Lead-Zinc-Boron Sealing Glass Compositions

Effort has been made in the past, without success, to provide the electronic industry with a glass material for sealing semi-conductor ceramic packages at the lowest possible temperature and with sufficient mechanical strength to maintain hermeticity during thermal shocks and other conditions as specified by the MIL-STD-883 specifications.

The technical requirements of an adequate sealing glass material are severe. The material problem has arisen particularly with the development of the dual-in-line type ceramic packaging technology and its wide acceptance as a relatively inexpensive multilead hermetic package for integrated semi-conductor circuits. The glass seal must not only bond two ceramic parts together but must also provide a strong hermetic seal with a substantially mismatched expansion metal lead frame within the glass layer.

Similarly in the formation of cathode ray tubes, in order not to damage the heat sensitive phosphor coating, metallic film shield or electrical contact, glass parts must be sealed at the lowest possible temperature.

Heretofore successful sealing materials for the above applications have been made with glasses, known generically as solder glasses, containing mainly lead, zinc and boron oxides, mixed as a powder with an inert, low expansion ceramic powder such as beta-eucryptite, fused silica, or zirconium silicate to modify the internal structure of the glass once the seal has been formed by heat induced recrystallization. The presence of a multitude of crystals within the glass layer, plus the presence of a low expansion ceramic filler, prevents the propagation of surface cracks through the glassy-polycrystalline seal which is subjected to considerable tensile stresses. These temperatures are too high to be used with a large proportion of semi-conductor devices, namely those known in the semi-conductor industry as MOS (Metal Oxide Silicon), LIC (Linear Integrated Circuits) and CCD (Charge Coupled Devices) integrated circuits, which are surface sensitive and prone to failure when heated over about 430.degree.C. Past attempts to lower the sealing temperature substantially below 480.degree.C have resulted in seals characterized by a low hermeticity or poor resistance to thermal shock.

The low melting glass-filler compositions of this invention overcome the above shortcomings of the prior art as they permit a glass seal to be made at approximately 400.degree.C. These glass seals tolerate imbedded metal leads with substantial expansion mismatch and maintain hermeticity even after a considerable number of liquid to liquid thermal shocks. This is a stress condition which even the higher temperature sealing glasses do not easily pass. Moreover, these glass-filler compositions provide hermetic sealing for surface sensitive semi-conductor devices in ceramic packages of large, as well as small, size.

Briefly, the invention comprises glass compositions containing lead, zinc, and boron oxides as the major components in which the zinc oxide content is made deliberately lower than the composition corresponding to the 2PbO-ZnO-B.sub.2 O.sub.3 molar ratio (2:1:1 molar ratio). Such glass compositions are very low melting and have softening points as low as 300.degree.C. These glass compositions are mixed in powder form with sufficient non-inert zinc oxide containing filler powder to convert the glass to a zinc oxide rich glass. This filler powder is used in amount such that its available zinc oxide content is at least sufficient to permit the hot mixture to partially or completely crystallize forming a solid crystalline phase in which the PbO-ZnO-B.sub.2 O.sub.3 molar ratio approaches 2:1:1. On melting, the glass initially flows to form a seal and this is converted from a lead-boron rich glass to a zinc oxide enriched glass preferably corresponding to the molar ratio of 2 moles of lead oxide to one mole of zinc oxide and one mole of boron oxide as available ZnO dissolves. The amount of zinc oxide containing filler added to the solder glass is sufficient to constitute 3 - 30% by weight of the glass-filler mixture. Very high mechanical strength is imparted by a polycrystalline structure containing well dispersed filler powder. The presence of the dispersed filler powder results from the employment of zinc oxide contributing fillers in amounts exceeding the amount required to produce a PbO-ZnO-B.sub.2 O.sub.3 ratio of 2:1:1. Employment of filler in amounts exceeding 30% by weight of the glass-filler mixtures should be avoided.

Experience has shown that adequate mechanical strength is mismatched glass-to-glass, glass-to-ceramic and ceramic-to-ceramic glass seals can best be obtained with glasses which become recrystallized after the seal is formed. This is particularly true in semi-conductor packaging seals in which metal leads are imbedded through the glass layer. A well known example is the type of ceramic packages generally known as the dual-in-line packages (CerDip) in which a complex etched or punched metal lead frame is imbedded between two glass layers supported by two alumina ceramic parts. The thermal expansion mismatch between the glass, the metal frame and the ceramic parts is appreciable and of the order of 15 to 20 .times. 10.sup..sup.-7 per .degree. C.

The term recrystallization, or devitrification, is used here in its conventional sense to mean a crystallization of glass wherein the glass is converted, or devitrified, to a crystalline phase, that is a rigid crystalline skeleton which may be associated with a glassy matrix and wherein thermal and other material characteristics or properties, such as viscosity and expansion, differ from those of the parent glass and are substantially determined by the crystalline phase.

The only glass materials which have been successful so far in being able to maintain hermeticity in these packages of the order of 10.sup..sup.-8 and 10.sup..sup.-9 std. cc/sec and mechanical strength after thermal cycling and thermal shock from about 150.degree. to -65.degree.C are recrystallizable glasses containing lead, zinc and boron oxides mixed with an inert, refractory metal oxide powder. These glasses recrystallize to near completeness to form a compound with the 2:2:1 lead oxide-zinc oxide-boron oxide stoichiometry.

The presence of a multitude of crystals within the glass seal, plus the presence of a low expansion, inert refractory metal oxide filler, prevents the propagation of surface cracks through the resulting glassy-polycrystalline seal. It is of importance when preparing this type of seal to choose a time-temperature cycle which insures completeness in the recrystallization of the glass. Improper or incomplete recrystallization severely weakens the mechanical strength and the hermeticity of the seal.

Every attempt in the past at developing and commercializing sealing glasses with a lower melting point by, for example, reducing the zinc oxide content, replacing part of the lead oxide by lead fluoride or adding other metal oxides or fluorides in the above glasses has produced seals which were substantially weaker and therefore undesirable.

Presently available sealing glasses are not suitable for the production of hermetically sealed ceramic packages, particularly those with the CerDip geometry, with a sealing range appreciably below 480.degree.C for a reasonably short time, that is less than 20 minutes at peak temperature.

The new sealing glass-filler compositions according to this invention combine a low melting lead oxide rich solder glass with a non-inert filler powder containing zinc oxide. We have noted that zinc oxide in pure or combined form has a tendency to dissolve in the glass when the glass is reheated, the rate of dissolution depending on the zinc oxide compound. The filler powder is non-inert in the sense that it dissolves in the solder glass and modifies the physical and chemical properties of that glass.

Heretofore dissolution of an added filler has been assumed to be undesirable because generally weak seals resulted from it, soluble filler materials have therefore been largely avoided. It has now been found that zinc oxide dissolves in and changes the composition of zinc poor PbO-ZnO-B.sub.2 O.sub.3 glasses to zinc richer glasses which can recrystallize to the 2PbO-ZnO-B.sub.2 O.sub.3 crystalline phase and have unusually high strength.

Accordingly it is an object of this invention to provide a method for modifying a very low melting, high lead solder glass by the addition of a sufficient amount of a filler material, which can be dissolved by the glass to provide enough missing zinc to produce a complete 2PbO-ZnO-B.sub.2 O.sub.3 crystalline phase with practically no glassy phase left within the seal.

Accordingly it is another object to combine a zinc bearing filler with a zinc-free lead borate glass or with a lead-zinc borate glass in which the zinc oxide content is lower than the required minimum of 13.6 percent by weight (and therefore quite insufficient to insure complete recrystallization of the glass). These latter glasses possess a combination of very low melting points and high fluidity which promote excellent wetting of the parts to be sealed at a very low temperature. Once the seal is formed the zinc has begun dissolving into the glass, thus changing the glass composition toward the 2PbO-ZnO-B.sub.2 O.sub.3 ternary phase diagram point and inducing recrystallization of the glass. On completion of the sealing cycle any glass phase left in the seal has dissolved enough zinc oxide and has fully recrystallized.

It is yet another object to describe a general method by which a glass powder is mixed with a finely dispersed zinc containing filler. On melting the glass-filler mixture, the composition of the glass changes to a zinc rich glass which can recrystallize fully to form a mechanically strong seal. Thus the concept of this invention is not limited to low melting glass-zinc filler mixtures but can be extended to include any glass with little or no tendency to recrystallize without the presence of zinc oxide.

Table 2 shows glass compositions, expressed in percent by weight, which illustrate lead-zinc-borate and lead-borate type glasses which have been found particularly suitable in making seals when combined with a zinc bearing ceramic powder and the combination is heated to temperatures of the order of 350.degree. to 450.degree.C.

In Table 3 the molar compositions of the several glasses shown in Table 2 are set forth.

While these glasses are particularly effective in making devitrified glass seals when finely divided and mixed with a zinc oxide contributing filler, it will be appreciated that the invention may also be practiced with other low zinc oxide glasses and under other conditions. Suitable low zinc glasses are not only those shown in Tables 2 and 3, but include those containing 75-90% by weight of lead oxide, 10-25% by weight boron oxide and 0-13% by weight of zinc oxide. The glass selected for making a given seal will depend on various factors including the properties of the materials being sealed, such as their expansion characteristics and softening point, the specified sealing conditions, particularly the temperature at which the seal is to be made or the permissible range of temperatures, and somewhat on the nature of the seal itself. With these factors established, one skilled in the glass art can then select or compound a semi-stable sealing glass material and determine the suitability of the glass material with the aid of sealing tests such as described subsequently.

The non-inert zinc oxide containing or contributing materials (simple or complex compounds, glasses or recrystallized glasses) which can be added in the form of a powder, either singly or in any combinations, to the above described low melting glasses in the range of 3.0 to 30% by weight, include the following: zinc aluminate, zinc borate, zinc carbonate, zinc chromate, zinc dichromate, zinc ferrate, zinc fluosilicate, zinc gallate, zinc hydroxide, zinc permanganate, zinc nitrate, zinc oxide, zinc orthophosphate, zinc aluminophosphate, zinc pyrophosphate, zinc silicate, zinc orthosilicate, zinc titanate, zinc zirconate, zinc stannate, zinc zirconium spinel, and zinc zirconium silicate.

Successful practice of the present invention requires a soft sealing glass. That is to say the glass must behave like a stable, soft sealing glass until a good seal is effected. A good seal between parts requires that the sealing glass be relatively soft and fluid at the sealing temperature so that it can flow over and completely wet the sealing surfaces of the preformed parts as well as completely fill the space between such surfaces. If the glass is too stiff, reentrant angles, folds and the like occur and the seal is mechanically and thermally weak. It is apparent then that the glass must be one which does not appreciably devitrify either during melting or in reheating prior to the formation of a seal.

It is quite desirable, however, that the sealing glassfiller material devitrify as rapidly as possible once a proper seal is formed. Preferably glass devitrification is initiated at the selected sealing temperature thus permitting the assembly to be raised to the sealing temperature and then held at that temperature for a short time, that is of the order of a few minutes to a quarter of an hour or so, while devitrification of the glass occurs.

For present purposes the expansion of the parent sealing glass is of relatively little importance, since the physical properties of the glass-filler mixture with the glass in its devitrified state determine the amount and nature of the stress developed in the seal and these properties tend to be quite different from those of the parent glass. While physical properties of devitrified glass-filler mixtures, particularly expansion data can be measured by conventional methods, it is more convenient to rely on mechanical strength and hermeticity data of the finished product. In the case of semi-conductor ceramic packages the MIL-STD-883 (issued by the Department of Defense on methods and procedures for testing mecroelectronic devices and their packages, including basic environmental tests) testing conditions should be used.

Accordingly, the glass seals made pursuant to this invention not only meet, but substantially exceed the more demanding test conditions of thermal shock (method 1011 -- Condition C), thermal cycling (method 1010), corrosion (method 1009), high temperature storage (method 1008), hermeticity (method 1014) and high humidity (method 1004). These methods are described in Code FSC 5962 published by the U.S. Department of Defense, May 1, 1968.

In preparing a sealing glass-ceramic material for the present purpose considerable care should be taken to avoid contamination of the glass during the mixing and smelting of the glass forming components and to insure a uniform composition throughout the melt. After the glass melt is cooled, it is reduced to a powdered form preferably being sufficiently fine to pass a standard 300 mesh screen. The powdered glass is thoroughly mixed with the desired zinc bearing filler which is present in quantities to constitute a 3.0 to 30 % by weight of the mixture and preferably also fine enough to pass through a 300 mesh screen. The glass-filler mixture may then be mixed with a conventional organic binder and vehicle to form a suspension or slurry for application to a sealing surface. Any organic material used should be capable of completely burning out or volatilizing well below the sealing temperature of the sealing material. A solution of 1-3% ethyl cellulose T-200 in amyl acetate or higher molecular weight solvent is effective. The ratio of glass to vehicle and binder will depend to a large extent on the manner of application, the viscosity of the suspension being adjusted to provide the desired thickness and coverage of powder on the sealing surface.

The suspension may be applied in various manners. Screen printing or spraying are desirable for the ceramic semi-conductor packaging parts. For cathode ray tubes, the suspension may be applied by feeding through a constricted tubular type of reservoir to form a ring or strip just covering the sealing surface, or dipping the part into a pool of suspended sealing glass mixture.

Where the coated articles must be handled or stored, the coating is preglazed, that is fused or at least partially fused prior to the actual sealing operation. In utilizing such preliminary glazing, it is important to avoid initiating devitrification since otherwise the sealing material may be sufficiently altered to interfere with the proper seal formation later on. The maximum permissible glazing temperature will depend then in large measure on the ease with which the glass-zinc mixture recrystallizes. It is generally desirable to employ lower glazing temperatures than the sealing temperature which may be of the order of 30.degree. to 50.degree.C below the sealing temperature.

During the sealing cycle, once the assembly has been heated to the sealing temperature and the sealing glass caused to wet the sealing surfaces and flow into the desired seal configuration, the sealing glass is held at its devitrification temperature for a sufficient time for the desired devitrification to be completed and thereafter cooled to room temperature.

The various features of the invention and the benefits which it provides are more fully set forth in the following examples.

An intimately mixed sealing glass material was produced by milling 80 parts by weight glass IV with 20 parts of zinc silicate, both as powders passing through a standard 300 mesh screen. This mixture was applied to the surface of alumina ceramic parts. Heating the parts together at 430.degree.C for 20 minutes produced a very strong thermally devitrified glass-zinc filler material sealing together the parts to form a hermetic cavity inside the ceramic parts. Similarly heating the glass alone or a mixture of 80% glass with 20% beta-eucryptite, fused silica or zircon, even at higher temperature for longer time, produced only partial recrystallization in the glass and the bond was weak and non-hermetic.

A series of sealing compositions was prepared by intimately mixing glass III with increasing amounts of zinc zirconium silicate ranging from 5 to 30% by weight. Both powders were 300 mesh. Heating at 440.degree.C for 20 minutes or at 460.degree.C for 3 minutes induced higher recrystallization with increased zinc filler content. The sealing strength increased remarkably above 15% by weight zinc filler.

Similarly lead borate glass X was intimately mixed 5 to 30% zinc zirconium silicate powders (300 mesh). The mixtures were heated at 410.degree.C. A longer time was required to induce maximum recrystallization than in example 2. The extent of recrystallization increased clearly as a function of zinc filler concentration and heating time. The glass alone or mixed with beta-eucryptite, silica or zircon showed no tendency to recrystallize.

Lead borate glass X was intimately mixed with zinc oxide powder to form a mixture containing 15% by weight of zinc oxide. The mixture was heated to 400.degree.C. Zinc oxide dissolved into the glass at a rapid rate causing it to devitrify.

Similarly lead borate glass X was intimately mixed with a series of zinc compounds. 30% by weight of the following 300 mesh powders were added: zinc silicate, zinc aluminate, zinc zirconate, zinc stannate, recrystallized zinc borosilicate glass powders. The mixtures were heated to 400.degree.C. Recrystallization of the glass was less rapid than in example 4 but became complete. Mechanical strength of the glass-zinc filler mixtures increased rapidly with zinc filler concentrations.

An intimately mixed sealing glass material was produced by milling 82 parts glass VI with 18 parts of zinc zirconium spinel (zinc zirconium alumina silicate - ZnO(Al.sub.2 O.sub.3).sub.0.855 (SiO.sub.2).sub.1.43 (ZrO.sub.2).sub.1.35) both as powders passing through a standard 300 mesh screen. 0.5 part of inert black colored stain was added. The mixture was applied to the surface of alumina ceramic parts (CerDip). The parts were preglazed at 390.degree.C. A prepunched metal lead frame was inserted in the melted base part and the package sealed at 430.degree.C for 15 minutes. Very tight and strong seals were obtained. These semi-conductor packages were subjected to 30 cycles liquid-to-liquid thermal shocks (MIL-STD-883, method 1011, condition C) without affecting their hermeticity.

An intimately mixed sealing glass material was produced by milling 85 parts by weight glass XI with 10 parts zinc silicate and 5 parts zinc aluminate (300 mesh powders). The mixture was applied on cathode ray tube parts. The parts were sealed at 410.degree.C. A strong, hermetic seal was produced.

It is readily apparent from these examples that lead borate and zinc poor lead-zinc-borate glasses can be used to advantage by the addition of zinc containing fillers. The fluidity and the recrystallization rate of these semi-stable sealing glass materials can be controlled by the proper selection of a glass from Table 2 and of zinc containing filler or combination of fillers. Thus, the so-called working properties and working range of these sealing materials can be adjusted over wide limits according to the particular application.

It should be noted that all of the glasses shown in Table 2 have a small content of SiO.sub.2. The presence of SiO.sub.2 in amount at least about 0.5% by weight of the glass-filler mixtures is highly desirable since the SiO.sub.2 slows crystallization of the glass and so permits better control in producing a proper seal. The selection of the solder glass and filler should be made with a view to producing a mixture having an SiO.sub.2 content of at least 0.5% by weight.

It should be noted also that lead-borate glasses (glasses VIII, IX and X in Table 2) and lead-zinc-borate glasses (the other glasses in Table 2) may contain minor proportions of other oxides as shown which make minor modifications of the glass properties. The terms lead-borate glass and lead-zinc-borate glass are used in the sense that these very minor proportions of modifying oxides may be present.