JPS63502583A - Low temperature melting glass composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] :1 night stay ■" The present invention relates to a novel low temperature melt sealing glass. The present invention is particularly suitable for melting at very low temperatures. Regarding glass. The glass may have ceramic fillers added or Electroceramic components such as alumina and beryllia without additives at 300°CN The area can be hermetically sealed.

Yihe skinhui The present invention is directed to a type of semiconductor that does not endure a melting cycle exceeding about 300°C. It addresses the problem of sealing elements and hybrid circuits with glass.

Such semiconductor devices include materials such as gallium arsenide and many other ■-V group compounds ( In other words, it is a compound consisting of Group Ⅰ elements and Group V elements of the 9 periodic table).

Ceramic and glass compositions such as television picture tubes and semiconductor ceramic packages Commercially available solder glass that can melt-seal components is useful in the temperature range of 420-500°C. It is well known in the art that these solder glasses Lead-boron produces extensive glass-forming areas in combination with lyca and alumina derived from the oxide binary system of

The lead oxide-boron oxide eutectic contains 13% by weight boron oxide and 87% by weight lead oxide. It is the most fluid glass in such a two-component system. Commercially available This is the starting point from which most soldered glass is derived. certain metals Oxides 2 such as silica, alumina, tin oxide and barium oxide are added to the glass melt. When added to the Improves hydrothermal properties.

Lead borate glass is melt-sealed by adding fine-grained ceramic filler with a small expansion coefficient. Over the past 20 years, semiconductor packages have been improved by adjusting the linear thermal expansion coefficient of the entire glass. very successful in meeting the requirements for mechanical strength and tightness in the It's here. However, when using lead borate glass or lead borosilicate glass, , there is a specific lower temperature limit, which prevents melt sealing at temperatures lower than 400-420°C. Ru.

Certain advanced semiconductor devices (e.g. gallium arsenide) and related ■-V With the advent of compound multilayer semiconductor devices (e.g. laser diodes), or less and can be processed to U.S. Army specifications (MIL-SPE There is an urgent need for a practical melt-sealed glass that can further satisfy CS 883).

To develop practical low-temperature melting glass for melting at 300℃ or lower. Various attempts have been made to date, but these attempts have been limited to materials with potential. were severely limited by the lack of choice. In particular, two things are expected: .

It uniquely combines the following properties: low melting point;

a mixture of metal oxides that is a true solution (supercooled liquid that does not form a glass), It has a low viscosity in the liquid phase and a small coefficient of linear thermal expansion, and is stable in the glass phase. A mixture of metal oxides, such as

A possible candidate is a lead-vanadium oxide binary system, but this The component system forms a eutectic at a lower temperature than the lead-boron oxide eutectic. This system is It tends to form glass during rapid cooling, but when reheated, less However, it recrystallizes rapidly, making it impractical.

In U.S. Pat. No. 3,408,212, Dumesnil et al. The effect of adding lead chloride to a lead-vanadium oxide mixture is described. narrow gala The gas forming region exists in the center of the ternary diagram of Pb0-PbFz-VzOs, and the improvement It has been found that the glass has a stable life span. These soft glass The linear thermal expansion coefficient of steel is very large (135 to 155 Xl0-’/”C), but in reality The glass form is not stable enough to be considered a commercial glass sealant.

Malmendier and 5ojka (U.S. Pat. No. 3.837.866) ) is the combination of ASzO* and AszOs with Pb0-VzOs eutectic and C5zO-VzOs Added to both eutectics.

The aim is to prevent recrystallization early and expand the composition range in which stable glass can be produced. I'm looking forward to it. However, the addition of arsenic oxide rapidly reduces the viscosity of the resulting glass. and therefore has fluidity at or below 300°C. stable This impedes its usefulness as solder glass.

Dumesnil et al., in U.S. Pat. No. 3,650,778, Weight % (D % BJs by weight.

and 10 to 25 wt% p2o, ing.

British Patent No. 1,552,648 discloses that up to 50% zirconium phosphate (ZrO Describes Pb0-VzOs-PzOs glass mixture mixed with z　・has) powder are doing.

Busdiecker (U.S. Patent No. 3,454.408) is added to vanadium to produce low-temperature solder glass with a large expansion coefficient. is listed. He is necessary for two inventions.

There is no mention of adding Bi2O3, which is an essential component. This invention is based on Nb , O, and T. Although it does not mention any of the Ol.

Both of these are highly desirable components in the melt-sealed glass of the present invention.

Mitsugai Shosagijo The present invention provides a lead-vanadium oxide binary system including (i) bismuth oxide; (ii) oxides of zinc, barium, or strontium; and (iii) phosphorus, niobium By adding tantalum oxide or tantalum oxide, it has very high fluidity. Stable glasses can be prepared. It is based on the discovery that These three oxides are , when added to lead and vanadium oxides, form a fluid and stable glass. This gives rise to a wide range of properties, and from such a range it becomes very practical for application as a low-temperature sealing material. A practical two-component glass is obtained.

The novel low-temperature melting glass composition of the present invention has a weight calculated on an oxide basis. Contains the following components in %: (a) P b 0 30-55%.

(b) VzOs 30-55%.

(C) Big (h 0.1-18%.

(a) pzos, N1) 20S+ TazOs+ or a combination thereof 0.1-10%.

(e) ZnO, Bad, SrO, or a combination thereof 0.1-10% .

Cocote, the total weight% of (C) + (d) + (e) is 0.3% and 20 %, and (a) partially contains up to 25% by weight of cesium oxide. There is a condition that it can be replaced.

This new glass composition has a melt sealing temperature of about 300°C.

The melting time is short, the temperature is high and the humidity is high (85°C/85% relative temperature). It has excellent thermal shock resistance and high chemical resistance under environmental conditions.

Preferred glass compositions of the invention have substantially It essentially consists of the following components: (a) P b O 35-45%.

(b) VzOs 35-45%.

(c) B i t 03 3-8%.

(d) Zn0 2-7%.

(e) pzos o ~ 5%.

(f) Nb 20S 0-5%.

(g) TazOs O~8%.

Here, the total weight% of (e) + (f) + (g) is 0.1 to 10% is within the range of

A ceramic particulate filler with a small coefficient of thermal expansion is added to the above-mentioned novel glass composition. Preferably, the Group V metal oxide is mixed at about 1% to about 50% by weight based on the mixture. 9 mixtures are another aspect of the present invention.

Addition of silver or gold to the novel glass composition or glass composition/filler mixture described above. A mixture in which the powder is mixed up to 90% by weight based on the entire mixture is the two according to the present invention. It's a different aspect.

Solder glass mixed with a filler of group V metal oxide in an amount of about 1 to about 50% by weight is 1 is yet another aspect of the present invention.

Chief student dish disaster ■ dog Depending on the particular application in which the glass of the invention is used as a sealant, additives or fillers may be added. agents can be combined with the basic two components of this glass. Examples of such additives and Copper oxide, silver oxide, and fluorine are typically added to the glass composition in an amount of 3% by weight. WO3 and H2O2 are mixed into the glass, typically in amounts up to 5% by weight. mixed into the composition.

Adding such amounts of copper oxide to a glass composition can cause the surface of metals such as gold to Improves adhesion to lath. If necessary, add silver oxide to improve the fluidity of the glass. can be improved.

Adding fluorine to this composition increases the coefficient of linear thermal expansion of the resulting glass. child 2. For example, mild steel, copper, copper alloys, aluminum, and aluminum alloys. Melt-sealing metals with large thermal expansion coefficients (thermal expansion coefficient > 155X10-’/”C) Compositions are provided that are suitable for use in. Glass anxiety due to the presence of fluorine To compensate for the increased quality, bismuth oxide and/or nitric oxide can increase the amount of bubbly.

The fine particulate ceramic filler is the glass powder of the present invention.

as a means of controlling the overall thermal expansion and contraction of the resulting fused glass mixture. Can be added. Increasing the amount of ceramic filler with a small coefficient of thermal expansion makes the melt-sealed glass There is a corresponding decrease in the linear expansion coefficient of It is a linear function of the ratio. Such fillers are typically ceramics with low expansion coefficients, Used to produce glass suitable for sealing glass or metals. melt The coefficient of thermal expansion of the sealing glass is Lilia or steatite parts) are strictly compatible.

It is critical to keep stress free at the seal joints. child This ensures strength and tightness under extreme conditions of thermal cycling and thermal shock. Ga The presence of a second crystalline phase in the lath is advantageous when the glass seal expands and contracts. It is also known that Adding fine particulate fillers.

Minimize propagation of cracks throughout the glass.

Used with lead soldered glass. Conventional refractory silicates (e.g. β-Yuk) liptite zirconium silicate, zinc silicate, cordierite) and titanium acid salts (e.g.

(lead titanate), but the low temperature melt sealing glass of the present invention does not contain such a filler. Do not moisten the surface sufficiently. however.

Manufactured from oxides of group V metals (P, As, sb, v, Nb, Ta) The refractory fillers are completely compatible with the glass of the present invention and are compatible with traditional fillers. It exhibits superior wettability and provides an excellent hermetic seal compared to is found. These new Group V metal fillers are suitable for use with solder glass of the present invention. It is also useful for soldering glass outside. Table 1 below lists this new class of fire-resistant fillers. Examples of fillers, if known, can be found in the table of linear thermal expansion coefficients. ``The given value is Xl0-'/'C As illustrated in Table 1, the term "Group V metal oxide" refers to the combination of Group V metals and acids. Represents a compound containing an element with or without other metals. of this new category Among the fillers, niobium pentoxide is preferred (its linear thermal expansion coefficient is approximately zero). radiation Products with very low radiation levels (alpha radiation dose <0.1 counts/d/hour) are commercially available. radiation-sensitive semiconductors such as silicon memory chips. Highly desirable for sheathing conductive elements. Other niobium-containing oxides such as niobium Lead titanium butate and lead bismuth titanium niobate are also excellent fillers.

Fillers are typically is mixed with the glass composition in an amount ranging from 1 to 50% by weight, based on the mixture.

A mixture of these.

The glass shards and refractory powder are placed in a ball mill and ground using traditional methods to remove most of the It is prepared by uniformly mixing the components into fine particles.

The resulting glass refractory mixture can be applied as such to the workpiece or Mix with organic solvent to form a paste.

Can be used to coat manufactured items. This work is then heated to melt the glass. to create a seal coating. organic solvents.

Preferably a synthesis solvent 9 boiling within the range of 150 to 220"C, e.g. Pitol, carpitol acetate, or a similar solvent.

Metal powder fillers, such as silver or gold, bond the die when encasing the semiconductor chip. 1. Up to 90% by weight, based on the mixture, of the glass powder of the invention for applications in which 9. Normally 70-80% of the equipment can be mixed. The metal-glass mixture is as described above. can be made into a paste for application to dies by formulating with organic solvents such as Ru. Refractory fillers such as those described above can be added to metal-glass mixtures to form electronic components. , control stress at the bond interface between metal, glass, or ceramic substrates It is possible.

Lead oxide in glass compositions can be partially replaced by cesium oxide up to 25% by weight It has also been found that Such a replacement would make the glass more fluid. It can be done to

First aspect of the use of these glasses and glass-filler mixtures of the invention The target is a low fused glass temperature in the 300°cel range, but it is characterized by a higher temperature. It should be understood that there may be special applications in which Therefore, there is no upper limit to the temperature. This is unique to the application of the glass material of the present invention.

Cupric oxide, cuprous oxide, litharge (PbzO4), lead dioxide (PbO□), or any chemical precursor of the oxide in the compositions described in this application may It is readily understood by those skilled in the art of glass manufacturing that it can be used to formulate It's about getting. Therefore, phosphorus pentoxide, lead phosphate, and bismuth phosphate.

Or it can be mixed into the glass batch in a non-volatile form such as zinc phosphate. similarly , fluorine can be mixed into the glass batch as zinc fluoride or lead fluoride.

If necessary, other common glass additives may be added to the glass formulation in amounts less than 5% of the total weight. Can be added in large quantities. These are TiO□.

SnO, CdO, Tea, As, 0. , B, O,, Sb, O,, Pea , and other transition metal oxides, cerium oxide, and other rare earth oxides.

The fused glass of the present invention can be applied onto metal, glass, or ceramic components at approximately 100% Coated with a thickness in the range of ~700 microns. These metal, glass, or Ceramic parts are usually square or rectangular with sides ranging from about 6 to 25 squares. , in the form of a flat plate with a thickness of 200 to 2500 microns, or in the form of a three-dimensional piece with a recess. Manufactured. The pattern (coating) of the fused glass on the entire surface or around the edges can be printed or and glazing. These parts are side-brazed ( side-brazed) packages, chip carriers, and bin doors Commercially known as Ray. Ceramic packages for electronic components, and gold The package can be sealed at low temperatures.

(Margin below) The following examples describe the preparation and composition of nine fused glasses of the present invention. these fruits The examples are not intended to limit the invention in any way.

Backyard■-Top Basic glass consists of 250g lead oxide, 250g vanadium pentoxide, 24g oxide Zinc, 61.5 g ammonium phosphate, and 30 g bismuth trioxide. Prepared by mixing. This mixture was heated in a porcelain crucible at 700°C for 20 After heating for minutes, the melt is poured through a cold steel rolling mill and subsequently crushed. made it easier. The resulting glass shards had the following composition at 9% by weight: PbO43.5% VzOs 43.5% Zn0 4.2% PzOs 3.6% Bi2035.2% The linear thermal expansion coefficient (25”C to 200°C) of this glass is 106 x 10-’/ "C, and the softening point according to DTA (differential thermal analysis) is 225°C. The glass was heated at 280°C as observed under a high magnification microscope (400X). Forms chemical bonds with alumina.

1 serving 1 The basic glass is 250g of lead oxide and 250g of vanadium oxide.

24g zinc oxide, 61.5g ammonium phosphate, 30g bismuth oxide , and 2 g of cuprous oxide. Make this mixture into porcelain After heating at 700°C in a crucible for several minutes, the melt was poured into a cold steel rolling mill. Glass shards were formed to facilitate threading and subsequent shredding.

The glass fragments obtained had the following composition at 9% by weight: PbO43.3% V, 0. 43.3% ZnO4.2% p, o, 3.7% Bit (h 5.2% Cu, OO, 35% The linear thermal expansion coefficient (25°C to 200°C) of this glass is 102 x 10-’/ 'C, and the softening point by DTA is 220°C.

Other examples of fused glass of the present invention can be obtained by following the procedures described in Examples 1 and 2. It was prepared as follows. These other examples (D.

E, F, G, and H) are the comparative glass compositions (A, B, and C). ) are shown in Table 2 below. The glass compositions of these comparative examples are the two glass compositions of the present invention. lacking one or more of the five essential components in the

(Margin below) hawk knee turtle Ingredients ABCDEFGH uuusssss S・Stable U = unstable In Table 2, Example A consists of lead oxide and vanadium oxide.

Represents the composition that melts at the lowest temperature (binary eutectic). It should be in the form of a homogeneous melt. The material forms an unstable glass when cooled rapidly from 700°C to room temperature. . Reheating this material above its softening point causes rapid recrystallization and melt sealing. It becomes impractical as glass. Glasses B and C are made of bismuth oxide and and phosphorous/niobium/tantalum oxides, and are similarly unstable. first Next, the oxides of zinc, phosphorus, and bismuth are added to the melt of lead oxide and vanadium oxide. With increasing additions, the resulting glass becomes increasingly more stable. Glass D, E, When F, G, and H are held at about 320°C, glass remains for a long time. It becomes stable to the extent that it is in a liquid state and is very fluid.

What is the stability of the glass (or the lifespan of the glass) in the table above?

Glass compositions are desirable amorphous and Defined as the ability to retain a fluid phase.

For illustration, E, F, G, and H, these glasses have a maximum temperature of 300°C. Maintains fluidity for 10 minutes. In contrast, glass A Recrystallizes almost instantly. ZnO.

When Bi2O2 and P2O are added together, the properties required for practical melt-sealing glass are achieved. It is clear that a minimum glass life can be obtained. Similarly, examples E, F, and G , and H.

Phosphorous pentoxide can be partially or completely replaced with niobium pentoxide or tantalum pentoxide. Can be exchanged.

Additionally, examples of stable glasses (referred to as ■ to N) are shown in Table 3 below. From Table 3, it is clear that Soft glass, which is very suitable for application as a melting material, is made of lead oxide and oxidized glass. mixture of vanadium, hismuth oxide, zinc oxide, and phosphorus/niobium/tan It can be produced by co-adding tal pentoxide.

(Margin below) moat-”- (Example 1% by weight) "10-'/"C vinegar[ The powder obtained by crushing the glass fragments prepared according to the example in Table 3 in a ball mill was passed through a mesh 150 sieve. This fine glass powder is made of zirconium silicate. 200% by weight based on the mixture and 10% by weight of butyl carbon. It was made into a paste using Lupitol solvent. the resulting paste.

Scrub onto pre-oxidized copper alloy parts (copper alloy containing small amount of silicon) Lean printing, drying, and heating melted the fused glass material. melted What is the thickness of the glass layer?

It was about 200 microns.

Turn the part with the glass layer over and use the pressure of the metal clip to remove it as it is. It was mounted on a microelectronic circuit package made of another prepared alloy. this structure Heat at a rate of 75°C per minute to a maximum temperature of 320″C for 5 minutes and then A hard and strong glass seal was produced by cooling to room temperature.

This structure was first subjected to a leakage test and then subjected to a series of thermal shock tests. this heat The impact test is called MIL-SPEC5883, Method 1014゜Condition C, and 1 This is a test in which temperature changes from 50 to -65°C are repeated 15 times. When tested like this However, this structure has a constant level of less than 1×10-”cc/sec He. It showed airtightness. This shows the extremely strong properties of the melt-sealed glass of the present invention. .

Calamity■-Earth Glass L in Table 3 was crushed into a fine powder and mixed with 75% by weight silver metal powder. Ta. Approximately 10% by weight of butyl carpitol acetate solvent was then added to the powder mixture. In addition, a sticky adhesive paste was formed. Apply this paste to a roll mill, Ceramic with a small amount of this silver glass paste after preparing a well-dispersed suspension coated the surface. Next, a silicon semiconductor chip was embedded in this paste. . After conditioning and drying, gradual heating of this structure to about 300°C results in a silico A strong bond was formed between the chip and the substrate.

Implementation 1 Glass L from Table 3 was ground with 20% by weight of niobium pentoxide powder. Then this 25g of the mixture was mixed with 75g of silver powder.

When treated in the same manner as in Example 4, it is extremely difficult to bond with copper alloy, sapphire, or glass substrates. A strong bond arose.

tip-l 9 composition was similar to Example 1 by replacing zinc oxide with barium oxide. A glass was prepared. Although a glass with good stability was obtained, it was not as good as the glass of Example 1. It did not have such fluidity. Using strontium oxide instead of zinc oxide.

A similar glass was prepared with essentially similar results.

As is clear from these examples, strontium oxide and barium oxide are similar to zinc oxide. Zinc oxide remains the preferred additive.

Real IL-1 Other fused glasses within the scope of the invention were prepared. These are shown in Table 4. these The glasses are called T, U, and V, and lead oxide is gradually replaced by cesium oxide. liquidity is increasing, thus increasing liquidity.

(Margin below) Pig [ The base glass was prepared by mixing the following ingredients: 250g lead oxide 250g vanadium oxide 24g zinc oxide 30g bismuth trioxide Log of Kuntal Pentoxide After heating this mixture in a porcelain crucible at 700″C for 20 minutes.

The resulting molten solution is easily poured through a cold steel rolling mill and subsequently crushed. I made it. The glass-like fragments have a linear thermal expansion coefficient of 106×10-’/”C (25 to 20 0'C) and is characterized by a DTA softening point of 225°C. Ru. The glass fragments obtained have the following composition at 9% by weight: PbO44, 3% VzOs 44.3% Zn0 4.3% Bt203 5.3% Ta205 1.8% This glass shard contains niobium pentoxide (also known as columbium pentoxide). Add the powder at 32% by weight (based on the mixture) and ball mill for several hours. Ta.

The glass/niobium oxide powder mixture is made by adding a small amount of the powder mixture to sapphire (single crystal aluminum). Lumina) by melting for a few seconds at about 300°C. obtained When I examined the glass one hour after it had cooled, there was no evidence of any ridges on the glass. It also showed no color interference occurring at the sapphire/sapphire interface.

And, this means that the fused glass mixture of the present invention has a thermal expansion coefficient similar to that of alumina ceramic. This means that it is completely compatible with

Close inspection of the surface of the molten mixture of glass/niobium oxide powder filler reveals that niobium oxide This indicates that glass powder tends to be significantly and rapidly wetted by molten glass. ing. Such properties are easily obtained with traditional silicate and titanate powders. Therefore, it is necessary to form a glass layer on semiconductor ceramic components in advance. This makes the process very easy.

The fused glass mixture is prepared by adding approximately 10% by weight of butylcarpitol solvent. Therefore, I made it into a paste. The resulting paste is covered with a stainless steel shielding screen. was used to screen print onto alumina parts. Let this part dry thoroughly.

Heat to approximately 290°C on a heater block to melt and create a pattern of fused glass. was bonded to the ceramic surface. The thickness of the molten glass pattern is 200-25 It was about 0 micron.

Turn over the alumina part on which the glass layer has been formed, and use the pressure of the metal clip to In that state, it was attached to a regular substrate for microelectronic circuits. This structure is 1 Heat for 5 minutes at a rate of 75-100°C per minute to a maximum temperature of approximately 330°C. It was then cooled to room temperature to produce a hard and strong glass seal.

The structure was first leak tested and then subjected to a series of thermal shock tests. this heat The impact test is called MIL-5PEC3883, Method 1014゜Condition C, and 1 This is a test in which temperature changes from 50 to -65°C are repeated 15 times. tested like this However, this structure has a constant level of less than 1×10-”cc/sec He. It showed airtightness.

Disaster relief five-e The base glass of Example 8 was sintered with PbO at 1150°C with 1% TiO□. - Mix with 30% by weight of NbzOs powder. This lead niobate material is It has a negative coefficient of thermal expansion between 00°C. The resulting glass/filler mixture is When coated on naceramic parts, similar strength and tightness results as in Example 8 were obtained. can get.

Pig IL 2nd dan The basic glass of Example 8 was mixed with 35% zirconium phosphate (ZrO□・P2O5). Mix. The coefficient of linear thermal expansion of this zirconium phosphate is 5×10-'/''C.

When the resulting glass/filler mixture is coated onto alumina ceramic parts, the Similar strength and tightness results as in Example 8 are obtained.

1 boat 1 The basic glass of Example 8 was mixed with 40 to 50% by weight of lead titanate (pbo・Ti0z). Mix. These lead titanates have a coefficient of linear expansion equal to -60X10-'°C. 10% by weight of V2O5 (expansion rate) at 600-800°C. = 6.3xlO-’/”c), with AS20S and Oyohi Sb2O5 Sintered. These three powders were tested according to Example 6. These 3 The two powders are easily wetted by the glass and substantially reduce the coefficient of thermal expansion of the binary glass. I let it go down.

Disaster relief five - ■ Nb, 0. 45% by weight of Ta205 powder (expansion coefficient = 20X10-'/ Example 8 was repeated, except that 0.degree. C.) was added to the glass.

The strength and tightness were similar to those obtained in Example 8.

Examples 13-17 below are made from niobium pentoxide, tantalum oxide, and Group V elements. Powders of other refractory fillers derived and solder glass other than the solder glass of the present invention This explains the compatibility with the

Implementation ■ Once A series of lead borate and lead borosilicate glasses (Table 5 below) were prepared in the usual manner. Prepared. Except that glass E required a higher temperature (1100°C) , these preparations involve batch components being heated at 900°C for 30 minutes in a platinum crucible. This was done by melting. Pour the melt through a stainless steel rolling mill Then, glass fragments were made. These glass shards are then ball milled Passed through a mesh 150 sieve.

Tang knee■ Ingredients ABCDEF The resulting glass powders A-F were mixed with mesh 325 niobium pentoxide powder. child The α-ray radiation dose of niobium pentoxide was lower than 0.1 count/ci at 7 o'clock. . The weight percentages of glass and niobium oxide powder are shown in Table 6 below. thermal expansion coefficient For the measurements, rod-shaped samples of melt-sealed glass were prepared (data shown in Table 6). capacity As you can easily see, the coefficient of thermal expansion of each glass is 1 element.

By adjusting the amount of niobium pentoxide added, the can be varied to suit alumina or any other substrate within the range.

(Margin below) , table-”- (Example 9% by weight) Alumina ceramic packages were prepared using the fused glass compositions 2.3.5. of Table 6. and 6 and thermal shock from 150°C to 65°C2 and 150°C. The airtightness was not lost even though the application was repeated several times.

Implementation ■ Once Borosilicate glass powder B (Table 5) is mixed with niobium pentoxide powder in increasing amounts. It matched. The resulting glass/filler mixture was pressed into a cylindrical container and sintered. Obtained When the linear thermal expansion coefficient of the sample was measured, it was found that the expansion coefficient was 110% compared to pure glass. 56 for a mixture containing 46% by weight of niobium pentoxide from XIO-'/''C The result was that the resistance decreased almost linearly up to X10-'/''C.

Implementation length Powder B (Table 5) of lead borosilicate glass was mixed with 200 weight of Ah03/Nbzos and and the composite oxide shown in Table 1, and sintered as in Example 14. linear thermal expansion The modulus decreased as a function of the specific coefficient of thermal expansion of each filler.

For back spots ■- A series of zinc borate glasses and zinc borosilicate glasses were prepared in Example 11 as in Example 13. 00°C to produce glass shards (Table 7 below).

, table −j− HIJK These fragments are combined with isopropyl alcohol in a high-purity alumina ball mill. A suspension of powder having a particle size of less than 5 microns was prepared by finely pulverizing the powder.

Niobium pentoxide (20% by weight) was added to each glass suspension and the resulting slurry was poured into Apply it to the surface of the silicon wafer with a blade and let it dry.

It was heated to 750-800°C in a diffusion cylindrical furnace. The thickness is 25-50 microns. The resulting glass thin film matched the coefficient of thermal expansion of the silicon wafer. These thin films are , extremely useful for surface protection of silicon devices and insulation of high voltage silicon power devices. Useful.

Implementation U Example 16 was repeated using 25% by weight tantalum pentoxide powder instead of niobium pentoxide. repeated. Similar results were obtained. Tantalum pentoxide coated on silicon surface lowering the dielectric constant of the glass composition.

Modifications of the above modes of carrying out the invention may be used in glass manufacturing, semiconductors or other electronic components. As will be apparent to those skilled in the field of packaging and related fields, the following requirements apply: intended to be within the scope of the requirements.

international search report 1mafiaeal Apt""1"'"'PCT10s871003911 R hate C stop I temple ml^p-ritsu-N=PCT10587100391

Claims (11)

[Claims] 1. Low-melting glass containing the following components in weight percent calculated on the basis of oxides: Composition: (a) PbO 30-55% (b) V2O5 30-55%, (c) Bi2O3 0.1-18% (d) P2O5, Nb2O5, Ta2O5, or a combination thereof 0.1 ~10%, (e) ZnO, BaO, SrO, or a combination thereof 0.1 ~10%, where the total weight percent of (c) + (d) + (e) is 0.3% and 20%. %, and (a) partially contains up to 25% by weight of cesium oxide. There is a condition that it can be replaced. 2. The composition comprises at least one additive selected from the group consisting of: The low-temperature melting glass according to claim 1, which contains: Up to 3% by weight Cu2O Up to 5% by weight M0O3 Up to 3% by weight Ag2O 5 WO up to 33% by weight F 3. Low-melting glass containing the following components in weight percent calculated on the basis of oxides: Composition: (a) PbO3 35-45%, (b) V2O5 35-45%, (c) Bi2O3 3-8%, (d) ZnO 2-7%, (e) P2O5 0-5%, (f) Nb2O5 0-5%, (g) Ta2O5 0-8%, Here, the total weight percent of (e) + (f) + (g) is within the range of 0.1 to 10%. be. 4. A ceramic particulate filler with a low coefficient of thermal expansion, based on the weight of the mixture, Claims 1, 2, or 3, mixed in an amount of about 1% to about 50% by weight. Glass as described in Section. 5. 5. The glass of claim 4, wherein the filler is a Group V metal oxide. 6. The filler is a niop-containing oxide, zirconium phosphate, or tantalum oxide. The glass according to claim 4. 7. 5. The glass of claim 4, wherein the filler is niopide pentoxide. 8. Silver or gold powder is mixed up to 90% by weight based on the mixture. Items listed in item 1, 2, 3, 4, 5, 6, or 7 of the scope of the request. glass on top. 9. Claims 1, 2, 3, 4, 5, 6, or 7 metal, glass, or ceramic coated with a pattern of the glass composition described in Manufactured articles used in melt-sealing electronic components, including the body of a box. 10. A soldering gas mixed with a filler that is a group V metal oxide in an amount of about 1 to about 50% by weight. Russ. 11. The hanging glass is lead borate glass, lead borosilicate glass, or borate glass. 11. The solder glass according to claim 10, which is zinc glass.