CN113745427A

CN113745427A - Sealed package and organic electroluminescent device

Info

Publication number: CN113745427A
Application number: CN202110582881.2A
Authority: CN
Inventors: 渡边智之
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2020-05-29
Filing date: 2021-05-27
Publication date: 2021-12-03
Also published as: JP2022003682A; KR20210147932A; TW202145615A

Abstract

The invention relates to a sealed package and an organic electroluminescent device. The present invention relates to a sealed package having: the sealing layer comprises a glass composition, the glass transition temperature of glass constituting the glass composition is 350 ℃ or lower, and the total thickness of a reaction layer obtained by reacting at least one of the first substrate and the second substrate with the sealing layer is 4nm to 25 nm.

Description

Sealed package and organic electroluminescent device

Technical Field

The invention relates to a sealed package and an organic electroluminescent device.

Background

Flat Panel Displays (FPDs) such as organic EL displays (OELDs) and Plasma Display Panels (PDPs) have a structure in which a light emitting device is sealed with a glass package obtained by sealing a pair of glass substrates. In addition, a liquid crystal display device (LCD) has a structure in which liquid crystal is sealed between a pair of glass substrates. In addition, a solar cell such as an organic thin film solar cell or a dye-sensitized solar cell has a structure in which a solar cell device (photoelectric conversion device) is sealed between a pair of glass substrates.

Among them, in the organic EL display, since the light emission characteristics of the organic electroluminescent device (organic EL device) are significantly deteriorated due to contact with moisture, it is necessary to closely isolate the organic EL device from the outside air. In addition, the organic EL device is damaged when exposed to high temperature, and thus a sealing method is extremely important.

Therefore, as a sealing method of an organic EL display, a method of using glass powder for a sealing material and sealing by local heating is considered to be effective. The glass powder is obtained by pulverizing glass, and is generally used by mixing it with an organic vehicle and slurrying the mixture. The pre-sintered layer (the reverse body and the run body) is manufactured by coating the slurry on a glass substrate through screen printing, dot coating (ディスペンス) and the like and baking. Next, another glass substrate is stacked, and the pre-firing layer is locally heated with a laser or the like to melt the glass powder and seal it.

As the glass used for the sealing material, for example, patent document 1 describes TeO used for sealing an organic EL display₂-ZnO-B₂O₃Glass-like. Patent document 2 discloses an electronic device including a pair of glass substrates and a sealing layer, in which a reaction layer that reacts with the sealing layer is formed in the glass substrates, the reaction layer having a maximum depth of 30nm or more from the interface between the glass substrates and the sealing layer.

Documents of the prior art

Patent document

[ patent document 1] Japanese patent No. 6357937 publication

[ patent document 2] Japanese patent No. 5692218 publication

Disclosure of Invention

Problems to be solved by the invention

In recent years, organic electroluminescent devices have also been used for display panels of smart phones, wearable terminals, and the like. As the demand for smartphones, wearable terminals increases, these terminals are required to have high strength against strong impact in the case of falling from a high place, and the like.

According to the studies of the present inventors, it is presumed that the impact resistance is largely affected by the thermal stress accumulated in the sealant and the adhesive strength of the substrate and the sealant. Thermal stresses are mainly accumulated in the sealing material, which is heated at the time of sealing, during cooling from around the glass transition temperature to room temperature. Therefore, if the glass transition temperature can be lowered in order to suppress thermal stress, sealing can be performed at a low temperature and impact resistance can be improved. In addition, the adhesive strength between the substrate and the sealant layer is also important for achieving high impact strength.

In contrast, the glass described in patent document 1 has a glass transition temperature as high as about 350 ℃. The glass frit described in patent document 2 has a softening point temperature of 420 ℃, and therefore a glass transition temperature is expected to be high. Therefore, the sealing property at low temperature is still in need of improvement.

The present invention has been made in view of the above, and an object thereof is to provide a sealed package and an organic electroluminescent device having excellent impact resistance.

Means for solving the problems

The present inventors have found that sealing properties at low temperatures and high adhesive strength between a substrate and a sealing layer can be achieved by using glass having a glass transition temperature of 350 ℃ or less as the sealing layer and adjusting the thickness of a reaction layer between the substrate and the sealing layer to an appropriate range, and have completed the present invention.

That is, the present invention provides a sealed package and an organic electroluminescent device having the following configurations.

[1] A sealed package, the sealed package having:

a first substrate, a second substrate disposed opposite to the first substrate, and a sealing layer disposed between and adhering the first substrate and the second substrate,

the sealing layer comprises a glass composition that is,

the glass transition temperature of the glass constituting the glass composition is 350 ℃ or lower,

a reaction layer obtained by reacting at least one of the first substrate and the second substrate with the sealing layer is formed in the sealed package, and

the thickness of the reaction layer is 4 nm-25 nm.

[2]As described in [1]]The sealed package of, wherein the glass comprises V₂O₅As the main component.

[3]As described in [ 2]]The sealed package, wherein the glass further comprises Bi₂O₃。

[4] The sealed package according to any one of the above [1] to [3], wherein the glass composition further contains at least one of a low-expansion filler and a laser absorbing substance.

[5] The sealed package according to any one of [1] to [4], wherein at least one of the first substrate and the second substrate is a glass substrate.

[6] An organic electroluminescent device, wherein the organic electroluminescent device has:

a first substrate, a second substrate disposed opposite to the first substrate, and a sealing layer disposed between and bonding the first substrate and the second substrate,

the sealing layer comprises a glass composition that is,

a reaction layer obtained by reacting at least one of the first substrate and the second substrate with the sealing layer is formed in the organic electroluminescent device, and

at least one of the reaction layers has a thickness of 4nm to 25 nm.

[7]As described in [6]]The organic electroluminescent element, wherein the glass contains V₂O₅As the main component.

[8]As described in [7 ]]The organic electroluminescent device, wherein the glass further contains Bi₂O₃。

[9] The organic electroluminescent device according to any one of [6] to [8], wherein the glass composition further comprises at least one of a low-expansion filler and a laser absorbing substance.

[10] The organic electroluminescent device according to any one of [6] to [9], wherein at least one of the first substrate and the second substrate is a glass substrate.

Effects of the invention

The sealed package and the organic electroluminescent device according to the present invention have excellent impact resistance against dropping from a high place and the like.

Drawings

Fig. 1 is a front view showing one embodiment of a sealed package.

Fig. 2 is a cross-sectional view of the sealed package shown in fig. 1 taken along line a-a.

Fig. 3A is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 3B is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 3C is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 3D is a process diagram showing an embodiment of a method for manufacturing a sealed package.

Fig. 4 is a top view of a first substrate used in the manufacture of the sealed package shown in fig. 1.

Fig. 5 is a cross-sectional view of the first substrate shown in fig. 4 taken along line B-B.

Fig. 6 is a plan view of a second substrate used in the manufacture of the sealed package shown in fig. 1.

Fig. 7 is a cross-sectional view taken along line C-C of the second substrate shown in fig. 6.

Fig. 8 is a conceptual diagram of a pre-firing layer obtained by pre-firing a glass powder mixture.

Fig. 9 is a conceptual diagram of a sealing layer obtained by heating a glass powder mixture by laser irradiation or the like.

Fig. 10 is a conceptual diagram of an organic electroluminescent device as an example of a sealed package.

Fig. 11 is a plan view of a glass substrate used in the manufacture of the sealed package of the embodiment.

Fig. 12 is a cross-sectional view of the glass substrate shown in fig. 11 taken along line D-D.

Fig. 13 is a cross-sectional view showing a sealed package of the embodiment.

Fig. 14 is a plan view of a sealed package provided with a support substrate on one surface.

Fig. 15 is a cross-sectional view taken along line F-F of the sealed package provided with the support substrate shown in fig. 14.

Fig. 16 is a diagram showing a method of measuring the falling ball strength.

Fig. 17 is a graph showing a relationship between the falling ball strength and the thickness of the reaction layer.

Fig. 18 is a schematic plan view of a glass substrate used for measuring the thickness of the reaction layer.

Description of the reference symbols

10: sealed package

11: first substrate

12: second substrate

13: electronic device section

15: sealing layer

15 a: pre-calcined layer

16: laser beam

30: sealed package

31. 32: glass substrate

35: sealing layer

35 a: pre-calcined layer

36: concave part

46: supporting substrate

47: heavy ball (heavy リ ball)

48: height of fall

100: sealing layer

100 a: pre-calcined layer

101：V₂O₅-TeO₂-ZnO glass

102：Bi₂O₃-ZnO-B₂O₃Glass-like

210: organic electroluminescent device

211: substrate

212: glass member

213: laminated structure

213 a: anode

213 b: organic thin film layer

213 c: cathode electrode

215: sealing layer

Detailed Description

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the embodiments described below. In the following drawings, members and portions having the same function are sometimes described by the same reference numerals, and redundant description may be omitted or simplified. In addition, the embodiments shown in the drawings are illustrated for the purpose of clearly explaining the present invention, and do not necessarily show actual dimensions or scales accurately.

< sealed Package >

The sealed package according to the present embodiment includes: the semiconductor device includes a first substrate and a second substrate arranged to face the first substrate, and a sealing layer for bonding the substrates together is provided between the first substrate and the second substrate. The sealing layer contains a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350 ℃ or lower. Further, a reaction layer obtained by reacting the sealing layer with at least one of the first substrate and the second substrate is formed between the sealing layer and at least one of the first substrate and the second substrate, and the reaction layer has a thickness of 4nm to 25 nm.

In the present specification, the glass composition means an inorganic mixture containing glass. The glass composition may contain at least one of a low-expansion filler and a laser absorbing substance in addition to the glass, or may contain only the glass.

Fig. 1 and 2 are a plan view and a cross-sectional view showing one embodiment of a sealed package. Fig. 3A to 3D are process views showing an embodiment of a method for manufacturing the sealed package shown in fig. 1. Fig. 4 and 5 are a plan view and a cross-sectional view of a first substrate used in the manufacture of the sealed package shown in fig. 1 and 2. Fig. 6 and 7 are a plan view and a cross-sectional view of a second substrate used in the manufacture of the sealed package shown in fig. 1 and 2.

The sealed package 10 constitutes an FPD (flat panel display) such as an OELD, a PDP (plasma display panel), an LCD (liquid crystal display), an illumination device (OEL illumination, etc.) using a light emitting device such as an Organic Electroluminescent (OEL) device, a solar cell such as a dye-sensitized solar cell, or the like.

That is, the sealed package 10 includes: the sealing sheet includes a first substrate 11, a second substrate 12 disposed to face the first substrate, and a sealing layer 15 disposed between the first substrate 11 and the second substrate 12 and bonding the first substrate and the second substrate together. The sealing layer 15 contains a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350 ℃ or lower.

The first substrate 11 is, for example, a device substrate on which the electronic device section 13 is mainly provided. The second substrate 12 is, for example, a sealing substrate mainly used for sealing. An electronic device section 13 is provided on the first substrate 11. The first substrate 11 and the second substrate 12 are arranged to face each other, and are bonded by a sealing layer 15 arranged in a frame shape therebetween.

A reaction layer (not shown) obtained by a reaction between the substrate and the sealing layer is formed between the sealing layer 15 and at least one of the first substrate 11 and the second substrate 12. The thickness of the reaction layer is 4 nm-25 nm. The sealing layer and the reaction layer will be described later.

Although there is no particular limitation as long as at least one of the first substrate 11 and the second substrate 12 is a substrate that forms a reaction layer with the sealing layer, a glass substrate is preferable in terms of excellent laser light transmittance and ability to heat the sealing layer efficiently. As the glass substrate, a soda lime glass substrate, an alkali-free glass substrate, or the like is more preferably used.

Examples of soda-lime glass substrates include: AS and PD200 (both trade names, manufactured by AGC corporation) and a glass substrate obtained by chemically strengthening these.

Examples of the alkali-free glass substrate include: AN100 (trade name manufactured by AGC), EAGEL2000 (trade name manufactured by corning), EAGEL GX (trade name manufactured by corning), JADE (trade name manufactured by corning), #1737 (trade name manufactured by corning), OA-10 (trade name manufactured by japan electric nitro company), TEMPAX (trade name manufactured by schottky), and the like.

The first substrate 11 and the second substrate 12 may be the same substrate or different substrates.

For example, if the lighting is OELD or OEL, the electronic device section 13 has an OEL device, if the lighting is PDP, the electronic device section 13 has a plasma light emitting device, if the lighting is LCD, the electronic device section 13 has a liquid crystal display device, and if the lighting is solar cell, the electronic device section 13 has a dye-sensitized solar cell device, that is, a dye-sensitized photoelectric conversion section device. The electronic component section 13 may have various known configurations, and is not limited to the illustrated configuration.

In the sealed package 10 of fig. 1 and 2, an OEL device, a plasma light emitting device, or the like is provided as the electronic device section 13 on the first substrate 11. When the electronic device section 13 is a dye-sensitized solar cell device or the like, device films such as a wiring film and an electrode film are provided on the opposing surfaces of the first substrate 11 and the second substrate 12, respectively, although not shown.

In the case where the electronic device section 13 is an OEL device or the like, a part of the space remains between the first substrate 11 and the second substrate 12. The space may be left as it is, or may be filled with a transparent resin or the like. The transparent resin may be bonded to the first substrate 11 and the second substrate 12, or may be in contact with only the first substrate 11 and the second substrate 12.

When the electronic device section 13 is a dye-sensitized solar cell device or the like, although not shown, the electronic device section 13 is disposed in the entire space between the first substrate 11 and the second substrate 12. The sealing object is not limited to the electronic device section 13, and may be a photoelectric conversion device or the like. The sealed package 10 may be a building material such as a multilayer glass that does not include the electronic component section 13.

[ sealing layer ]

The sealing layer of the present embodiment includes a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350 ℃ or lower. Hereinafter, this glass is sometimes referred to as "low-melting glass".

The glass composition can form a sealing layer at a low temperature by containing a low-melting glass. Therefore, it is possible to suppress thermal stress that is accumulated during cooling of the sealing material heated at the time of sealing from the vicinity of the glass transition temperature to room temperature. As a result, the impact strength of the resulting sealed package can be improved.

The glass transition temperature (Tg) of the low-melting glass may be 350 ℃ or lower, and from the viewpoint of obtaining more excellent low-temperature sealing properties, Tg is preferably 340 ℃ or lower, and more preferably 330 ℃ or lower. The lower limit of the glass transition temperature is not particularly limited, but is preferably 290 ℃ or higher. By setting the glass transition temperature to 290 ℃ or higher, in the case where an organic vehicle containing a resin is mixed with a glass composition to prepare a glass paste, it is possible to prevent the resin from remaining in the sealing layer due to softening of the glass before the resin is removed.

The glass transition temperature (Tg) of the low melting point glass was measured using a differential thermal analyzer, and the first inflection point was defined as the glass transition temperature.

One kind of glass or two or more kinds of glasses may be used as a material constituting the low melting point glass.

When the low-melting glass contains one kind of glass, the glass transition temperature of the glass may be in the above range.

When two or more types of glass are used as the materials constituting the low-melting glass, the glass transition temperature (Tg) of the obtained low-melting glass may be measured by a differential thermal analyzer, and the glass transition temperature may be within the above range as estimated from the first inflection point.

When two or more types of glass are used as the material constituting the low-melting glass, the total content of glass as a material having a glass transition temperature of 350 ℃ or lower, relative to the total amount of glass as a material constituting the low-melting glass, is preferably 80% by volume or higher, and more preferably 85% by volume or higher, although it cannot be uniquely determined depending on the level of the glass transition temperature of each glass. The upper limit of the total content is not particularly limited, and all glasses as materials may have a glass transition temperature of 350 ℃ or less, that is, 100% by volume.

The composition of the low-melting glass is not particularly limited as long as it has the above-mentioned characteristics, but it preferably contains V₂O₅As the main component. V₂O₅Is a glass-forming oxide, is a component which forms a network of glass and makes the glass have a low glass transition temperature. In addition, V₂O₅Is also effective as a laser light absorbing component.

In the present specification, the main component means a component having the largest content in terms of mol% based on oxides among components constituting the glass. When two or more kinds of glasses are used as the materials constituting the low-melting glass, the composition of the low-melting glass is determined based on the composition of each glass in mol% based on oxides and the content ratio (volume%) of the glass.

Specifically, V₂O₅The content of (b) is preferably 10% or more, more preferably 20% or more, further preferably 25% or more, and further preferably 30% or more. In addition, from the viewpoint of preventing the lowering of water resistance and the lowering of glass stability during the production of glass, and thus the glass is liable to devitrify₂O₅The content of (b) is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, and still more preferably 35% or less.

Low melting point glass is preferableFurther comprises Bi₂O₃. In the case of using a glass substrate as a substrate, Bi is used for forming a sealing layer₂O₃Easily react with the glass substrate, and easily form a reaction layer. The reaction layer improves adhesive strength and can provide a sealed package with better impact resistance.

Specifically, Bi₂O₃The content of (b) is preferably 0.5% or more, more preferably 1.0% or more, still more preferably 1.5% or more, and still more preferably 2.0% or more. In addition, from the viewpoint of maintaining good low-temperature sealing properties, Bi₂O₃The content of (b) is preferably 20.0% or less, more preferably 15.0% or less, still more preferably 10.0% or less, and still more preferably 7.0% or less.

(Low melting glass)

Hereinafter, one embodiment of the composition of the low-melting glass contained in the glass composition as the sealing layer will be described. The composition is not particularly limited as long as the glass transition temperature is within the above range and the reaction layer having an appropriate thickness can be formed with the substrate. When two or more kinds of glasses are used as materials constituting the low-melting glass, the composition defined by the composition of each glass in mol% based on oxides and the content ratio (volume%) thereof (hereinafter referred to as "average composition") may be as follows.

The low-melting glass of the present embodiment does not substantially contain an alkali metal oxide, and preferably contains 10.0 to 50.0% of V in mol% based on the oxide₂O₅14.5 to 45.0 percent of TeO₂5.0 to 45.0 percent of ZnO and 0.5 to 20.0 percent of Bi₂O₃。

In the following description of the respective components, unless otherwise specified, "%" in the content of the respective components of the low-melting glass means on an oxide basis, that is, in terms of mole% in terms of oxide.

When the low melting point glass contains an alkali metal oxide, there is a possibility that the alkali component diffuses into the material to be sealed such as the substrate and the member to be sealed deteriorates when the material to be sealed is exposed to high temperature during or after sealing. Therefore, the low-melting glass preferably contains substantially no alkali metal oxide. The term "substantially free" means that the additive is not contained except for inevitable impurities, that is, is not intentionally added.

Therefore, the low melting point glass may contain a trace amount of alkali metal oxide as an inevitable impurity. The content of the alkali metal oxide in the low-melting glass is preferably 1000ppm or less, more preferably 500ppm or less.

In the present specification, the alkali metal oxide means Li₂O、Na₂O and K₂The content of O, alkali metal oxide means the total content thereof. Further, ppm means mass ppm.

V₂O₅Is a glass-forming oxide, forms a network of glass and is a low softening component, i.e. V₂O₅Is a component for lowering the glass transition temperature, and therefore V is preferably contained₂O₅. In addition, V₂O₅Is also effective as a laser light absorbing component. From the viewpoint of excellent low-temperature sealing properties and high impact strength by lowering the glass transition temperature in this way, V is preferably contained₂O₅As the main component. In addition, V₂O₅The content of (b) is preferably 10.0% or more, more preferably 15.0% or more, still more preferably 20.0% or more, and still more preferably 25.0% or more.

V is considered to prevent the lowering of water resistance and the deterioration of glass stability during the production of glass, thereby preventing the glass from being easily devitrified₂O₅The content of (b) is preferably 50.0% or less, more preferably 45.0% or less, still more preferably 40.0% or less, and still more preferably 35.0% or less.

TeO₂Is a glass oxide, forms a glass network and is a low softening component, and therefore preferably contains TeO₂. TeO is a material that improves low-temperature sealing properties by lowering the glass transition temperature and prevents crystallization during sintering (sintering) sealing₂The content of (b) is preferably 14.5% or more, more preferably 16.0% or more, still more preferably 18.0% or more, and still more preferably 20.0% or more. In addition, TeO is considered to prevent the thermal expansion coefficient from becoming too large₂The content of (b) is preferably 45.0% or less, more preferably 40.0% or less, still more preferably 35.0% or less, and still more preferably 30.0% or less.

ZnO is preferably contained as a component for lowering the thermal expansion coefficient. The content of ZnO is preferably 5.0% or more, more preferably 10.0% or more, still more preferably 15.0% or more, and still more preferably 20.0% or more. On the other hand, from the viewpoint of preventing the glass from devitrifying due to the decrease in glass stability in the production of the glass, the content of ZnO is preferably 45.0% or less, more preferably 40.0% or less, still more preferably 35.0% or less, and still more preferably 30.0% or less.

Bi₂O₃Is a component which easily reacts with the substrate at the time of sealing and improves adhesive strength by forming a reaction layer. Thus, Bi₂O₃The low melting point glass of the present embodiment is important, and is preferably V₂O₅Are contained together. By reacting Bi₂O₃The content of (b) is at least a certain amount, and the effect of improving the adhesive strength can be sufficiently obtained. On the other hand, by using Bi₂O₃The content of (b) is not more than a certain level, and the glass transition temperature is not excessively high, so that good low-temperature sealing properties can be maintained. Further, in the case where the substrate is a glass substrate, it is possible to suppress excessive reaction with the glass substrate to cause SiO in the glass substrate₂High melting point components enter the glass composition. As a result, it is possible to prevent the residual stress of the sealing layer after sealing from becoming large without raising the fixing point.

In use of V₂O₅-TeO₂Bi capable of improving adhesive strength while maintaining low-temperature sealing properties in the case of using a ZnO glass as a low-melting glass₂O₃The appropriate content of (A) is 0.5% -20.0%. Bi₂O₃The content of (B) is more preferably 1.0% or more, still more preferably 1.5% or more, and still more preferably 2.0%Above, in addition, Bi₂O₃The content of (b) is more preferably 15.0% or less, still more preferably 10.0% or less, and still more preferably 7.0% or less.

At a velocity of V₂O₅As a main component and further contains Bi₂O₃The low-melting glass of (2) is composed of V from the viewpoint of suppressing crystallization at the time of firing sealing and stabilizing the glass₂O₅/TeO₂V of₂O₅And TeO₂The ratio of the amounts of (A) to (B) is preferably 0.5 or more, more preferably 1.0 or more, and V is₂O₅/TeO₂V of₂O₅And TeO₂The content ratio of (b) is preferably 2.5 or less, more preferably 2.0 or less.

CuO is a component having an effect of reducing the thermal expansion coefficient, and is preferably contained because CuO has an effect of improving water resistance. CuO is also effective as a laser light absorbing component. By containing CuO, the amount of pigment to be added for the purpose of laser absorption can be reduced when preparing a glass paste for forming a sealing layer, and instead, a large amount of low-swelling filler can be contained. This makes it possible to obtain a glass paste having a lower thermal expansion coefficient. From the above viewpoint, the content of CuO is preferably 1.0% or more, more preferably 2.0% or more, and further preferably 5.0% or more. On the other hand, the CuO content is preferably 10.0% or less, more preferably 8.0% or less, and further preferably 7.5% or less, from the viewpoint of preventing crystallization of the glass at the time of firing sealing.

Fe₂O₃Since it is also effective as a laser light absorbing component, Fe may be contained₂O₃. By containing Fe₂O₃When the glass paste is produced, the amount of the pigment to be added for the purpose of laser absorption can be reduced, and instead, a large amount of the low-expansion filler can be contained. This makes it possible to obtain a glass paste having a lower thermal expansion coefficient. From the above viewpoint, Fe₂O₃The content of (b) is preferably 1.0% or more. However, if CuO or MnO is contained, Fe is not contained₂O₃The above effects can be obtained. In additionOn the other hand, from the viewpoint of preventing crystallization of glass at the time of firing sealing and further suppressing the lowering of low-temperature sealability with the increase of glass transition temperature, Fe₂O₃The content of (b) is preferably 7.0% or less, more preferably 5.0% or less, and further preferably 2.0% or less.

MnO is a component effective as a laser light absorption component, and therefore, MnO may be contained. By containing MnO, the amount of pigment to be added for the purpose of laser absorption can be reduced when producing a glass paste, and instead, a large amount of low expansion filler can be contained. This makes it possible to obtain a glass paste having a lower thermal expansion coefficient. From the above viewpoint, the content of MnO is preferably 1.0% or more. However, if CuO or Fe is contained₂O₃The above-described effects can be obtained even if MnO is not included. On the other hand, the content of MnO is preferably 7.0% or less, more preferably 5.0% or less, and further preferably 2.0% or less, from the viewpoint of preventing crystallization of the glass at the time of firing sealing.

From the viewpoint of obtaining the laser light absorption effect appropriately, the material is composed of (CuO + Fe)₂O₃+ MnO) represents CuO or Fe₂O₃The total content of MnO and MnO is preferably 1.0% or more, more preferably 2.0% or more, even more preferably 4.0% or more, and even more preferably 5.0% or more. In addition, from the viewpoint of avoiding crystallization of the glass at the time of laser firing sealing, the total content is preferably 10.0% or less, more preferably 8.0% or less, and further preferably 7.5% or less.

CuO、Fe₂O₃And MnO are effective components as laser light absorbing components. In view of the balance between the effect of low-temperature sealing property by the laser absorption and the avoidance of crystallization of glass, CuO is preferably contained in a large amount in these components. Specifically, the CuO content is defined by { CuO/(CuO + Fe) }₂O₃+ MnO) } CuO, Fe₂O₃The ratio of the sum of the content of MnO and MnO is preferably 30% or more (0.3 or more), more preferably 50% or more (0.5 or more), and further preferably 70% or more (0.7 or more). The above ratio may be 100%, that is, only CuO may be contained.

B₂O₃Is a glass oxide, is a component for forming a glass network and improving the stability of the glass, and therefore B is preferably contained₂O₃. In the presence of B₂O₃In the case of (3), the content is preferably 0.5% or more, more preferably 1.0% or more, and still more preferably 1.5% or more. On the other hand, from avoiding excessive inclusion of B₂O₃And B is because the glass is unstable and is easily crystallized during firing and sealing₂O₃The content of (b) is preferably 10.0% or less, more preferably 7.5% or less, and further preferably 5.0% or less.

BaO is an effective component for stabilizing the glass, and therefore BaO may be contained. When BaO is contained, the content is preferably 2.0% or more. On the other hand, the content of BaO is preferably 10.0% or less, more preferably 8.0% or less, from the viewpoint of keeping the glass transition temperature and the thermal expansion coefficient within appropriate ranges.

Al₂O₃And Nb₂O₅Has the effect of reducing the coefficient of thermal expansion, and further Al₂O₃And Nb₂O₅Has an effect of improving water resistance, and therefore, Al may be contained separately₂O₃And Nb₂O₅. Containing Al₂O₃And Nb₂O₅Al in the case of (1)₂O₃And Nb₂O₅The content of (b) is preferably 2.0% or more. On the other hand, Al is considered from the viewpoint of keeping the glass transition temperature within an appropriate range₂O₃And Nb₂O₅The content is preferably 10.0% or less, more preferably 8.0% or less, respectively.

Is composed of (V)₂O₅+TeO₂V + ZnO)₂O₅、TeO₂The sum of the contents of (Al) and (ZnO) is preferably 78.0 to 89.0%₂O₃+Nb₂O₅) Al shown in₂O₃And Nb₂O₅The total content of (b) is preferably 5.0% to 11.0%. When the amount is within the above range, both water resistance and stabilization of the glass can be easily achieved. In addition, from the same sideFor the same reason, (V)₂O₅+TeO₂+ ZnO) is more preferably 79.0% or more, and (V)₂O₅+TeO₂+ ZnO) is more preferably 88.0% or less. Furthermore, (Al)₂O₃+Nb₂O₅) More preferably 6.0% or more, and (Al)₂O₃+Nb₂O₅) More preferably 10.0% or less.

The low melting point glass may contain components other than the above components (hereinafter referred to as "other components") within a range not impairing the object of the present invention. The total content of other components is preferably 10.0% or less.

As other ingredients, there may be mentioned: CaO, TiO₂、ZrO₂、CeO₂、La₂O₃、CoO、MoO₃、Sb₂O₃、WO₃、GeO₂And the like.

In addition, from the viewpoint of reducing the influence on the environment, the low-melting glass preferably contains substantially no lead, i.e., PbO.

(method of producing sealing layer)

The sealing layer contains a glass composition, and the glass constituting the glass composition is a low-melting glass. The method for producing the sealing layer is not particularly limited, and can be produced, for example, by the following method.

First, a raw material mixture is prepared. The raw material is not particularly limited as long as it is used for producing a general oxide glass, and oxides, carbonates, and the like can be used. The kind and ratio of the raw materials are appropriately adjusted so that the composition of the resulting glass is within the above range, thereby making a raw material mixture.

When two or more kinds of glasses as materials of the low melting point glass are different in composition, the respective compositions of the glasses different in composition are not particularly limited, and the kind and ratio of raw materials, the combination of glasses, and the like may be appropriately selected so that the average composition thereof falls within the above range.

The raw material mixture is heated by a known method to obtain a melt. The temperature for heating and melting (melting temperature) is preferably 1000 to 1200 ℃, more preferably 1050 ℃ or higher, and the temperature for heating and melting is more preferably 1150 ℃ or lower. The time for heating and melting is preferably 30 minutes to 90 minutes.

Then, the melt is cooled and solidified to obtain glass as a material of low melting point glass. The cooling method is not particularly limited, and for example, a method using a rolling mill (rolling machine), a press, a method of quenching by dropping into a cooling liquid, or the like can be used.

The glass obtained is preferably completely amorphous, i.e., has a degree of crystallization of 0%. However, the crystallized portion may be contained within a range not to impair the effects of the present invention.

The form of the glass of the above-obtained material is arbitrary. Examples thereof include: block, plate, sheet (flake), powder, etc. Among them, the powder is preferable from the viewpoint that the glass is easily melted when the sealing layer is formed, and that the glass is easily mixed when two or more kinds of glasses having different compositions are used as the material of the low melting point glass. Further, by making the powder, the properties as a sealing material can be easily examined.

The particle size in the case of being made into a powder can be appropriately selected depending on the application, but the particle size of the glass powder is usually about 0.1 μm to about 100. mu.m. The glass powder preferably has a particle size of 5.0 μm or less, more preferably 2.5 μm or less, from the viewpoint of being slurried at the time of forming the sealing layer so that sedimentation separation does not occur at the time of coating and drying, and further, the obtained sealing layer does not become too thick.

The particle size of the powder in the present specification means a volume-based 50% particle diameter (D) in a cumulative particle size distribution₅₀). Specifically, the particle diameter is the particle diameter at which the cumulative amount of the particle diameter distribution measured by the laser diffraction/scattering particle size distribution measuring apparatus is 50% on a volume basis in the cumulative particle diameter curve of the particle diameter distribution.

The glass powder is obtained by, for example, pulverizing the glass obtained as described above. In this case, the particle size of the powder can be adjusted according to the conditions of pulverization. Further, in addition to the pulverization of the glass, classification may be performed by using a sieve or the like as necessary.

Examples of the method of pulverization include: rotary ball mills, vibratory ball mills, planetary mills, jet mills, attritors, media-agitating mills (bead mills), jaw crushers, roll crushers, and the like.

In particular, when the particle size is made as small as 5.0 μm or less, wet grinding is preferably used. Wet pulverization is a method of pulverizing in a solvent such as water or alcohol using a medium containing alumina or zirconia or a bead mill.

Next, a sealing layer including a glass composition made of a low-melting glass is formed by firing the glass powder between the first substrate and the second substrate. When two or more kinds of glass are used as the material of the low-melting glass, a glass powder mixture obtained by mixing powders of these glasses is fired. The calcination may be preceded by a pre-calcination.

As glass powder mixtures, e.g. with V₂O₅-TeO₂-ZnO glass as a base component, and Bi is added thereto₂O₃-ZnO-B₂O₃Glass-like glass, the low-melting glass of the present embodiment is obtained when the sealing layer is formed. The base component is contained in an amount of 50 vol% or more, preferably 70 vol% or more, and preferably 99.9 vol% or less, based on the total volume of the glass powder mixture.

The glass powder may be used as it is, but is preferably slurried, that is, used as a glass slurry, from the viewpoint of improving the handling property. When two or more kinds of glass are used as the material of the low melting point glass, a plurality of kinds of glass powders may be mixed to prepare a glass powder mixture and then slurried, or a plurality of kinds of slurries including glass powders having different compositions may be prepared and then mixed. The glass paste contains an organic vehicle, but the organic vehicle is removed together with the solvent and the resin in the step of forming the sealing layer. Therefore, the constituent components of the organic vehicle do not remain in the sealing layer.

The glass slurry is adjusted by a known method using a rotary mixer having an agitating blade, a roll mill, a bead mill, or the like.

According to the sealing method, it is preferable that the glass composition of the sealing layer further contains at least one of a low-expansion filler and a laser absorbing substance in addition to the glass powder.

Hereinafter, the pre-firing and firing of a glass powder mixture, which are cases where two or more kinds of glass are used as materials of the low melting point glass, will be described. Here, it is noted that, for V, V₂O₅-TeO₂-ZnO glass as a base component, Bi₂O₃-ZnO-B₂O₃The case where the glass-like substance is an additive component will be described, but the present invention is not limited thereto.

The precalcination is preferably carried out at a ratio V as base component₂O₅-TeO₂The ZnO glass is heated at a temperature of from about 10 ℃ to about 50 ℃ in terms of the softening point. When the precalcination is carried out at such a temperature, V at softening is obtained as shown in FIG. 8₂O₅-TeO₂Bi dispersed in the-ZnO glass 101₂O₃-ZnO-B₂O₃A pre-fired layer 100a of glass-like 102.

Next, when the pre-baked layer 100a is heated and baked by laser irradiation or the like, it is preferable that the pre-baked layer 100a be made to contain Bi as an additive component₂O₃-ZnO-B₂O₃The glass-like material is heated to a temperature at which the glass-like material is sufficiently melted. When the calcination is carried out at such a temperature, Bi is included₂O₃-ZnO-B₂O₃The entire glass 102 is melted, and V as a base component is considered to be obtained as shown in FIG. 9₂O₅-TeO₂Part of ZnO glass 101 and Bi as an additive component₂O₃-ZnO-B₂O₃The glass-like 102 portion is mixed with the sealing layer 100.

Due to V as a basic component₂O₅-TeO₂The glass transition temperature of the ZnO glass is low, so that the sealing layer 100 isThe residual stress after cooling to room temperature is small. In addition, Bi contained in the additive component₂O₃Is excellent in high reactivity and adhesive strength. Therefore, the sealing layer 100 is excellent in impact resistance.

In fig. 9, V is₂O₅-TeO₂Part of ZnO glass 101 and Bi₂O₃-ZnO-B₂O₃The portions of the glass-like 102 are clearly separated, but fig. 9 is a schematic view, and the boundaries of these portions are not necessarily clear in the sealing layer 100.

Heating the pre-firing layer 100a by laser irradiation or the like to form Bi₂O₃-ZnO-B₂O₃When the glass-like substance 102 is molten, Bi is added₂O₃-ZnO-B₂O₃Glass-like 102 and V₂O₅-TeO₂Near the interface of the ZnO glass 101, these glasses are mixed together. Thus, in the resulting sealing layer, V₂O₅-TeO₂The part of the-ZnO glass 101 may contain Bi₂O₃-ZnO-B₂O₃Glass-like, Bi₂O₃-ZnO-B₂O₃The portion of the glass-like member 102 may contain V₂O₅-TeO₂-ZnO based glasses.

The foregoing is not limited to the case where the glass powder mixture is directly pre-calcined and calcined in the form of powder, and the same is true for the case where the pre-calcination and calcination are performed in the form of glass slurry.

The low-expansion filler has a lower thermal expansion coefficient than the low-melting glass, and is added for the purpose of lowering the thermal expansion coefficient of the sealing layer. The low expansion filler has a coefficient of thermal expansion of about-15 x 10^-7/° c about 45 x 10^-7/℃。

The low-expansion filler is not particularly limited, and is preferably at least one selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate compounds, soda lime glass and borosilicate glass. Examples of the zirconium phosphate compound include: (ZrO)₂P₂O₇、NaZr₂(PO₄)₃、KZr₂(PO₄)₃、Ca_0.5Zr₂(PO₄)₃、NbZr(PO₄)₃、Zr₂(WO₃)(PO₄)₂And a complex compound thereof.

The particle size of the low-expansion filler is preferably 0.1 to 5.0. mu.m, more preferably 0.1 to 2.0. mu.m.

The content of the low expansion filler is set so that the thermal expansion coefficient of the sealing layer approaches that of the substrate as the sealed material. The content of the low-expansion filler is preferably 1 vol% or more, more preferably 5 vol% or more, and still more preferably 10 vol% or more, based on the total of the glass powder, the low-expansion filler, and the laser absorbing substance. On the other hand, the content of the low-expansion filler is preferably 50% by volume or less, more preferably 45% by volume or less, and still more preferably 40% by volume or less, from the viewpoint of ensuring good fluidity when the sealing material is melted.

The laser absorbing substance is added for the purpose of sufficiently melting the sealing material by absorbing the laser irradiated at the time of sealing and improving the low-temperature sealability.

The laser light absorbing material is not particularly limited, except that CuO and Fe described above are formed in the glass composition₂O₃Examples of the Cu, Fe, and Mn as MnO include inorganic pigments which are compounds such as at least one metal selected from Cr, Ni, Ti, Co, and Zn, or oxides containing the metal. In addition, the laser light absorbing substance may be a pigment other than these substances.

The particle size of the laser light absorbing material is preferably 0.1 to 5.0. mu.m, more preferably 0.1 to 2.0. mu.m.

From the viewpoint of obtaining the effect of the laser absorbing substance appropriately, CuO and Fe are contained in the glass powder, the low-expansion filler and the laser absorbing substance in total, excluding CuO and Fe₂O₃The total content of the laser absorbing materials other than MnO and the other laser absorbing materials is preferably 0.1 vol% or more, more preferably 1 vol% or more, and further preferably 3 vol% or more. Another one isIn view of ensuring good fluidity when the sealing material is melted and obtaining excellent adhesive strength, the content of the laser absorbing substance is preferably 20% by volume or less, more preferably 18% by volume or less, and still more preferably 15% by volume or less.

As the organic vehicle, for example, a vehicle in which a resin as a binder component is dissolved in a solvent can be used.

Examples of the resin as the binder component include: methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, benzyl cellulose, propyl cellulose, nitro cellulose, and the like. As the solvent in this case, for example, terpineol, Texanol, butyl carbitol acetate, ethyl carbitol acetate, and the like can be used.

As the resin as the binder component, an acrylic resin containing an acrylic monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, or the like may be used. As the solvent in this case, for example, methyl ethyl ketone, terpineol, Texanol, butyl carbitol acetate, ethyl carbitol acetate, and the like can be used.

In the present specification, the term (meth) acrylate refers to at least one of acrylate and methacrylate.

As the resin as the binder component, polyalkylene carbonate such as polyethylene carbonate and polypropylene carbonate may be used. As the solvent in this case, for example, there can be used: acetyl triethyl citrate, propylene glycol diacetate, diethyl succinate, ethyl carbitol acetate, glyceryl triacetate, Texanol, dimethyl adipate, ethyl benzoate, mixtures of propylene glycol monophenyl ether and triethylene glycol dimethyl ether, and the like.

The ratio of the resin to the solvent in the organic vehicle is not particularly limited, and the viscosity of the glass paste is adjusted to be within an appropriate range by adjusting the viscosity of the organic vehicle.

The ratio of resin to solvent in the organic vehicle is preferably resin: solvent ═ 3: 97 to about 30: 70 (mass ratio).

The ratio of the total of the glass powder, the low-expansion filler and the laser absorbing substance in the glass paste to the organic vehicle is appropriately adjusted according to the desired viscosity of the glass paste. Specifically, the total of: organic vehicle about 65: 35 to about 90: 10 (mass ratio).

In addition to the above, other known additives may be added to the glass paste and the glass composition as needed and within limits not prejudicial to the object of the present invention.

(reaction layer)

The reaction layer is a layer formed by a reaction between the substrate and the sealing layer. Therefore, the reaction layer is a mixed layer containing a plurality of elements including the constituent element of the substrate and the constituent element of the sealing layer. By forming this reaction layer between the substrate and the sealing layer, the adhesion state between the substrate and the sealing layer is strengthened.

From the viewpoint of obtaining the above-described effects, the thickness of the reaction layer is set to 4nm or more. The thicker the reaction layer, the higher the adhesive strength and the higher the impact strength. Therefore, the thickness of the reaction layer is preferably 5nm or more, more preferably 7nm or more, and still more preferably 10nm or more.

The reaction layer may be formed between the sealing layer and at least one of the first substrate and the second substrate, but is preferably formed between the sealing layer and both of the first substrate and the second substrate, from the viewpoint of higher adhesive strength of the package to be sealed.

In the case where the reaction layer is formed between the two substrates, the thickness of either reaction layer may be 4nm to 25nm, and the thickness of both reaction layers is more preferably 4nm to 25 nm.

On the other hand, the reason why the thickness of the reaction layer is set to 25nm or less is based on the following 3 points.

The thickness of the reaction layer varies depending on the temperature at which the sealing layer is formed. When the reaction layer is thickened, the sealing temperature needs to be increased, and when sealing is performed by laser irradiation, for example, the laser output needs to be increased. However, when the laser output power becomes too high, the wiring and the like located below the portion where the sealing layer is formed are damaged. Therefore, excessive laser output power cannot be applied. Therefore, there is an upper limit to the thickness of the reaction layer.

In addition to the above, when the reaction layer is too thick, a layer located on the opposite side of the substrate from the sealing layer, for example, if it is a Thin Film Transistor (TFT), reacts with a passivation film, an electrode, or the like, and generates excessive bubbles. Therefore, there is an upper limit to the thickness of the reaction layer in terms of a decrease in the material strength itself and a decrease in the impact strength.

In addition, the thickness of the reaction layer also varies depending on the composition of the glass constituting the glass composition. For example in the form of a gas containing V₂O₅In the case of glass as the main component, Bi may be used₂O₃The content of (a) to adjust the thickness of the reaction layer. Specifically, when Bi is increased₂O₃At the content of (B), the reaction layer becomes thick, but when Bi is contained₂O₃When the content of (b) is too large, vitrification becomes difficult or crystallization immediately occurs even if vitrification occurs. Since the process margin at the time of sealing is narrowed in this way, Bi is increased₂O₃It is not practical to make the reaction layer thick.

For the above reasons, the thickness of the reaction layer is 25nm or less. The thickness is preferably 20nm or less, more preferably 16nm or less.

The formation of the reaction layer can be confirmed by the following method as a practical method.

First, a portion of the sealed package is cut out to facilitate grinding and sample fabrication. One substrate was removed from the sample by polishing. In the case where the adhesive strength is low and peeling occurs in the sealing layer, the step of polishing the substrate may be omitted. Next, the sample from which one substrate was removed was immersed in an etching solution to remove the sealing layer. As the etching liquid, an acid solution capable of dissolving the constituent elements of the sealing layer is used. For example, when bismuth-based glass is used as the sealing layer, a 30% nitric acid aqueous solution or the like is used.

Since the reaction layer is a mixed layer of the constituent element of the substrate and the constituent element of the sealing layer, the reaction layer is removed simultaneously with the removal of the sealing layer.

By obtaining a substrate in which the reaction layer is left in the form of the concave portion, it can be confirmed that the reaction layer is generated. The surface shape of the substrate having such a concave portion can be confirmed by a non-contact surface roughness meter, for example, a white light interferometer. The specific thickness of the reaction layer is the depth of the concave portion, which is a trace of the reaction layer formed, measured by a white light interferometer using the method described in the examples described later.

< method for manufacturing sealed Package >

An example of the method for manufacturing the sealed package according to the present embodiment will be described, but the sealed package according to the present invention is not limited thereto. In addition, the configuration thereof may be appropriately changed as needed within a limit not departing from the gist of the present invention.

The glass paste obtained in the above was coated on a second substrate in a frame shape, and then dried to form a coating layer. Examples of the coating method include printing methods such as screen printing and gravure printing, and a dot coating method.

Drying is usually carried out at a temperature of 120 ℃ or higher for 10 minutes or longer in order to remove the solvent contained in the glass paste. If the solvent remains in the coating layer, the resin added as the organic carrier as the binder component may not be sufficiently removed in the subsequent pre-calcination.

The coating layer is pre-calcined to form a pre-calcined layer 15a (fig. 6 and 7). The precalcination is carried out in the following manner: the coating layer is heated to a temperature not higher than the glass transition temperature of the low-melting glass contained in the sealing material to remove the resin as the binder component, and then heated to a temperature not lower than the softening point of the low-melting glass contained in the sealing material.

Next, the second substrate 12 provided with the pre-baked layer 15a and the first substrate 11 are stacked such that the first substrate 11 faces the pre-baked layer 15a (fig. 3A and 3B). In accordance with the specification of the sealed package 10, the electronic component section 13 is provided on the first substrate 11 (fig. 4 and 5).

Then, the pre-firing layer 15a is irradiated with a laser beam 16 through the second substrate 12 to perform firing (fig. 3C). The laser beam 16 is irradiated while being scanned along the frame-like pre-baked layer 15 a. The frame-shaped sealing layer 15 is formed between the first substrate 11 and the second substrate 12 by irradiating the laser beam 16 to the entire periphery of the pre-baked layer 15 a. The laser beam 16 may be irradiated onto the pre-baking layer 15a through the first substrate 11.

The type of the laser beam 16 is not particularly limited, and a semiconductor laser, a carbon dioxide gas laser, an excimer laser, a YAG laser, a HeNe laser, or the like is used. The irradiation conditions of the laser beam 16 are selected in accordance with the thickness, line width, cross-sectional area in the thickness direction, and the like of the pre-baked layer 15 a.

The output of the laser beam 16 is preferably 2W or more, and more preferably 5W or more, from the viewpoint of sufficiently melting the pre-baked layer 15 a. The output power of the laser beam 16 is preferably 150W or less, and more preferably 120W or less, from the viewpoint of suppressing the occurrence of cracks in the first substrate 11 and the second substrate 12.

In this manner, the sealed package 10 obtained by hermetically sealing the electronic device section 13 between the first substrate 11 and the second substrate 12 with the sealing layer 15 is manufactured (fig. 3D).

Although the method of firing by irradiation of the laser beam 16 has been described above, the method of firing is not necessarily limited to the method of firing by irradiation of the laser beam 16.

The firing method may be other methods depending on the heat resistance of the electronic device section 13, the structure of the sealed package 10, and the like. For example, in the case where the heat resistance of the electronic device section 13 is high or in the case where the electronic device section 13 is not provided, the irradiation of the laser beam 16 may be replaced in the following manner: the entire assembly shown in fig. 3B is placed in a calcining furnace such as an electric furnace, and the sealing layer 15 is formed by heating the entire assembly including the pre-calcining layer 15 a.

< organic electroluminescent device >

The organic electroluminescent device according to the present embodiment includes a first substrate and a second substrate disposed to face the first substrate, and a sealing layer for bonding the substrates together is provided between the first substrate and the second substrate. The sealing layer contains a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350 ℃ or lower. Further, a reaction layer obtained by reacting the sealing layer with at least one of the first substrate and the second substrate is formed between the sealing layer and at least one of the first substrate and the second substrate, and the thickness of the reaction layer is 4nm to 25 nm.

The sealing layer and the reaction layer in the organic electroluminescent device are the same as those described in (sealing layer) and (reaction layer) in < sealing package >, respectively, and preferred embodiments are also the same.

Hereinafter, an example of an organic electroluminescent device constituting an OELD will be described with reference to fig. 10, but the organic electroluminescent device according to the present invention is not limited thereto. In addition, the configuration thereof may be appropriately changed as needed within a limit not departing from the gist of the present invention.

In the organic electroluminescent device 210 according to the present embodiment, a stacked structure 213 is stacked on a substrate 211. The stacked structure 213 includes a cathode 213c, an organic thin film layer 213b, and an anode 213a in this order from the substrate 211 side. The organic electroluminescent device 210 has: a glass member 212 and a sealing layer 215, the glass member 212 being placed so as to cover the outer surface side of the laminated structure 213 and so as to face the substrate 211, the sealing layer 215 adhering the substrate 211 and the glass member 212 together.

The sealing layer 215 contains the glass composition, and the glass transition temperature of the glass constituting the glass composition is 350 ℃ or lower. A reaction layer (not shown) having a thickness of 4nm to 25nm is formed between the sealing layer 215 and at least one of the substrate 211 and the glass member 212.

[ examples ]

The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples. Examples 4-1 to 4-6 are examples, and examples 5-1 to 5-3 are comparative examples. Examples 1-1 to 1-4 and 2-1 to 2-5 are examples of producing low-melting glass in examples, and examples 3-1 to 3-3 are examples of producing low-melting glass in comparative examples.

Examples 1-1 to 1-4 and 3-1 to 3-3

(production of glass powder)

The raw materials were mixed so as to have a composition in mol% in the column "glass composition" in tables 1 and 3, and melted in an electric furnace at 1050 to 1150 ℃ for 1 hour using a platinum crucible. Next, the obtained molten glass is molded into a sheet-like glass.

The sheet glass was pulverized by a rotary ball mill and classified by a sieve, thereby obtaining glass powders of examples 1-1 to 1-4 and 3-1 to 3-3 having a particle size of 0.5 to 15 μm.

[ examples 2-1 to 2-5]

(production of glass powder mixture)

The glass powders of examples 1-2 to 1-4 were mixed so as to have the volume ratios shown in Table 2, thereby obtaining glass powder mixtures of examples 2-1 to 2-5. The average composition of each glass powder mixture is shown in table 2. In Table 2, "glass 1-2" means the glass powder of example 1-2, and the same meanings apply to other similar descriptions.

The glass transition Temperature (TG) as a glass characteristic was measured for the obtained glass powder or glass powder mixture of each example using a differential thermal analyzer (manufactured by japan chemical corporation, Thermo Plus TG 8110). The measurement conditions were: alumina was used as a reference sample in the atmosphere, and the temperature rise rate was set to 10 ℃/min, and the temperature range was set to room temperature to 500 ℃. As described above, the first inflection point is defined as the glass transition temperature.

The obtained results are shown in tables 1 to 3.

TABLE 1

TABLE 2

TABLE 3

Examples 4-1 to 4-6 and 5-1 to 5-3

(production of glass paste)

The glass powder or glass powder mixture and the laser light absorbing substance (Fe) of each example were blended so as to have the proportions (vol%) shown in tables 4 and 5₂O₃-CuO-MnO) and a low expansion filler (zirconium phosphate), to obtain a glass composition powder. Further, ethyl cellulose (resin) and diethylene glycol mono 2-ethylhexyl ether (solvent) were blended so as to have the proportions (mass%) shown in table 4, to prepare organic vehicles. Then, glass composition powder and an organic vehicle were formulated in the mass ratio shown in table 4, and diluted with diethylene glycol mono 2-ethylhexyl ether to a viscosity suitable for screen printing, thereby preparing a glass paste. The particle size of the laser light absorbing material was 0.8 μm, and the particle size of the low expansion filler was 0.9 μm.

In tables 4 and 5, "glass 1-1" means the glass powder of example 1-1, and the same meanings as described above with respect to the other elements.

(preparation of sealed Package)

As shown in fig. 11 and 12, the glass paste was coated in a frame shape on the surface of a glass substrate 32 including AN100 (25 mm × 25mm × 0.5mm thick) as AN alkali-free glass using a 400-mesh screen. Then, the film was dried at 120 ℃ for 10 minutes, and pre-calcined at 420 ℃ for 10 minutes to 480 ℃ for 10 minutes, thereby forming a pre-calcined layer 35 a. When the precalcined layer 35a is used as the sealing layer 35, the width is set to about 500 μm, and the thickness is set to about 4 to 8 μm.

Then, the glass substrate 31 and the glass substrate 32 provided with the pre-firing layer 35a are stacked so that the glass substrate 31 and the pre-firing layer 35a are in contact with each other to form an assembly. The assembly was irradiated with a laser beam (semiconductor laser) having a wavelength of 940nm and a spot diameter of 1.6mm from the glass substrate 32 side at a scanning speed of 10 mm/sec, to melt the pre-baked layer 35a and rapidly quench and solidify it. Thus, as shown in fig. 13, a sealed package 30 in which the glass substrate 32 is bonded to the glass substrate 31 via the sealing layer 35 is produced.

The output powers of the laser beams were set to values shown in tables 4 and 5, but in examples 4-3 to 4-6, a plurality of output powers were selected, and differences in the thickness and the ball drop strength of the reaction layer caused by the selected output powers were examined.

(measurement of thickness of reaction layer)

In the sealed package 30, the thickness of the reaction layer obtained by the reaction between the glass substrate 32 and the sealing layer 35 was measured by the following method.

The glass substrate 31 is peeled off from the sealed package 30. Next, distilled water was used to mix 1: the ratio of 1 was determined by diluting an aqueous nitric acid solution (60%) to prepare an etching solution, and the sealing layer and the reaction layer were removed by immersing the sample from which the glass substrate 31 was removed in the etching solution for 48 hours. Next, the sample was washed with distilled water and wiped.

The object obtained as described above is only the glass substrate 32, and when the reaction layer is formed, as shown in fig. 18, the reaction layer is left on the surface thereof as the concave portions 36 after the reaction layer is formed. Interference fringes on the side of the glass substrate 32 on which the sealing layer was formed, that is, the side having the concave portions 36 were photographed using a white light interferometer (ZYGO New View 6200, manufactured by ZYGO corporation, usa), and the thickness of the reaction layer was obtained based on height information obtained from the interference fringes.

The specific measurement method was carried out according to the following procedure. A zoom lens of 0.5 times and an objective lens of 10 times are used.

The height of the region of the main surface of the glass substrate on the side of the glass substrate 32 on which the reaction layer is formed, that is, on the side in contact with the sealing layer, where the reaction layer is not formed, that is, the recessed portion 36, is set to the glass thickness Ha. On the other hand, the height of the frame-shaped region in which the reaction layer, i.e., the concave portion 36 is formed is set to the glass thickness Hb. The thickness of the reaction layer is an average value obtained by measuring the difference between Ha and Hb (Ha-Hb) at 3.

Here, Ha is measured for height in the range of 1.4mm in width at an arbitrary position in the region where the concave portion 36 is not formed, and the average value thereof is taken as the glass thickness Ha. Further, Hb is a value calculated by the following method. First, the height of the concave portion in the width direction α is measured with an arbitrary point of the region where the concave portion 36 is formed as the center. Next, a moving average of 3 points was taken for the waveform of the measured height in the width direction α of the concave portion. In the height waveform obtained by taking the moving average value, the height is measured in the range of 1.4mm in the direction β perpendicular to the width direction of the preceding concave portion, with the point having the lowest height, that is, the point having the deepest depth of the concave portion, as the center. The average value of the measured heights was defined as the glass thickness Hb.

(Ha-Hb) at the first position is obtained from Ha and Hb obtained by the above. The same measurement was repeated at the other two places, and the average value of the obtained (Ha-Hb) values at 3 places was taken as the thickness of the reaction layer.

When calculating (Ha-Hb) at one site, a site in proximity to each other is selected as the regions where Ha and Hb are measured. This takes into account the fact that the glass substrate before the reaction layer is formed has a non-uniform thickness.

(measurement of falling ball Strength)

As the evaluation of the impact resistance, the falling ball strength was measured.

As shown in fig. 14 and 15, a support substrate 46 of 100mm × 100mm × 3.4mm in thickness was fixed to one surface of the sealed package 30 using a thermosetting adhesive 43 as a test piece for strength evaluation.

Then, as shown in fig. 16, the weight ball 47 is dropped from the side of the non-bonded strength evaluation test piece in the range where the strength evaluation test piece is bonded to the support substrate 46. The mass of the heavy ball 47 and the falling height 48 were changed, and the falling energy at this time was taken as the falling ball strength, and calculated using the following equation.

The falling energy was gradually increased, and the maximum falling energy when the pair of

glass substrates

31 and 32 of the sealed package 30 were not peeled off was measured as the falling ball strength. The phrase "the pair of

glass substrates

31 and 32 of the sealed package 30 do not peel" means that peeling does not occur 2 or more times in three tests. The results of the ball drop strength measurement are shown in tables 4 and 5.

Fig. 17 shows the relationship between the falling ball strength and the thickness of the reaction layer.

Falling ball Strength [ mJ]Mass of heavy ball [ g]X height of falling]X acceleration of gravity [ m/s²]

TABLE 5

The reaction layer was formed in a sufficient thickness in the sealed packages of examples 4-1 to 4-6, and the reaction layer exhibited excellent impact strength. On the other hand, in the sealed packages of examples 5-1 to 5-3 as comparative examples, low melting point glass having a glass transition temperature of 350 ℃ or less was used for the sealing layer, but as a result, no reaction layer was formed, or even if a reaction layer was formed, the thickness was small, and the impact strength was poor.

The present application is based on Japanese patent application No. 2020-.

Claims

1. A sealed package, the sealed package having:

the sealing layer comprises a glass composition that is,

the thickness of the reaction layer is 4 nm-25 nm.

2. The sealed package of claim 1, wherein the glass comprises V₂O₅As the main component.

3. The sealed package of claim 2, wherein the glass further comprises Bi₂O₃。

4. The sealed package of any of claims 1-3, wherein the glass composition further comprises at least one of a low expansion filler and a laser absorbing material.

5. The sealed package of any of claims 1 to 4, wherein at least one of the first substrate and the second substrate is a glass substrate.

6. An organic electroluminescent device, wherein the organic electroluminescent device has:

the sealing layer comprises a glass composition that is,

at least one of the reaction layers has a thickness of 4nm to 25 nm.

7. The organic electroluminescent device of claim 6, wherein the glass comprises V₂O₅As the main component.

8. The organic electroluminescent device according to claim 7, wherein the glass further comprises Bi₂O₃。

9. The organic electroluminescent device according to any one of claims 6 to 8, wherein the glass composition further comprises at least one of a low expansion filler and a laser absorbing substance.

10. The organic electroluminescent device according to any one of claims 6 to 9, wherein at least one of the first substrate and the second substrate is a glass substrate.