. No. 3,408,212, describe the effect of adding large amounts of lead fluoride to a lead-vanadium oxide mixture. A narrow glass-forming region is found to exist in the center of _the PbO- _PbF2 - _V2O5 ternary diagram with improved glass lifetime stability. These soft glasses have a very large coefficient of linear thermal expansion (135-155×
10 ^-7 /°C), but is not stable enough in glass form to be considered a practical glass sealant. Malmendier and Sojka (U.S. Patent No. 3837866)
), As ₂ O ₃ and As ₂ O ₅ are combined with PbO−V ₂ O ₅ eutectic,
It is stated that Cs ₂ O−V ₂ O ₅ is added to both eutectics to prevent recrystallization at an early stage and to expand the compositional range in which stable glass can be produced. However, the addition of arsenic oxide tends to rapidly increase the viscosity of the resulting glass, thus precluding its usefulness as a stable solder glass with flowability at or below 300°C. Dumesnil et al., in U.S. Pat _. No. 3,650,778, described 10 _to 60 wt.
7.5-13 wt% _{B2O3 ,} and 10-25 wt%
A lead-free glass composition containing P ₂ O ₅ is described. British Patent No. 1552648 describes PbO mixed with up to 50% zirconium phosphate (ZrO ₂ P ₂ O ₅ ) powder.
_{-V2O5 - P2O5} glass mixtures are described _. Busdiecker (U.S. Patent No. 3,454,408)
The paper describes the production of low-temperature solder glass with a large expansion coefficient by adding ZnO to copper vanadate. He did not mention adding Bi ₂ O ₃ , which is a necessary and essential component of the present invention. Although this invention does not mention either Nb ₂ O ₅ or Ta ₂ O ₅ , both of these are highly desirable components in the melt-sealed glass of the present invention. DISCLOSURE OF THE INVENTION The present invention provides a lead-vanadium oxide binary system containing (i) bismuth oxide; (ii) an oxide of zinc, barium, or strontium; and (iii) an oxide of phosphorus, niobium, or tantalum. It is based on the discovery that very fluid and stable glasses can be prepared by adding together These 3
The two oxides, when added together to the oxides of lead and vanadium, yield a large region that forms a free-flowing and stable glass, which makes them very practical for applications as low-temperature sealants. A five-component glass is obtained. The novel low melting glass composition of the present invention contains the following components in weight percent calculated on oxides: (a) PbO 30-35%, (b) _{V2O5 30-55} %, (c) Bi ₂ O ₃ 0.1-18%, (d) P ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , or a combination thereof 0.1-10%, (e) ZnO, BaO, SrO, or a combination of these 0.1-10%, where the total weight% of (c) + (d) + (e) is 0.3%
and 20%, with the proviso that (a) may be partially replaced by up to 25% by weight of cesium oxide. This new glass composition has a melting temperature of approximately 300
℃, has a short melting time, and has excellent thermal shock resistance and high chemical resistance under high temperature and high humidity environments (85℃/85% relative temperature). Preferred glass compositions of the invention consist essentially of the following components in weight percent calculated on oxide: (a) 35-45% PbO, (b) _35-45 % _V2O5 . , (c) Bi ₂ O ₃ 3-8%, (d) ZnO 2-7%, (e) P ₂ O ₅ 0-5%, (f) Nb ₂ O ₅ 0-5%, (g) Ta ₂ O ₅ 0-8%, where the total weight percent of (e) + (f) + (g) is 0.1%
Within the range of ~10%. A mixture of the novel glass composition described above with a ceramic particulate filler having a low coefficient of thermal expansion, preferably a Group V metal oxide, in an amount of from about 1 to about 50% by weight, based on the mixture, is provided by the present invention. This is another aspect of A mixture of the novel glass composition or glass composition/filler mixture described above with up to 90% by weight of silver or gold powder, based on the total mixture, is another aspect of the invention. Solder glasses mixed with about 1 to about 50 weight percent fillers that are group metal oxides are yet another aspect of the invention. Modes of Carrying Out the Invention Depending on the particular application in which the glass of the invention is used as a sealant, additives or fillers may be combined with the five basic components of the glass. As examples of such additives, copper oxide, silver oxide, and fluorine are typically mixed into the glass composition in an amount of 3% by weight, and _WO3 and _MoO3 are typically mixed in an amount of 5% by weight. mixed into the glass composition in amounts up to Adding such amounts of copper oxide to a glass composition improves the adhesion between the glass and the surface of a metal such as gold. If necessary, add silver oxide,
It can improve the fluidity of glass. Adding fluorine to this composition increases the coefficient of linear thermal expansion of the resulting glass. This allows for metals with high thermal expansion coefficients such as mild steel, copper, copper alloys, aluminum, and aluminum alloys (thermal expansion coefficient > 155×
10 ^-7 /°C) is provided. The amount of bismuth oxide and/or niobium pentoxide may be increased to compensate for the increased instability of the glass due to the presence of fluorine. Particulate ceramic fillers may be added to the glass powder of the present invention as a means of controlling the overall thermal expansion and contraction of the resulting fused glass mixture. Increasing the amount of ceramic filler with a low coefficient of thermal expansion causes a corresponding decrease in the coefficient of linear expansion of the fused glass, but this decrease is actually a linear function of the glass/filler volume ratio. Such fillers are typically used to produce glasses suitable for sealing low expansion ceramics, glasses or metals. A close match of the coefficient of thermal expansion of the fused glass to the ceramic parts to be joined (e.g., alumina, beryllia or steatite parts) is essential to maintain the absence of stress at the seal joint. Decisive.
This ensures strength and tightness under extreme conditions of thermal cycling and thermal shock. It is also known that the presence of a second crystalline phase in the glass is advantageous when the glass seal expands and contracts. Adding particulate filler minimizes the propagation of cracks throughout the glass. Conventional refractory silicates (e.g., β-eucryptite, zirconium silicate, zinc silicate, cordierite) and titanates (e.g., titanates) used with lead solder glasses may be used; The low-temperature sealing glass of the present invention does not sufficiently wet the surface of such fillers. However, group V metals (P, As, Sb, V, Nb, Ta)
Refractory fillers made from oxides of the invention can be perfectly compatible with the glasses of the invention, exhibit superior wetting properties compared to conventional fillers, and provide excellent hermetic seals. It is found that These new Group V metal fillers are also useful in solder glasses other than the solder glasses of the present invention. Table 1 below lists examples of this new class of refractory fillers, along with values for the coefficient of linear thermal expansion, if known.

【table】

TABLE As illustrated in Table 1, the term "Group V metal oxide" refers to a compound containing a Group V metal and oxygen, with or without other metals. Of this new class of fillers, niobium pentoxide is preferred (its coefficient of linear thermal expansion is approximately zero). Items with very low radioactivity levels (alpha radiation dose <0.1
(counts/cm ² /hour) are commercially available and are highly desirable for packaging semiconductor devices sensitive to radiation, such as silicon memory chips. Other niobium-containing oxides, such as lead titanium niobate and lead bismuth titanium niobate, are also excellent fillers. Fillers, whether conventional or new Group V oxide types, are typically mixed with the glass composition in amounts ranging from 1 to 50% by weight based on the mixture. These mixtures are prepared by placing the glass shards and refractory powder in a ball mill and grinding in a conventional manner to obtain fine particles that are homogeneously mixed with the majority of the ingredients. The resulting glass refractory mixture can be applied to a workpiece by itself or mixed with an organic solvent to form a paste and used to coat a workpiece. The workpiece is then heated to melt the glass and create a seal coating. The organic solvent is preferably a synthetic solvent boiling in the range 150-220°C, such as butyl carbitol, carbitol acetate, or similar solvents. Metal powder fillers such as silver or gold can be used on the basis of the glass powder of the present invention and mixtures for die bonding applications in packaging semiconductor chips.
It can be mixed in amounts up to 90% by weight, usually 70-80% by weight. The metal-glass mixture can be made into a paste for application to a die by formulating with an organic solvent as described above. Refractory fillers, such as those described above, may be added to metal-glass mixtures to control stress at the bond interface between an electronic component and a metal, glass, or ceramic substrate. It has also been found that lead oxide in glass compositions can be partially replaced by up to 25% by weight of cesium oxide. Such substitutions may be made to make the glass more fluid. Although the primary objective in the use of these glasses and glass-filler mixtures of the present invention is low fused glass temperatures in the 300°C range, it is recognized that there may be special applications requiring higher temperatures. You should understand. Therefore, the fact that there is no upper limit on temperature means that
This is unique to the application of the glass material of the present invention. Cupric oxide, cuprous oxide, litharge (Pb ₃ O ₄ ),
It will be readily appreciated by those skilled in the art of glass manufacturing that lead dioxide (PbO ₂ ), or any chemical precursor of the oxide in the compositions described in this application, may be used to formulate the glass. be. Thus, phosphorus pentoxide may also be mixed into the glass batch in a non-volatile form such as lead phosphate, bismuth phosphate, or zinc phosphate. Similarly, fluorine can be mixed into the glass batch as zinc fluoride or lead fluoride. If desired, other conventional glass additives may be added to the glass formulation in amounts less than 5% of the total weight. These include TiO ₂ , SnO ₂ , CdO, TeO ₂ ,
As ₂ O ₃ , B ₂ O ₃ , Sb ₂ O ₃ , FeO, and other transition metal oxides, cerium oxide, and other rare earth oxides. The fused glass of the present invention is coated onto metal, glass, or ceramic components to a thickness ranging from about 100 to 700 microns. These metals, glass,
Or ceramic parts usually have a side of about 6~
Square or rectangular in the range of 25mm with a thickness of 200
It is manufactured in the form of a flat plate of ~2500 microns or a three-dimensional shape with a recess. The pattern (coating) of the fused glass on the entire surface or on the same edge is formed by printing and glazing. These components may be encapsulated at low temperatures by ceramic and metal packaging of electronic components, commercially known as side-brazed packages, chip carriers, and pin grid arrays. The following examples describe the preparation and composition of the fused glass of the present invention. These examples are not intended to limit the invention in any way. Example 1 A base glass was prepared by mixing 250 g lead oxide, 250 g vanadium pentoxide, 24 g zinc oxide, 61.5 g ammonium phosphate, and 30 g bismuth trioxide. After heating the mixture at 700° C. for 20 minutes in a porcelain crucible, the melt was poured through a cold steel rolling mill to facilitate subsequent milling. The glass fragments obtained had the following composition in weight percent: PbO 43.5% V ₂ O ₅ 43.5% ZnO 4.2% P ₂ O ₅ 3.6% Bi ₂ O ₃ 5.2% Coefficient of linear thermal expansion of this glass (25℃~200℃) is 106
×10 ^-7 /°C, and the softening point according to DTA (differential thermal analysis) is 225°C. This glass forms chemical bonds with alumina at 280°C, as observed under a high magnification microscope (400x). Example 2 A base glass was prepared by mixing 250 g lead oxide, 250 g vanadium oxide, 24 g zinc oxide, 61.5 g ammonium phosphate, 30 g bismuth oxide, and 2 g cuprous oxide. . After heating this mixture in a porcelain crucible at 700°C for several minutes, the melt was poured into a cold steel rolling mill and passed through.
Glass shards were formed to facilitate subsequent shredding. The obtained glass shards are expressed in weight%
It had the following composition: PbO 43.3% V ₂ O ₅ 43.3% ZnO 4.2% P ₂ O ₅ 3.7% Bi ₂ O ₃ 5.2% Cu ₂ O 0.35% The coefficient of linear thermal expansion of this glass (25℃~ 200℃) is 102
×10 ^-7 /°C, and the softening point by DTA is 220°C. Other examples of melt-sealed glasses of the invention were prepared according to the procedures described in Examples 1 and 2.
These other examples (designated D, E, F, G, and H) are shown in Table 2 below, along with comparative glass compositions (designated A, B, and C). These comparative glass compositions lack one or more of the five essential components in the glasses of the invention.

[Table] In Table 2, Example A represents a composition consisting of lead oxide and vanadium oxide that melts at the lowest temperature (binary eutectic). This material, in the form of a homogeneous melt, forms an unstable glass when cooled rapidly from 700 °C to room temperature. When this material is reheated above its softening point, rapid recrystallization occurs;
It becomes impractical as a melt-sealed glass. Glasses B and C lack bismuth oxide and phosphorus/niobium/tantalum oxides, respectively, and are similarly unstable. As zinc, phosphorus, and bismuth oxides are gradually added to the initial lead oxide and vanadium oxide melt, the resulting glass becomes increasingly stable. Glass D, E, F, G, and H
becomes stable to the extent that it is glassy and very fluid for extended periods of time when held at about 320°C. Glass stability (or glass life) in the table above is defined as the ability of the glass composition to retain the desired amorphous and fluid phase at or slightly above the pour point. Example D,
In E, F, G, and H, these glasses
Remains fluid for at least 10 minutes at 300°C.
In contrast, Glass A recrystallizes almost instantaneously within a few seconds. ZnO, Bi ₂ O ₃ , and
It is clear that the co-addition of P ₂ O ₅ provides the minimum glass life required for a practical fused glass. Similarly, as is clear from Examples E, F, G, and H, phosphorus pentoxide may be partially or completely replaced with niobium pentoxide or tantalum pentoxide. Furthermore, examples of stable glasses (referred to as I to N)
are shown in Table 3 below. As is clear from Table 3,
A soft glass very suitable for application as a sealant is produced by adding bismuth oxide, zinc oxide, and phosphorus/niobium/tantalum pentoxide to a mixture of lead oxide and vanadium oxide. obtain.

【table】

[Table] Example 3 Glass fragments prepared according to Example L in Table 3 were ground in a ball mill, and the resulting powder was milled on a mesh of 150
sifted. This fine glass powder is based on a mixture of zirconium silicate powder,
It was mixed at 20% by weight and made into a paste using 10% by weight butyl carbitol solvent. The resulting paste was screen printed with pre-oxidized copper alloy onto the part (copper alloy containing a small amount of silicon), dried and heated to melt the fused glass material. The thickness of the molten glass layer was approximately 200 microns. The part with the glass layer formed thereon was turned over and mounted intact onto another copper alloy microelectronic circuit package by the pressure of metal clips. This structure was heated at a rate of 320 degrees Celsius per minute.
It was heated to a maximum temperature of 0.degree. C. for 5 minutes and then cooled to room temperature to create a hard, strong glass seal. The structure was first leak tested and then subjected to a series of thermal shock tests. This thermal shock test
MIL-SPECS 883, Method 1014, referred to as Condition C,
This is a test in which temperature changes from 150 to -65°C are repeated 15 times. When tested in this way, this structure:
It showed a certain level of airtightness lower than 1×10 ^-8 cc/sec He. This shows the extremely strong properties of the melt-sealed glass of the present invention. Example 4 Glass L in Table 3 was crushed into a fine powder, and 75
% by weight of silver metal powder. Then about 10
A weight percent of butyl carbitol acetate solvent was added to this powder mixture to form a die attach paste. The paste was roll milled to form a well-dispersed suspension, and then a small amount of the silver glass paste was coated onto the ceramic surface. Next, a silicon semiconductor chip was embedded in this paste. After conditioning and drying, this structure is approximately
Gradual heating to 300°C created a strong bond between the silicon chip and the substrate. Example 5 Glass L from Table 3 was ground with 20% by weight of niobium pentoxide powder. Then, add 25g of this mixture to 75g
of silver powder. Processing as in Example 4 resulted in very strong bonding with copper alloy, sapphire, or glass substrates. Example 6 A glass similar in composition to Example 1 was prepared by replacing zinc oxide with barium oxide. Although a glass with good stability was obtained, it did not have fluidity like the glass of Example 1. Similar glasses were prepared using strontium oxide in place of zinc oxide with essentially similar results. As is clear from these examples, strontium oxide and barium oxide can be substituted for zinc oxide, but zinc oxide remains the preferred additive. Example 7 Other fused glasses within the scope of the present invention were prepared. These are shown in Table 4. These glasses are
Called T, U, and V, lead oxide is increasingly replaced by cesium oxide, thus increasing flowability.

【table】

Table Example 8 A basic glass was prepared by mixing the following ingredients: 250 g lead oxide 250 g vanadium oxide 24 g zinc oxide 30 g bismuth trioxide 10 g tantalum pentoxide This mixture was After heating at 700° C. for 20 minutes in a crucible, the resulting molten solution was poured through a cold steel rolling mill to facilitate subsequent milling. Glass-like fragments have a coefficient of linear thermal expansion of 106×
10 ^-7 /℃ (25~200℃), and the DTA softening point is
It is characterized by a temperature of 225°C. The resulting glass shards have the following composition in weight percent: PbO 44.3% V ₂ O ₅ 44.3% ZnO 4.3% Bi ₂ O ₃ 5.3% Ta ₂ O ₅ 1.8% Niobium pentoxide ( 32% by weight powder of columbium pentoxide)
(based on the mixture) and ball milled for several hours. The glass/niobium oxide powder mixture is prepared by depositing a small amount of the powder mixture on saphire (single crystal alumina) at approx.
Tested by melting for a few seconds at 300°C. When the resulting glass was cooled and examined one hour later, there was no evidence of any ridges on the glass.
There was also no evidence of color interference occurring at the saphire interface. This indicates that the fused glass mixture of the present invention perfectly matches the coefficient of thermal expansion of alumina ceramic. Close inspection of the surface of the glass/niobium oxide powder filler molten mixture shows that the niobium oxide powder tends to be significantly and rapidly wetted by the molten glass. Such properties are not easily obtained with traditional silicate and titanate powders and therefore greatly facilitate the process of pre-forming glass layers on semiconductor ceramic parts. The fused glass mixture was made into a paste by adding about 10% by weight of butyl carbitol solvent. The resulting paste was screen printed onto alumina parts using a stainless steel shielding screen. Dry this part thoroughly and heat it to about 290℃ on a heater block to melt it.
A pattern of fused glass was bonded to the ceramic surface. The thickness of the molten glass pattern is 200~250
It was about microns in size. The glass-coated alumina component was turned over and attached intact to a typical microelectronic circuit substrate using the pressure of a metal clip. The structure was heated at a rate of 75-100°C per minute to a maximum temperature of about 330°C for 5 minutes and then cooled to room temperature to create a tight, strong glass seal. The structure was first leak tested and then subjected to a series of thermal shock tests. This thermal shock test
MIL-SPECS 883, Method 1014, referred to as Condition C,
This is a test in which temperature changes from 150 to -65°C are repeated 15 times. When tested in this way, this structure:
It showed a certain level of airtightness lower than 1×10 ^-8 cc/sec He. Example 9 The basic glass of Example 8 with 1% _TiO2
Mix with 30% by weight _{of PbO.Nb2O5} powder sintered at 1150℃. This lead niobate material can be used at 25℃ and 500℃
It has a negative coefficient of thermal expansion between . Obtained glass/
Coating the filler mixture onto alumina ceramic parts provides strength and tightness results similar to Example 8. Example 10 The basic glass of Example 8 is mixed with 35% zirconium phosphate (ZrO ₂ .P ₂ O ₅ ). The coefficient of linear thermal expansion of this zirconium phosphate is 5×10 ^-7 /°C.
When the resulting glass/filler mixture is coated onto alumina ceramic parts, similar strength and tightness results as in Example 8 are obtained. Example 11 The basic glass of Example 8 is mixed with 40-50% by weight of lead titanate (PbO.TiO2 ₎ . These lead titanates have a coefficient of linear expansion equal to -60 × 10 ^-7 °C, and at 600 to 800 °C, 10% by weight each
V ₂ O ₅ (expansion rate = 6.3×10 ^-7 /℃), As ₂ O ₅ , and
Sintered with Sb ₂ O ₅ . These three powders were tested according to Example 6. These three powders were easily wetted by the glass and substantially reduced the coefficient of thermal expansion of the original glass. Example 12 Example 8 was repeated, except that instead of Nb ₂ O ₅ 45% by weight of Ta ₂ O ₅ powder (expansion coefficient = 20×10 ⁻⁷ /° C.) was added to the glass. The strength and tightness were similar to those obtained in Example 8. Examples 13-17 below illustrate the compatibility of powders of niobium pentoxide, tantalum oxide, and other refractory fillers derived from Group V elements with solder glasses other than the solder glasses of the present invention. It is something. Example 13 A series of lead borate and lead borosilicate glasses (Table 5 below) were prepared in a conventional manner. These preparations were carried out by melting the batch components in a platinum crucible at 900°C for 30 minutes, except that Glass E required higher temperatures (1100°C). The melt was poured through a stainless steel rolling mill to produce glass shards. These glass fragments were then ball milled and passed through a 150 mesh sieve.

[Table] The obtained glass powders A to F were mixed with mesh 325 niobium pentoxide powder. The alpha radiation dose of this niobium pentoxide was lower than 0.1 counts/cm ² /hour. The weight percentages of glass and niobium oxide powder are shown in Table 6 below. To measure the coefficient of thermal expansion, rod samples of fused glass were prepared (data shown in Table 6). As can be easily seen, the coefficient of thermal expansion of each original glass can be varied from 50 to 120 x 10 ^-7 /°C to alumina or any other substrate by adjusting the amount of niobium pentoxide added. Can be changed to suit.

[Table] An alumina ceramic package was sealed with fused glass compositions 2, 3, 5, and 6 of Table 6,
Thermal shock from 150°C to -65°C to 150°C was repeated 15 times, but the airtightness remained. Example 14 Borosilicate glass powder B (Table 5) was mixed with niobium pentoxide powder in increasing amounts. The resulting glass/filler mixture was pressed into a cylindrical container and sintered. When the linear thermal expansion coefficient of the obtained sample was measured, the expansion coefficient was 110 × that of pure glass.
An approximately linear decrease from 10 ^-7 /°C to 56 x 10 ^-7 /°C for a mixture containing 46% by weight niobium pentoxide was obtained. Example 15 Lead borosilicate glass powder B (Table 5) was mixed with 20% by weight of Al ₂ O ₃ Nb ₂ O ₅ and the composite oxide shown in Table 1, and sintered as in Example 14. Ta. The coefficient of linear thermal expansion decreased as a function of the specific coefficient of thermal expansion of each filler. Example 16 A series of zinc borate and zinc borosilicate glasses were prepared at 1100°C as in Example 13 and glass shards were made (Table 7 below).

【table】

[Table] These fragments were finely ground with isopropyl alcohol in a high purity alumina ball mill to prepare a suspension of powder with a particle size of less than 5 microns. Niobium pentoxide (20 wt%) was added to each glass suspension, and the resulting slurry was applied to the surface of silicon wafers with a dotter blade, dried, and heated to 750–800 °C in a diffusion cylindrical furnace. . The resulting glass thin film, with a thickness of 25-50 microns, was compatible with the coefficient of thermal expansion of silicon wafers.
These thin films are extremely useful for surface protection of silicon devices and insulation of high voltage silicon power devices. Example 17 Example 16 was repeated using 25% by weight tantalum pentoxide powder instead of niobium pentoxide. Similar results were obtained. Tantalum pentoxide lowers the dielectric constant of glass compositions coated onto silicon surfaces. Modifications of the above-described modes of carrying out the invention, which will be apparent to those skilled in the art of glass manufacturing, packaging of semiconductors or other electronic components, and related fields, are intended to be within the scope of the following claims.