TW202145615A - Sealed package and organic electroluminescent element comprising a first substrate, a second substrate arranged opposite to the first substrate, and a sealing layer arranged therebetween - Google Patents

Abstract

This invention relates to a sealed package, comprising: a first substrate, a second substrate arranged opposite to the first substrate, and a sealing layer arranged between the first substrate and the second substrate and adhering the first substrate and the second substrate, wherein the sealing layer contains a glass composition, wherein the glass transition temperature of the glass constituting the glass composition is 350 DEG or less. The total thickness of the reaction layer obtained by reacting at least one of the first substrate and the second substrate with the sealing layer is 4 nm to 25 nm.

Description

Hermetic packaging and organic electroluminescent components

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

Flat panel display devices (FPD) such as organic EL displays (Organic Electro-Luminescence Display: OELD), plasma display panels (PDP), etc. have a glass package sealed with a pair of glass substrates to seal light-emitting elements the structure. In addition, a liquid crystal display device (LCD) has a structure in which liquid crystal is sealed between a pair of glass substrates. Furthermore, 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 element (photoelectric conversion element) is sealed between a pair of glass substrates.

Among them, the organic EL display will significantly deteriorate the light-emitting characteristics of the organic electroluminescent element (organic EL element) due to contact with moisture, so the organic EL element needs to be strictly shielded from the outside atmosphere. In addition, since the organic EL element is damaged when exposed to high temperature, the sealing method is extremely important.

Therefore, as a sealing method of an organic EL display, the method of using glass powder as a sealing material and sealing by local heating is considered to be effective. The glass powder refers to a glass powder obtained by pulverizing glass, and it is usually used by mixing it with an organic vehicle and slurrying it. The paste is coated on a glass substrate by screen printing or dispensing, and then fired to form a pre-fired layer. Next, another glass substrate is stacked, and the pre-fired layer is locally heated by using a laser or the like to melt the glass powder to achieve sealing.

In this way, as the glass used as a sealing material, for example, Patent Document 1 describes a TeO ₂ -ZnO-B ₂ O _3- based glass for sealing an organic EL display. In addition, Patent Document 2 discloses an electronic device including a pair of glass substrates and a sealing layer, and a reaction layer with the sealing layer is generated inside the glass substrate, and the maximum depth of the reaction layer from the interface with the sealing layer is above 30 nm. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6357937 [Patent Document 2] Japanese Patent No. 5692218

[Problems to be Solved by Invention]

In recent years, organic electroluminescent devices are also used in display panels of smart phones or wearable terminals. As the demand for smart phones or wearable terminals increases, higher strength is required for strong shocks generated when such terminals are dropped.

According to the research of the present inventors, it is presumed that the impact resistance strength is greatly influenced by the thermal stress accumulated in the sealing layer and the adhesion strength between the base material and the sealing layer. The thermal stress is mainly accumulated in the sealing layer during the process of cooling the heated sealing material from around the glass transition temperature to room temperature during sealing. Therefore, if the glass transition temperature can be lowered to suppress thermal stress, it can be sealed at a low temperature, and the impact strength can be improved. In addition, the adhesion strength between the base material and the sealing layer is also important to achieve higher impact strength.

On the other hand, the glass transition temperature of the glass described in patent document 1 is as high as 350 degreeC or more in general. Since the glass frit described in Patent Document 2 has a softening point temperature of 420° C., it is predicted that the glass transition temperature is also high. Therefore, the sealing performance at low temperature still has room for improvement.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a hermetic package and an organic electroluminescent device which are excellent in impact resistance. [Technical means to solve problems]

The present inventors found that by using glass with a glass transition temperature of 350°C or lower as the sealing layer and keeping the thickness of the reaction layer between the substrate and the sealing layer within an appropriate range, the sealing performance at low temperatures and the sealing between the substrate and the sealing layer can be achieved The higher bonding strength of the layers is achieved, thereby completing the present invention.

That is, the present invention provides a hermetically sealed package and an organic electroluminescent device having the following structures. [1] A hermetic package comprising: a first substrate; a second substrate disposed opposite to the first substrate; and a sealing layer disposed between the first substrate and the second substrate, and wherein the The first substrate is bonded to the second substrate; the sealing layer includes a glass composition; the glass transition temperature of the glass constituting the glass composition is 350° C. or lower; at least one of the first substrate and the second substrate is formed For the reaction layer formed by reacting with the sealing layer, the thickness of the reaction layer is 4 nm to 25 nm. [2] The hermetic package according to the above [1], wherein the glass contains V ₂ O ₅ as a main component. [3] The hermetic package according to the above [2], wherein the glass further contains Bi ₂ O ₃ . [4] The hermetic package according to any one of the above [1] to [3], wherein the glass composition further comprises at least one of a low expansion filler and a laser absorbing substance. [5] The hermetic package according to any one of the above [1] to [4], wherein at least one of the first substrate and the second substrate is a glass substrate. [6] An organic electroluminescent element comprising: a first substrate; a second substrate disposed opposite to the first substrate; and a sealing layer disposed between the first substrate and the second substrate, and bonding the first substrate and the second substrate; the sealing layer includes a glass composition; the glass transition temperature of the glass constituting the glass composition is 350° C. or lower; and at least one of the first substrate and the second substrate is formed. One is a reaction layer formed by reacting with the sealing layer, and at least one of the reaction layers has a thickness of 4 nm to 25 nm. [7] The organic electroluminescent device according to the above [6], wherein the glass contains V ₂ O ₅ as a main component. [8] The organic electroluminescent device according to the above [7], wherein the glass further contains Bi ₂ O ₃ . [9] The organic electroluminescent device according to any one of the above [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 element according to any one of the above [6] to [9], wherein at least one of the first substrate and the second substrate is a glass substrate. [Effect of invention]

The hermetically sealed package and the organic electroluminescent element of the present invention are excellent in impact resistance against drops and the like.

Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to embodiment demonstrated below. In addition, in the following drawings, the same reference numerals are attached to the members and parts that perform the same functions, and the same reference numerals are used for description, and repeated descriptions are omitted or simplified. In addition, in order to explain the present invention clearly, the embodiments described in the drawings are presented in a modeled manner, and do not necessarily accurately represent the actual size or scale.

＜Sealed package＞ The hermetic package of the present embodiment includes a first substrate and a second substrate arranged opposite to the first substrate, and has a sealing layer between the first substrate and the second substrate for adhering these substrates. The sealing layer contains a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350° C. or lower. Furthermore, between at least one of the first substrate and the second substrate and the sealing layer, a reaction layer formed by reacting the same is formed, and the thickness is 4 nm to 25 nm. In this specification, a glass composition refers to an inorganic mixture comprising glass. The above-mentioned glass composition may contain, in addition to glass, at least one of a low-expansion filler and a laser absorbing substance, or may be only glass.

1 and 2 are a plan view and a cross-sectional view showing an embodiment of a hermetic package. 3A to 3D are step diagrams showing one embodiment of the method of manufacturing the hermetic package shown in FIG. 1 . 4 and 5 are a plan view and a cross-sectional view of a first substrate used for manufacturing the hermetic package shown in FIGS. 1 and 2 . FIGS. 6 and 7 are a plan view and a cross-sectional view of a second substrate used for manufacturing the hermetic package shown in FIGS. 1 and 2 .

The hermetic package 10 constitutes FPDs such as OELDs, PDPs, and LCDs, lighting devices (OEL lighting, etc.) using light-emitting elements such as organic electroluminescence (OEL) elements, or solar cells such as dye-sensitized solar cells. That is, the hermetic package 10 includes: a first substrate 11; a second substrate 12 arranged to face the first substrate; and a sealing layer 15 arranged between the first substrate 11 and the second substrate 12 and connecting the first substrate 11 to the second substrate 12. The substrate is bonded to the second substrate. Moreover, the sealing layer 15 contains a glass composition, and the glass transition temperature of the glass which comprises a glass composition is 350 degrees C or less.

The first substrate 11 is, for example, an element substrate on which the electronic component portion 13 is mainly provided. The second substrate 12 is, for example, a closed substrate mainly used for sealing. The electronic element portion 13 is provided on the first substrate 11 . The 1st board|substrate 11 and the 2nd board|substrate 12 are arrange|positioned facing each other, and are connected by the sealing layer 15 arrange|positioned between them in a frame shape.

Between at least one of the first substrate 11 and the second substrate 12 and the sealing layer 15, a reaction layer (not shown) formed by reacting the substrate and the sealing layer is formed. The thickness of the reaction layer is 4 nm to 25 nm. The sealing layer and the reaction layer will be described below.

The first substrate 11 and the second substrate 12 are not particularly limited, as long as at least one of the two can form a reaction layer with the sealing layer, the laser transmittance is excellent and the sealing layer can be efficiently heated , preferably a glass substrate. As for the glass substrate, it is more preferable to use a soda lime glass substrate, an alkali-free glass substrate, or the like. As for the soda-lime glass substrate, for example, AS, PD200 (both are manufactured by AGC Corporation, trade names), or those obtained by chemical strengthening of these can be mentioned. As an alkali-free glass substrate, for example, AN100 (manufactured by AGC, trade name), EAGEL2000 (manufactured by Corning, trade name), EAGEL GX (manufactured by Corning, trade name), JADE (manufactured by Corning, trade name) ), #1737 (manufactured by Corning Corporation, trade name), OA-10 (manufactured by Nippon Electric Glass Co., Ltd., trade name), TEMPAX (manufactured by Schott, trade name), etc. The first substrate 11 and the second substrate 12 may use the same substrate or different substrates.

Regarding the electronic component part 13, for example, in the case of OELD or OEL lighting, it has an OEL element; in the case of a PDP, it has a plasma light-emitting element; in the case of an LCD, it has a liquid crystal display element; in the case of a solar cell, it has a It has a dye-sensitized solar cell element, that is, a dye-sensitized photoelectric conversion part element. The electronic component part 13 can adopt various well-known structures, and is not limited to the structure shown in figure.

In the hermetic package 10 of FIGS. 1 and 2 , an OEL element, a plasma light-emitting element, and the like are provided on the first substrate 11 as the electronic element portion 13 . When the electronic element portion 13 is a dye-sensitized solar cell element or the like, element films such as wiring films and electrode films are provided on the opposing surfaces of the first substrate 11 and the second substrate 12, but this is not shown. .

When the electronic element portion 13 is an OEL element or the like, a part of the space remains between the first substrate 11 and the second substrate 12 . The space can be kept in its original state or filled with transparent resin. The transparent resin may be attached to the first substrate 11 and the second substrate 12, or may only be in contact with each other.

When the electronic element portion 13 is a dye-sensitized solar cell element or the like, the electronic element portion 13 is entirely arranged between the first substrate 11 and the second substrate 12, but this is not shown. In addition, the sealing object is not limited to the electronic element part 13, A photoelectric conversion device etc. may be sufficient as it. Also, the hermetic package 10 may be a construction material such as a laminated glass without the electronic component portion 13 .

[Sealing Layer] The sealing layer in this embodiment contains a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350° C. or lower. Hereinafter, this glass is referred to as "low melting point glass".

The glass composition can form a sealing layer at low temperature by including low-melting glass. Therefore, the thermal stress accumulated in the process of cooling the heated sealing material from the vicinity of the glass transition temperature to room temperature at the time of sealing can be suppressed. As a result, the impact resistance of the obtained hermetic package can be improved.

The glass transition temperature (Tg) of the low-melting glass should just be 350°C or lower, and Tg is preferably 340°C or lower, more preferably 330°C or lower, from the viewpoint of obtaining better low-temperature sealing properties. The lower limit of the glass transition temperature is not particularly limited, but is preferably 290°C or higher. By setting the glass transition temperature to be 290° C. or higher, when an organic vehicle containing a resin is mixed with a glass composition to form a glass paste, the glass can be prevented from softening and the resin remaining in the sealing layer before the resin is removed. Furthermore, the glass transition temperature (Tg) of the low-melting glass was measured using a differential thermal analyzer, and the first inflection point was set as the glass transition temperature.

One kind of glass may be sufficient as the material which comprises a low melting point glass, and two or more types may be sufficient as it. When the low-melting glass includes one kind of glass, the glass transition temperature of the glass should be within the above-mentioned range. In the case where there are two or more kinds of glass as the material constituting the low-melting glass, the glass transition temperature (Tg) of the obtained low-melting glass can be measured using a differential thermal analyzer, and estimated from the first inflection point, The glass transition temperature should just be in the said range.

In the case where there are two or more types of glass as the material constituting the low-melting glass, the total content of the glass as the material whose glass transition temperature is 350°C or lower relative to the total amount of the glass as the material constituting the low-melting glass depends on each The glass transition temperature of the glass varies and cannot be uniquely determined, but it is preferably 80% by volume or more, more preferably 85% by volume or more. The upper limit of the total content is not particularly limited, and the glass transition temperature of all the glasses that can be used as materials is 350° C. or lower, that is, the total content is 100% by volume.

The composition of the low-melting glass is not particularly limited as long as it has the above-mentioned properties, but it preferably contains V ₂ O ₅ as a main component. V ₂ O ₅ is a glass-forming oxide, and is a component that forms the network structure of the glass and achieves a lower glass transition temperature. Moreover, it is also effective as a laser absorption component. In addition, in this specification, the main component refers to the component whose content is the largest in terms of molar % based on oxide among the components constituting the glass. In addition, when there are two or more kinds of glass as the material constituting the low-melting glass, the lower melting point is determined based on the composition indicated by the molar % on the oxide basis and the content ratio (volume %) of each glass. Composition of melting point glass. Specifically, _{the content of V 2} O ₅ is preferably 10% or more, more preferably 20% or more, still more preferably 25% or more, and still more preferably 30% or more. In addition, from the viewpoint of preventing the water resistance from being lowered or the glass stability from being lowered and the glass becoming easily devitrified during glass production, _{the content of V 2} O ₅ is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less, more preferably 35% or less.

The low-melting glass preferably further contains Bi ₂ O ₃ . In particular, when a glass substrate is used as a substrate, Bi ₂ O ₃ easily reacts with the glass substrate when the sealing layer is formed, so that the reaction layer is easily formed. With the reaction layer, the subsequent strength is increased, and better impact resistance strength of the hermetic package can be obtained. Specifically, _{the content of Bi 2} O ₃ 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. Moreover, from the viewpoint of maintaining good low-temperature sealing properties, _{the content of Bi 2} O ₃ 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 serving as the sealing layer will be described. In addition, the composition is not limited to the following, and is not particularly limited as long as the glass transition temperature is within the above-mentioned range, and a reaction layer with an appropriate thickness can be formed with the substrate. In addition, when there are two or more kinds of glass as the material constituting the low-melting glass, it is only necessary that the composition shown by the molar % on the oxide basis of each glass and the content ratio (volume %) of the same are determined. The determined composition (hereinafter referred to as "average composition") may be as follows.

The low-melting glass in this embodiment preferably does not substantially contain alkali metal oxides, and contains 10.0-50.0% of V ₂ O ₅ , 14.5-45.0% of TeO _{2 in} molar % based on oxides, 5.0-45.0% of ZnO, and 0.5-20.0% of Bi ₂ O ₃ . In the description of each component below, unless otherwise specified, the "%" in the content of each component in the low-melting glass is based on oxides, that is, expressed in molar % in terms of oxides.

When the low-melting glass contains an alkali metal oxide, when the sealing material is exposed to high temperature during or after sealing, the alkali component may diffuse into the sealing material such as the substrate, and the sealing member may be deteriorated. Therefore, it is preferable that the low-melting glass does not substantially contain an alkali metal oxide. In addition, "substantially free" means that it is not contained except for unavoidable impurities, that is, it means that it is not intentionally added. Therefore, the low-melting glass may contain a trace amount of alkali metal oxide as an unavoidable impurity. The content of the alkali metal oxide in the low-melting glass is preferably 1000 ppm or less, more preferably 500 ppm or less. In addition, in this specification, the alkali metal oxide means Li ₂ O, Na ₂ O and K ₂ O, and the content of the alkali metal oxide means the total content of these. In addition, ppm means mass ppm.

V ₂ O ₅ is a glass-forming oxide that forms a glass network structure, and is a low-softening component, that is, a component that lowers the glass transition temperature, so it is preferably contained in the low-melting glass. In addition, V ₂ O ₅ is also effective as a laser absorbing component. _{As described above, it is preferable to contain V 2} O ₅ as a main component because the low-temperature sealing performance is excellent by lowering the glass transition temperature and high impact strength is obtained. Moreover, _{the content of V 2} O ₅ 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. _{The content of V 2} O ₅ is preferably 50.0% or less, more preferably 45.0% or less, and still more preferably 40.0% from the viewpoint of preventing water resistance from decreasing and glass stability from decreasing and glass becoming devitrified easily during glass production. Below, more preferably, it is 35.0% or less.

TeO ₂ is a glass oxide that forms a glass network structure and is a low softening component, so it is preferably contained in a low melting point glass. From the viewpoint of improving low-temperature sealing properties and preventing crystallization during calcination and sealing by lowering the glass transition temperature, _{the content of TeO 2} is preferably 14.5% or more, more preferably 16.0% or more, and more preferably 18.0% or more, More preferably, it is 20.0% or more. Moreover, from the viewpoint of preventing the thermal expansion coefficient from becoming too large, _{the content of TeO 2} 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.

It is preferable to contain ZnO as a component which lowers a 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, the content of ZnO is preferably 45.0% or less, more preferably 40.0% or less, more preferably 35.0% or less, and still more preferably 30.0%, from the viewpoint of preventing glass stability from decreasing and glass devitrification during glass production. %the following.

Bi ₂ O ₃ is a component that easily reacts with the substrate during sealing to improve the bonding strength by forming a reaction layer. Therefore, Bi ₂ O ₃ is important for the low-melting glass of the present embodiment, and it is preferable to include it in the low-melting glass together _{with V 2} O _{5 .} By setting _{the content of Bi 2} O ₃ to a certain amount or more, the effect of improving the bonding strength can be sufficiently obtained. On the other hand, by making _{the content of Bi 2} O ₃ less than or equal to a certain amount, the glass transition temperature does not become too high, and favorable low-temperature sealing properties can be maintained. Furthermore, when the substrate is a glass substrate, excessive reaction with the glass substrate can be suppressed, and high melting point components such as _{SiO 2 in the glass substrate can be introduced into the glass composition.} As a result, the anchor point does not rise, and the residual stress of the sealing layer after sealing is prevented from increasing.

In the case of using V ₂ O _{5 -TeO 2} -ZnO glass as the low melting point glass, the preferable content _{of Bi 2} O _{3 which} can improve the bonding strength while maintaining the low temperature sealing property is 0.5-20.0%. The content of Bi ₂ O ₃ is more preferably 1.0% or more, more preferably 1.5% or more, still more preferably 2.0% or more, and more preferably 15.0% or less, still more preferably 10.0% or less, and still more preferably 7.0% or less.

In _{the low-melting glass containing V 2} O ₅ as a main component and further containing Bi ₂ O ₃ , from the viewpoint of stabilizing the glass by suppressing crystallization during firing and sealing, V represented _{by V 2} O ₅ /TeO _{2 The ratio of the content of 2} O ₅ to TeO ₂ is preferably 0.5 or more, more preferably 1.0 or more, and more preferably 2.5 or less, more preferably 2.0 or less.

CuO is a component which has the effect of lowering the thermal expansion coefficient and has the effect of improving the water resistance, so it is preferably contained in the low-melting glass. Furthermore, CuO is also effective as a laser absorbing component. By containing CuO, the amount of pigment added for laser absorption can be reduced when the glass paste is formed when the sealing layer is formed, and instead, more low-expansion fillers can be contained. Thereby, glass paste with a lower thermal expansion coefficient can be obtained. From the above viewpoints, the content of CuO is preferably 1.0% or more, more preferably 2.0% or more, and still more preferably 5.0% or more. On the other hand, from the viewpoint of preventing glass crystallization during firing and sealing, the content of CuO is preferably 10.0% or less, more preferably 8.0% or less, and still more preferably 7.5% or less.

Fe ₂ O ₃ is also effective as a laser absorbing component, so it can also be included in the low-melting glass. By containing Fe ₂ O ₃ , it is possible to reduce the amount of pigments added for laser absorption when making glass paste, and instead, contain more low-expansion fillers. Thereby, glass paste with a lower thermal expansion coefficient can be obtained. From the above viewpoints, _{the content of Fe 2} O ₃ is preferably 1.0% or more. However, if CuO or MnO is already contained, even if Fe ₂ O ₃ is not contained, the above-mentioned effects can be obtained. _{On the other hand, the content of Fe 2} O ₃ is preferably 7.0% or less, more preferably 5.0% or less, from the viewpoint of preventing glass crystallization during firing and sealing, and further suppressing a decrease in low-temperature sealing properties as the glass transition temperature rises. More preferably, it is 2.0% or less.

MnO is an effective component as a laser absorbing component, so it can also be included in low melting glass. By containing MnO, it is possible to reduce the addition amount of pigments for laser absorption when making glass paste, and to contain more low-expansion fillers instead. Thereby, glass paste with a lower thermal expansion coefficient can be obtained. From the above viewpoints, the content of MnO is preferably 1.0% or more. However, if CuO or Fe ₂ O ₃ is already contained, the above-mentioned effects can be obtained even if MnO is not contained. On the other hand, from the viewpoint of preventing glass crystallization during firing and sealing, the content of MnO is preferably 7.0% or less, more preferably 5.0% or less, and still more preferably 2.0% or less.

From the viewpoint of obtaining a better laser absorption effect, _{the total content of CuO, Fe 2} O _{3 and MnO represented by (CuO+Fe 2} O ₃ +MnO) is preferably 1.0% or more, more preferably 2.0% or more, and further It is preferably 4.0% or more, and more preferably 5.0% or more. Moreover, in order to avoid glass crystallization at the time of laser firing and sealing, the total of the content is preferably 10.0% or less, more preferably 8.0% or less, and still more preferably 7.5% or less.

CuO, Fe ₂ O ₃ and MnO are all relatively effective components as laser absorbing components. In order to strike a balance between the effect of the low temperature sealing property by the laser absorption and the avoidance of glass crystallization, it is preferable to contain a large amount of CuO among these components. Specifically, the ratio of the CuO content represented by {CuO/(CuO+Fe ₂ O ₃ +MnO)} to the total content of CuO, Fe ₂ O ₃ and MnO is preferably 30% or more (0.3 or more), more preferably 50% or more (0.5 or more), more preferably 70% or more (0.7 or more). Moreover, the said ratio may be 100%, that is, only CuO may be contained.

B ₂ O ₃ is a glass oxide, and is a component that forms a glass network structure to improve glass stability, so it is preferably contained in a low-melting glass. When the case containing B ₂ O _3, the content thereof is preferably 0.5% or more, more preferably 1.0% or more, and further preferably 1.5% or more. _{On the other hand, the content of B 2} O ₃ is preferably 10.0% or less, more preferably 7.5% or less, and still more preferably 5.0% from the viewpoint of preventing the glass from being unstable due to excessive content and being easily crystallized during firing and sealing. %the following.

BaO is a relatively effective component for glass stabilization, so it can be contained in low-melting glass. When contained in a low-melting glass, the content of BaO is preferably 2.0% or more. On the other hand, in order to keep the glass transition temperature or the thermal expansion coefficient within an appropriate range, the content of BaO is preferably 10.0% or less, more preferably 8.0% or less.

Al ₂ O ₃ and Nb ₂ O ₅ have the effect of lowering the expansion coefficient and also have the effect of improving the water resistance, so they may be contained in the low-melting glass. When contained in a low-melting glass, _{the content of Al 2} O ₃ and Nb ₂ O ₅ is preferably 2.0% or more, respectively. On the other hand, in order to keep the glass transition temperature within an appropriate range, the content of Al ₂ O ₃ and Nb ₂ O ₅ is preferably 10.0% or less, and more preferably 8.0% or less.

Represented by the _{(V 2 O 5 + TeO 2} + ZnO) V 2 O 5, the total content of TeO ₂ and ZnO of 78.0 to 89.0%, and _{(Al 2 O 3 + Nb 2} O 5) represented by the Al ₂ O ₃ and The total content of Nb ₂ O ₅ is preferably 5.0 to 11.0%. When it exists in the said range, it becomes easy to achieve both water resistance and stabilization of glass. Moreover, for the same reason, (V ₂ O ₅ +TeO ₂ +ZnO) is more preferably 79.0% or more, and more preferably 88.0% or less. In addition, (Al ₂ O ₃ +Nb ₂ O ₅ ) is more preferably 6.0% or more, and more preferably 10.0% or less.

The low-melting glass may contain components other than the above-mentioned components (hereinafter referred to as "other components") within a range that does not impair the purpose of the present invention. The total content of other components is preferably 10.0% or less.

The other components _{include: CaO, TiO 2, ZrO 2} , CeO 2, La 2 O 3, CoO, MoO 3, Sb 2 O 3, WO 3, GeO 2 and the like.

Moreover, from the viewpoint of reducing the load on the environment, it is preferable that the low-melting glass does not contain substantially lead, that is, substantially does not contain PbO.

(Manufacturing method of sealant layer) The sealant layer contains a glass composition, and the glass constituting the glass composition is low-melting glass. The manufacturing method of a sealing layer is not specifically limited, For example, it can manufacture by the method shown below.

First, prepare the stock mixture. The raw material is not particularly limited, as long as it is a raw material usually used for the production of oxide-based glass, and oxides, carbonates, and the like can be used. The kinds and ratios of the raw materials are appropriately adjusted so that the composition of the obtained glass falls within the above-mentioned range, thereby producing a raw material mixture.

In the case where two or more kinds of glasses with different compositions are used as the material of the low-melting glass, the respective compositions of the glasses with different compositions are not particularly limited, as long as the kinds and ratios of raw materials, the combination of glasses, etc. are appropriately selected so as to be suitable. The average composition may be within the above range.

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

Then, the glass which is a material of a low melting point glass is obtained by cooling and making a molten material solidify. The cooling method is not particularly limited, and for example, a method of using a rolling machine or a pressing machine, or a method of quenching by adding dropwise to a cooling liquid, etc., can be adopted. The obtained glass is preferably completely amorphous, that is, the crystallinity is 0%. However, a crystallized part may be included as long as the effect of the present invention is not impaired.

The glass form of the material obtained above is arbitrary. For example, a block shape, a plate shape, a thin plate shape (flaky shape), a powder shape, etc. are mentioned. Among them, in order to be easy to melt when forming a sealing layer, and to easily mix two or more types of glasses with different compositions when the glass used as the material of the low-melting glass is in a powder form. Moreover, by making into powder form, it becomes easy to check the performance as a sealing material.

The particle size of the powder can be appropriately selected according to the application, and the particle size of the glass powder is usually about 0.1 μm to 100 μm. In addition, the particle size of the glass powder is preferably 5.0 μm or less, more preferably from the viewpoint that the sealing layer is formed by slurrying and coating or drying without precipitation and separation, so that the obtained sealing layer does not become too thick. is 2.5 μm or less. Furthermore, the particle size of the powder in this specification means the volume-based 50% particle size (D ₅₀ ) in the cumulative particle size distribution. Specifically, in the cumulative particle size curve of the particle size distribution measured using a laser diffraction/scattering particle size distribution measuring device, the particle size when the cumulative amount accounts for 50% on a volume basis.

The glass powder can be obtained, for example, by pulverizing the glass obtained above. In this case, the particle size of the powder can be adjusted according to the grinding conditions. Moreover, in addition to the grinding|pulverization of glass, you may classify|categorize using a sieve etc. as needed. Regarding the method of pulverization, for example: rotary ball mill, vibration ball mill, planetary mill, jet mill, attritor, medium stirring mill (bead mill), jaw crusher, roller crusher, etc.

In particular, in the case of making the particle size as fine as 5.0 μm or less, it is preferable to use wet pulverization. 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, the glass powder is fired between the first base material and the second base material, thereby forming a sealing layer containing a glass composition containing low-melting glass. In the case where there are two or more types of glass to be the material of the low-melting glass, the calcination of the glass powder mixture obtained by mixing the powders of these glasses is performed. Pre-calcination can also be carried out before calcination.

This glass powder mixture is obtained when, for example, V ₂ O ₅ -TeO ₂ -ZnO-based glass is used as a base component, and Bi ₂ O ₃ -ZnO-B ₂ O ₃ -based glass is added to form a sealing layer. Low melting point glass in the embodiment. In addition, the base component means that the content is 50 vol % or more, preferably 70 vol % or more, and preferably 99.9 vol % or less with respect to the total volume of the glass powder mixture.

The glass powder may be used as it is, but from the viewpoint of improving workability, it is preferable to paste it, that is, to use it as a glass paste. When there are two or more types of glass to be the material of the low-melting glass, a plurality of glass powders can be mixed to form a glass powder mixture, and then slurry is performed, or a plurality of glass powders with different compositions can be prepared. After making the slurries, the slurries are mixed. The glass paste contains an organic vehicle, which 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 adjustment of the glass slurry can be performed by a known method using a rotary mixer equipped with a stirring blade, a roll mill, a bead mill, and the like.

The glass composition of the sealing layer preferably includes, in addition to the glass powder, at least one of a low-expansion filler and a laser-absorbing substance according to the sealing method.

Hereinafter, the case where there are two or more types of glass serving as the material of the low-melting glass will be described, that is, the preliminary firing and firing of the glass powder mixture will be described. In addition, the case where V ₂ O ₅ -TeO ₂ -ZnO-based glass is a base component and Bi ₂ O ₃ -ZnO-B ₂ O _3- based glass is an additive component will be described here, but the present invention is not limited to this. Wait.

Pre-calcination is preferably performed at a _{temperature higher than the softening point of V 2} O ₅ -TeO ₂ -ZnO-based glass by about 10 to 50°C. If the pre-calcination is performed at such a temperature, a pre-calcined layer 100a can be obtained. As shown in FIG. 8, the pre-calcined layer 100a _{has Bi 2 dispersed in the softened V 2} O ₅ -TeO ₂ -ZnO-based glass 101 as shown in FIG. 8 . O ₃ -ZnO-B ₂ O ₃ based glass 102 .

Next, in the case where the pre-fired layer 100a is heated and fired by laser irradiation or the like, it is preferable to use the pre-fired layer 100a so that the Bi ₂ O ₃ -ZnO-B ₂ O ₃ based glass as an additive component is sufficient. Heating at the melting temperature. _{It is considered that the whole body including the Bi 2} O ₃ -ZnO-B ₂ O ₃ based glass 102 is melted when calcined at such a temperature, and as shown in FIG. 9 , V ₂ O ₅ - which is a base component can be obtained. The sealing layer 100 in which a portion of the TeO ₂ -ZnO-based glass 101 and a portion of the Bi ₂ O ₃ -ZnO-B ₂ O _{3 -based glass 102 as an additive component are mixed.}

_{Since the glass transition temperature of the V 2} O ₅ -TeO ₂ -ZnO-based glass as the basic component of the sealing layer 100 is low, the residual stress after cooling to room temperature is small. In addition, the adhesive strength is also excellent _{due to the high reactivity of Bi 2} O ₃ contained in the additive component. Therefore, the impact resistance of the sealing layer 100 is excellent. Furthermore, in FIG. 9, the part of the V ₂ O ₅ -TeO ₂ -ZnO based glass 101 is _{clearly separated from the part of the Bi 2} O ₃ -ZnO-B ₂ O ₃ based glass 102, but FIG. 9 is a schematic diagram, The boundaries of these parts in the sealing layer 100 are not necessarily clear.

_{When the Bi 2} O ₃ -ZnO-B ₂ O ₃ -based glass 102 is melted by heating the pre-fired layer 100a by laser irradiation or the like _{, the Bi 2} O ₃ -ZnO-B ₂ O ₃ -based glass 102 and V _In the vicinity of the interface of the 2 O ₅ -TeO ₂ -ZnO-based glass 101 , these glasses are mixed with each other. Therefore, in the obtained sealing layer, a portion of the V ₂ O ₅ -TeO ₂ -ZnO-based glass 101 may contain Bi ₂ O ₃ -ZnO-B ₂ O ₃ -based glass, Bi ₂ O ₃ -ZnO-B _{A portion of the 2} O ₃ -based glass 102 may contain V ₂ O ₅ -TeO ₂ -ZnO-based glass. In addition, the above is not limited to the case where the glass powder mixture is pre-fired and fired in the form of a powder, and the same is also true when the pre-fire and firing are performed in the form of a glass paste.

The low-expansion filler has a low thermal expansion coefficient of glass with a lower melting point, and is added for the purpose of reducing the thermal expansion coefficient of the sealing layer. The thermal expansion coefficient of the low expansion filler is about -15×10 ^-7 /℃～45×10 ^-7 /℃.

The low-expansion filler is not particularly limited, but is preferably selected from the group consisting of silica, alumina, zirconia, zirconium silicate, cordierite, zirconium phosphate-based compounds, soda lime glass, and borosilicate glass at least one of the group. The zirconium phosphate-based compounds include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , NbZr(PO ₄ ) _3. Zr ₂ (WO ₃ )(PO ₄ ) ₂ , complex compounds of these, and the like.

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

The content of the low-expansion filler is set so that the thermal expansion coefficient of the sealing layer is close to the thermal expansion coefficient of the substrate, which is the material to be sealed. 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 relative to the total of the glass powder, the low-expansion filler and the laser absorbing substance. On the other hand, from the viewpoint of ensuring good fluidity when the sealing material is melted, the content of the low-expansion filler is preferably 50 vol % or less, more preferably 45 vol % or less, and still more preferably 40 vol % or less.

The purpose of adding the laser-absorbing substance is to fully melt the sealing material by absorbing the laser irradiated during sealing, thereby improving the low-temperature sealing performance. The laser absorbing material is not particularly limited, and in addition to _{Cu, Fe, and Mn constituting the above-mentioned CuO, Fe 2} O ₃ , and MnO in the glass composition, Cr, Ni, Ti, Co, Zn, and the like may be exemplified. At least one metal or compounds such as oxides containing the metal, i.e. inorganic pigments, etc. In addition, the laser absorbing material may be a pigment other than these.

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

From the viewpoint of better obtaining the effect of the laser absorbing material, compared with the total of glass powder, low expansion filler and laser absorbing material, the laser absorbing material containing other laser absorbing materials other _{than CuO, Fe 2} O _{3 and MnO} The total content of the radiation absorbing substances is preferably 0.1% by volume or more, more preferably 1% by volume or more, and still more preferably 3% by volume or more. On the other hand, from the viewpoint of ensuring good fluidity of the sealing material during melting and obtaining excellent bonding strength, the content of the laser absorbing substance is preferably 20 vol % or less, more preferably 18 vol % or less, and more preferably is 15% by volume or less.

As the organic vehicle, for example, one obtained by dissolving a resin as a binder component in a solvent is used. As for the resin as a binder component, for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, etc. may be mentioned. . As a solvent in this case, for example, terpineol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TEXANOL), butyl carbitol acetate, Ethyl carbitol acetate, etc.

As for the resin as the binder component, acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate can also be used. Body of acrylic resin. As a solvent in this case, for example, methyl ethyl ketone, terpineol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TEXANOL), butyl card can be used. carbitol acetate, ethyl carbitol acetate, etc. Furthermore, in this specification, (meth)acrylate means at least one of acrylate and methacrylate.

Regarding the resin used as the binder component, polyalkylene carbonates such as polyethylene carbonate and polypropylene carbonate can also be used. As a solvent in this case, for example, acetyl triethyl citrate, propylene glycol diacetate, diethyl succinate, ethyl carbitol acetate, triacetin, 2,2, 4-Trimethyl-1,3-pentanediol monoisobutyrate (TEXANOL), dimethyl adipate, ethyl benzoate, a mixture of propylene glycol monophenyl ether and triethylene glycol dimethyl ether, etc.

The ratio of resin to solvent in the organic vehicle is not particularly limited. By adjusting the viscosity of the organic vehicle, the viscosity of the glass paste is within a preferred range. The ratio of resin to solvent in the organic carrier is preferably resin:solvent=about 3:97 to 30:70 (mass ratio).

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

In the glass paste or glass composition, in addition to the above, other known additives may be blended as necessary and within the limits that do not violate the purpose of the present invention.

(Reaction layer) The reaction layer is a layer formed by the reaction between the substrate and the sealing layer. Therefore, it becomes a mixed layer containing a plurality of elements, and these plural elements are the constituent elements of the substrate and the constituent elements of the sealing layer. By forming the reaction layer between the substrate and the sealing layer, the bonding state between the substrate and the sealing layer is enhanced. To obtain the above effects, the thickness of the reaction layer should be set to 4 nm or more. The thicker the thickness of the reaction layer is, the higher the adhesive strength is, and the impact resistance is also improved. Therefore, the thickness of the reaction layer is preferably 5 nm or more, more preferably 7 nm or more, and still more preferably 10 nm or more.

The reaction layer only needs to be formed between at least one of the first substrate and the second substrate and the sealing layer, but when it is formed between both the first substrate and the second substrate and the sealing layer, a hermetic package is formed. It is preferable because the strength of the adhesive becomes high. When the reaction layer is formed between the sealing layer and the two substrates, the thickness of either reaction layer may be 4 nm to 25 nm, more preferably, the thickness of both reaction layers is 4 nm to 25 nm.

On the other hand, the reasons for setting the thickness of the reaction layer to be 25 nm or less are as follows. The thickness of the reaction layer varies according to the temperature at which the sealing layer is formed. When making the reaction layer thick, it is necessary to increase the sealing temperature, for example, when sealing by laser irradiation, it is necessary to increase the laser output. However, if the laser output is made too high, the wiring and the like located under the portion where the sealing layer is formed will be damaged. Therefore, excessive laser output cannot be applied. Therefore, there is an upper limit on the thickness of the reaction layer.

In addition, if the reactive layer is too thick, the reactive layer reacts with the layer on the opposite side of the substrate to the side where the sealing layer is located, and in the case of a thin film transistor (TFT), for example, reacts with a passivation film or an electrode, etc., And excessive generation of air bubbles. As a result, the strength of the material itself will be reduced, and the impact resistance will also be reduced. Based on this, there is also an upper limit to the thickness of the reaction layer.

Furthermore, the thickness of the reaction layer also varies depending on the composition of the glass constituting the glass composition. For example, in _{the case of glass containing V 2} O ₅ as the main component, the thickness of the reaction layer _{can be adjusted according to the content of Bi 2} O _{3 .} Specifically, when _{the content of Bi 2} O ₃ is increased, the reaction layer becomes thick, but when _{the content of Bi 2} O ₃ is too large, it becomes difficult to vitrify, and even if it is vitrified, it is immediately crystallized. In this way, the process range during sealing is narrowed, so it is not practical to increase the thickness of the reaction layer _{by increasing the content of Bi 2} O _{3 .}

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

The generation of the reaction layer can be confirmed by the method shown below as a practical method.

First, a portion of the hermetic package is cut out in a manner that can be easily ground to prepare a sample. From the sample, a substrate was ground and removed. Furthermore, when the adhesive strength is low and peeling in the sealing layer, the polishing step of the substrate can 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 solution, an acid solution capable of dissolving the constituent elements of the sealing layer is used. For example, when a bismuth-based glass is used as a sealing layer, a 30% nitric acid aqueous solution or the like is used. The reaction layer is a mixed layer of the constituent elements of the substrate and the constituent elements of the sealing layer, so when the sealing layer is removed, the reaction layer is also removed at the same time.

In this way, a substrate in which the formation trace of the reaction layer remained in the form of a concave portion was obtained, whereby it was confirmed that the reaction layer was generated. The surface shape of the board|substrate which has such a recessed part can be confirmed by a non-contact surface roughness meter, for example, a white interferometer. The specific thickness of the reaction layer was defined as the depth of the concave portion, which is the trace of the formation of the reaction layer, and the depth was measured by a white interferometer using the method described in the following examples.

<Manufacturing method of hermetic package> An example of the manufacturing method of the hermetic package of the present embodiment will be described, but the hermetic package of the present invention is not limited to these. Moreover, the structure can be suitably changed as needed within the limit which does not violate the summary of this invention.

After applying the glass paste obtained above on the second substrate in a frame shape, it is dried to form a coating layer. Examples of the coating method include printing methods such as screen printing and gravure printing; dispensing methods and the like. Drying is performed to remove the solvent contained in the glass paste, and is usually performed at a temperature of 120°C or higher for 10 minutes or longer. If the solvent remains in the coating layer, there is a possibility that the resin added as an organic vehicle as a binder component cannot be sufficiently removed in the subsequent pre-baking.

The coating layer becomes the pre-fired layer 15a by pre-firing (FIG. 6 and FIG. 7). The pre-firing is performed by heating the coating layer to a temperature below the glass transition temperature of the low-melting glass contained in the sealing material to remove the resin as a binder component, and then heating the coating layer to a temperature below the glass transition temperature of the low-melting glass contained in the sealing material. The temperature above the softening point of the low-melting glass.

Next, the 2nd board|substrate 12 and the 1st board|substrate 11 provided with the pre-fired layer 15a are arrange|positioned and laminated|stacked so that the 1st board|substrate 11 and the pre-fired layer 15a may face each other (FIG. 3A, FIG. 3B). Furthermore, on the first substrate 11 , the electronic component portion 13 is provided according to the specification of the hermetic package 10 ( FIGS. 4 and 5 ).

After that, the pre-fired layer 15a is irradiated with the laser beam 16 through the second substrate 12 to perform firing ( FIG. 3C ). The laser beam 16 is scanned and irradiated along the frame-shaped pre-fired layer 15a. The frame-shaped sealing layer 15 is formed between the first substrate 11 and the second substrate 12 by irradiating the laser beam 16 over the entire circumference of the pre-fired layer 15a. Furthermore, the laser light 16 may be irradiated to the pre-fired layer 15 a through the first substrate 11 .

The type of laser light 16 is not particularly limited, and semiconductor lasers, carbon dioxide gas lasers, excimer lasers, YAG (Yttrium-Aluminum-Garnet, yttrium-aluminum-garnet) lasers, HeNe lasers, and the like can be used. The irradiation conditions of the laser light 16 are selected according to the thickness, line width, cross-sectional area in the thickness direction, etc. of the pre-calcined layer 15a. From the viewpoint of sufficiently melting the pre-calcined layer 15a, the output of the laser light 16 is preferably 2 W or more, more preferably 5 W or more. In addition, from the viewpoint of suppressing the occurrence of cracks in the first substrate 11 and the second substrate 12, the output of the laser beam 16 is preferably 150 W or less, more preferably 120 W or less.

In this way, the hermetic package 10 in which the electronic element portion 13 is hermetically sealed by the sealing layer 15 between the first substrate 11 and the second substrate 12 is produced ( FIG. 3D ).

As mentioned above, the method of calcining by irradiation of laser light 16 has been described, but the method of calcination is not limited to the method of calcination by irradiation of laser light 16 . For the firing method, other methods may be adopted according to the heat resistance of the electronic element portion 13, the structure of the sealing package 10, and the like. For example, when the heat resistance of the electronic component part 13 is high, or when the electronic component part 13 is not provided, the entire assembly as shown in FIG. 3B can be placed in the electric furnace instead of the irradiation of the laser light 16 . In a calcining furnace, the entire assembly including the pre-calcined layer 15 a is heated to form the sealing layer 15 .

<Organic electroluminescence element> The organic electroluminescence element of the present embodiment includes a first substrate and a second substrate arranged opposite to the first substrate, and has the substrates between the first substrate and the second substrate. Then the sealing layer. The sealing layer contains a glass composition, and the glass transition temperature of the glass constituting the glass composition is 350° C. or lower. Moreover, between at least one of the first substrate and the second substrate and the sealing layer, a reaction layer formed by reacting the same is formed, and the thickness of the reaction layer is 4 nm to 25 nm.

The sealing layer and the reaction layer in the organic electroluminescent element are respectively the same as those described in (sealing layer) and (reaction layer) in the above-mentioned <sealing package>, and the preferred aspects are also the same.

Hereinafter, an example of the organic electroluminescence element constituting the OELD will be described with reference to FIG. 10 , but the organic electroluminescence element of the present invention is not limited to this. Moreover, the structure can be suitably changed as needed within the limit which does not violate the summary of this invention.

In the organic electroluminescent element 210 of the present embodiment, the laminate structure 213 is laminated on the substrate 211 . The laminated structure 213 has a cathode 213c, an organic thin film layer 213b, and an anode 213a in this order from the substrate 211 side. The glass member 212 placed so as to face the substrate 211 and the sealing layer 215 bonding the substrate 211 and the glass member 212 are provided so as to cover the outer surface side of the laminated structure 213 . The sealing layer 215 contains the above-mentioned glass composition, and the glass transition temperature of the glass constituting the glass composition is below 350°C. Furthermore, between at least one of the substrate 211 and the glass member 212 and the sealing layer 215, a reaction layer (not shown) with a thickness of 4 nm to 25 nm is formed. [Example]

Hereinafter, 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. In addition, Examples 1-1 to 1-4 and Examples 2-1 to 2-5 are the production examples of the low-melting glass in the examples, and Examples 3-1 to 3-3 are the production examples of the low-melting glass in the comparative examples. .

[Examples 1-1 to 1-4 and 3-1 to 3-3] (Manufacture of glass powder) The composition shown in the column of "glass composition" in Tables 1 and 3 is expressed in mol% , prepare the raw materials, mix them, and melt them in a platinum crucible for 1 hour in an electric furnace at 1050-1150 °C. Next, the obtained molten glass is shaped into a sheet glass. The thin plate glass was pulverized by a rotating ball mill and classified by a sieve to obtain glass powders of Examples 1-1 to 1-4 and Examples 3-1 to 3-3 with a particle size of 0.5 μm 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 in the volume ratio shown in Table 2 to obtain the glasses of Examples 2-1 to 2-5 powder mixture. The average composition of each glass powder mixture is shown in Table 2. In addition, in Table 2, "glass 1-2" means the glass powder of Example 1-2, and other similar descriptions also have the same meaning.

About the obtained glass powder or glass powder mixture of each example, the glass transition temperature (Tg) which is a glass characteristic was measured using a differential thermal analyzer (Thermo Plus TG8110 by Rigaku Co., Ltd.). The measurement conditions are as follows: In the air, using alumina as a reference sample, the temperature increase rate is set to 10°C/min, and the temperature range is set to room temperature to 500°C. As described above, let the first inflection point be the glass transition temperature. The obtained results are shown in Tables 1 to 3.

[Table 1] Table 1 1-1 1-2 1-3 1-4 Glass composition [mol%] B ₂ O ₃ 1.5 0.0 0.0 20.4 ZnO 26.5 27.0 26.0 33.3 BaO 3.7 4.0 4.0 0.0 Al ₂ O ₃ 2.9 2.0 3.0 1.2 Bi ₂ O ₃ 3.4 0.0 0.0 45.1 V ₂ O ₅ 31.4 36.0 33.5 0.0 CuO 0.0 0.0 0.0 0.0 TeO ₂ 25.9 27.0 28.5 0.0 MnO ₂ 0.0 0.0 0.0 0.0 Fe ₂ O ₃ 0.0 0.0 0.0 0.0 Nb ₂ O ₅ 4.6 4.0 5.0 0.0 glass properties Glass transition temperature Tg [℃] 324 310 318 355

[Table 2] Table 2 2-1 2-2 2-3 2-4 2-5 Mixing ratio [vol%] Glass 1-2 89 0 0 0 0 Glass 1-3 0 96 93 90 88 Glass 1-4 11 4 7 10 12 Glass composition [mol%] B ₂ O ₃ 2.2 0.9 1.5 2.1 2.7 ZnO 27.7 26.3 26.5 26.8 27.0 BaO 3.6 3.8 3.7 3.6 3.5 Al ₂ O ₃ 1.9 2.9 2.9 2.8 2.8 Bi ₂ O ₃ 4.9 2.0 3.4 4.7 6.0 V ₂ O ₅ 32.1 32.0 31.0 30.0 29.0 CuO 0.0 0.0 0.0 0.0 0.0 TeO ₂ 24.1 27.2 26.4 25.5 24.7 MnO ₂ 0.0 0.0 0.0 0.0 0.0 Fe ₂ O ₃ 0.0 0.0 0.0 0.0 0.0 Nb ₂ O ₅ 3.6 4.8 4.6 4.5 4.3 glass properties Glass transition temperature Tg [℃] 307 319 316 320 320

[table 3] table 3 3-1 3-2 3-3 Glass composition [mol%] B ₂ O ₃ 0.0 0.0 1.0 ZnO 27.5 0.0 14.9 BaO 3.8 0.0 1.0 Al ₂ O ₃ 1.9 0.0 1.0 Bi ₂ O ₃ 0.0 10.6 4.0 V ₂ O ₅ 35.0 27.3 0.0 CuO 0.0 0.0 0.0 TeO ₂ 27.0 62.1 78.2 MnO ₂ 0.0 0.0 0.0 Fe ₂ O ₃ 0.0 0.0 0.0 Nb ₂ O ₅ 4.8 0.0 0.0 glass properties Glass transition temperature Tg [℃] 304 274 325

[Examples 4-1 to 4-6 and Examples 5-1 to 5-3] (Manufacture of glass paste) The glass powder or The glass powder mixture, the laser absorbing substance (Fe ₂ O ₃ -CuO-MnO), and the low expansion filler (zirconium phosphate) were used to obtain a glass composition powder. Moreover, ethyl cellulose (resin) and diethylene glycol mono-2-ethylhexyl ether (solvent) were prepared so that it might become the ratio (mass %) shown in Table 4, and the organic vehicle was prepared. Then, the glass composition powder and the organic vehicle were prepared in the mass ratio shown in Table 4, and diluted with diethylene glycol mono-2-ethylhexyl ether to obtain a viscosity suitable for screen printing, thereby preparing glass paste. Furthermore, the particle size of the laser absorbing material is 0.8 μm, and the particle size of the low expansion filler is 0.9 μm. In addition, in Table 4 and Table 5, "glass 1-1" means the glass powder of Example 1-1, and the same meaning is the same in other descriptions.

(Preparation of hermetic package) As shown in Figures 11 and 12, the above-mentioned glass paste was applied in a frame shape using a 400-mesh screen on AN100 (manufactured by AGC Company, 25 mm×25 mm× The surface of the glass substrate 32 with a thickness of 0.5 mm). Then, drying is performed under the conditions of 120° C.×10 minutes, and further pre-sintering is performed under the conditions of 420° C. to 480° C.×10 minutes to form the pre-sintering layer 35 a. In addition, when the pre-fired layer 35a is used as the sealing layer 35, the thickness is about 500 μm, and the film thickness is about 4 μm to 8 μm. Thereafter, the glass substrate 31 and the glass substrate 32 provided with the pre-fired layer 35a are overlapped in such a manner that the glass substrate 31 and the pre-fired layer 35a are in contact to form an assembly. Further, the assembly was irradiated with laser light (semiconductor laser) having a wavelength of 940 nm and a spot diameter of 1.6 mm from the glass substrate 32 side at a scanning speed of 10 mm/s to melt and quench the pre-fired layer 35a. In this way, a hermetic package 30 is produced, in which, as shown in FIG. 13 , the glass substrate 32 is attached to the glass substrate 31 via the sealing layer 35 . Furthermore, the output of the laser light was set to the values shown in Table 4 and Table 5, but for Examples 4-3 to 4-6, a plurality of outputs were selected, and the thickness and falling ball strength of the reaction layer caused by this were investigated. difference.

(Measurement of the thickness of the reaction layer) The thickness of the reaction layer formed by the reaction between the glass substrate 32 and the sealing layer 35 in the sealing package 30 was measured by the following method. The glass substrate 31 is peeled off from the sealing package 30. Next, an etching solution was prepared by diluting an aqueous nitric acid solution (60%) with distilled water at a ratio of 1:1, and the sample from which the glass substrate 31 had been removed was immersed in the etching solution for 48 hours, thereby removing the sealing layer and the reaction layer. Next, the sample was washed with distilled water and wiped clean. The above-mentioned obtained is only the glass substrate 32, and when the reaction layer is formed, as shown in FIG. Using a white interferometer (Zygo New View 6200 manufactured by Zygo Corporation, USA), the interference fringes on the side of the glass substrate 32 where the sealing layer is formed, that is, the side with the concave portion 36, are photographed, and based on the height information obtained from the above interference fringes , to obtain the thickness of the reaction layer.

The specific measurement method was implemented according to the following procedure. Use 0.5x for the variable focal length lens and 10x for the objective. In the main surface of the glass substrate 32 on the side where the reaction layer is formed, that is, the side in contact with the sealing layer, the height of the region 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, that is, the concave portion 36 is formed, is defined as the glass thickness Hb. The thickness of the reaction layer refers to the average value when the difference (Ha-Hb) between the above-mentioned Ha and Hb is measured at three locations. Here, regarding Ha, the height was measured in a range of width 1.4 mm at an arbitrary position in the region where the concave portion 36 was not formed, and the average value was taken as the glass thickness Ha. In addition, Hb is the value calculated by the method shown below. First, the height in the width direction α of the concave portion is measured around an arbitrary point in the region where the concave portion 36 is formed. Next, the waveform of the height in the width direction α of the concave portion measured was taken as a moving average at three points. In the waveform of the moving average height, take the point with the lowest height, that is, the point with the deepest depth of the concave portion as the center, in the direction β perpendicular to the width direction of the concave portion above, within the range of 1.4 mm Determine the height. The average value of the measured heights was made into glass thickness Hb. According to the Ha and Hb obtained above, the (Ha-Hb) of the first place is obtained. The same measurement was repeated at the other two places, and the average value of the (Ha-Hb) values at the three obtained places was set as the thickness of the reaction layer. Furthermore, when calculating the (Ha-Hb) in one place, the area where Ha and Hb are determined is close to the selected place. It is considered that the thickness of the glass substrate before forming the reaction layer is not uniform.

(Measurement of falling ball strength) For the evaluation of impact resistance, the measurement of falling ball strength was performed. As shown in FIGS. 14 and 15 , the sealing package 30 was used as a test piece for strength evaluation, and a support substrate 46 of 100 mm×100 mm×thickness 3.4 mm was fixed on one side thereof with a thermosetting adhesive 43 . Then, as shown in FIG. 16, the weight ball 47 was dropped from the side where the test piece for strength evaluation was not attached to the support substrate 46 toward the region where the test piece for strength evaluation was attached. The mass of the weight ball 47 and the drop height 48 were changed, and the drop energy at this time was regarded as the drop ball strength, and the following formula was used to calculate. The drop energy was gradually increased, and the maximum drop energy of one of the sealing packages 30 without peeling off the glass substrates 31 and 32 was measured as the drop ball strength. In addition, the above-mentioned "one of the sealing packages 30 does not peel off from the glass substrates 31 and 32" means the case where the glass substrates 31 and 32 are not peeled off twice or more in three tests. The measurement results of the falling ball strength are shown in Tables 4 and 5. In addition, the relationship between the falling ball strength and the thickness of the reaction layer is summarized in FIG. 17 . Falling ball strength [mJ]=mass of weight ball [g]×falling height [m]×gravitational acceleration [m/s ² ]

[Table 4] Table 4 4-1 4-2 4-3 4-4 4-5 4-6 Glass composition powder mixing ratio [vol%] Glass 1-1 72 0 0 0 0 0 Glass 2-1 0 71 0 0 0 0 Glass 2-2 0 0 72 0 0 0 Glass 2-3 0 0 0 72 0 0 Glass 2-4 0 0 0 0 72 0 Glass 2-5 0 0 0 0 0 72 Low expansion filler (zirconium phosphate) twenty four 25 twenty four twenty four twenty four twenty four Laser Absorber (Fe ₂ O ₃ -CuO-MnO) 4 4 4 4 4 4 Organic carrier mixing ratio [mass %] Resin (ethyl cellulose) 15 15 15 15 15 15 Solvent (Diethylene glycol mono-2-ethylhexyl ether) 85 85 85 85 85 85 Glass composition powder: organic carrier (mass ratio) 74:26 76:24 76:24 76:24 76:24 76:24 Laser output [W] 38 36 34 37 35 37 39 36 38 41 41 43 45 Reaction layer [nm] 7.5 6.1 4.2 7.5 5.9 6.1 7.3 6.5 8.4 11.2 9.2 14.7 16.0 Falling ball strength [mJ] 50 50 42 50 42 50 50 46 50 65 54 58 65

[table 5] table 5 5-1 5-2 5-3 Glass composition powder mixing ratio [vol%] Glass 3-1 72 0 0 Glass 3-2 0 70 0 Glass 3-3 0 0 66 Low expansion filler (zirconium phosphate) twenty four 30 25 Laser Absorber (Fe ₂ O ₃ -CuO-MnO) 4 0 9 Organic carrier mixing ratio [mass %] Resin (ethyl cellulose) 15 15 15 Solvent (Diethylene glycol mono-2-ethylhexyl ether) 85 85 85 Glass composition powder: organic carrier (mass ratio) 76:24 76:24 76:24 Laser output [W] 31 45 34 Reaction layer [nm] 0.0 2.3 0.0 Falling ball strength [mJ] 19 6 14

In the hermetically sealed packages of Examples 4-1 to 4-6 as examples, a reaction layer with a sufficient thickness was formed, showing excellent impact resistance. On the other hand, in the sealed packages of Examples 5-1 to 5-3 as comparative examples, although the low-melting glass with a glass transition temperature of 350° C. or lower was used for the sealing layer, the reaction layer was not formed, or even though the reaction layer was formed layer but thinner, resulting in poorer impact strength. This application is based on Japanese Patent Application No. 2020-094667 filed on May 29, 2020 and Japanese Patent Application No. 2020-115907 filed on July 3, 2020, the contents of which are incorporated herein by reference.

10: Hermetic package 11: First substrate 12: Second substrate 13: Electronic component part 15: Sealing layer 15a: Pre-fired layer 16: Laser light 30: Hermetically sealed package 31: Glass substrate 32: Glass substrate 35: Sealing layer 35a: Pre-fired layer 36: Recessed portion 43: Thermosetting adhesive 46: Support substrate 47: Weight ball 48: Drop height 100: Sealing layer 100a: Pre-fired layer 101: V ₂ O ₅ -TeO ₂ -ZnO system Glass 102: Bi ₂ O ₃ -ZnO-B ₂ O ₃ based glass 210 : Organic electroluminescent element 211 : Substrate 212 : Glass member 213 : Laminated structure 213a : Anode 213b : Organic thin film layer 213c : Cathode 215 : Sealing layer

FIG. 1 is a front view showing one embodiment of a hermetic package. FIG. 2 is a cross-sectional view taken along line A-A of the hermetic package shown in FIG. 1 . FIG. 3A is a step diagram showing one embodiment of a method of manufacturing a hermetic package. FIG. 3B is a step diagram showing an embodiment of a method of manufacturing a hermetic package. FIG. 3C is a step diagram showing an embodiment of a method of manufacturing a hermetic package. FIG. 3D is a step diagram showing one embodiment of a method of manufacturing a hermetic package. FIG. 4 is a plan view of a first substrate used in the manufacture of the hermetic package shown in FIG. 1 . FIG. 5 is a sectional view taken along the line B-B of the first substrate shown in FIG. 4 . FIG. 6 is a plan view of a second substrate used in the manufacture of the hermetic 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-calcined layer obtained by pre-calcining 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 hermetic package. FIG. 11 is a top view of a glass substrate used in the manufacture of the hermetic package of the embodiment. FIG. 12 is a cross-sectional view taken along the line D-D of the glass substrate shown in FIG. 11 . FIG. 13 is a cross-sectional view showing the hermetic package of the embodiment. FIG. 14 is a top view of a hermetic package with a support substrate provided on one side. FIG. 15 is a cross-sectional view taken along the 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 the relationship between the falling ball strength and the thickness of the reaction layer. 18 is a schematic plan view of a glass substrate used for measuring the thickness of the reaction layer.

Claims (10)

A hermetic package comprising: a first substrate; a second substrate disposed opposite to the first substrate; and a sealing layer disposed between the first substrate and the second substrate, and the first substrate is attached to the above-mentioned second substrate; and The above-mentioned sealing layer comprises a glass composition, The glass transition temperature of the glass constituting the above-mentioned glass composition is 350°C or lower, a reaction layer formed by reacting at least one of the first substrate and the second substrate with the sealing layer, The thickness of the above reaction layer is 4 nm to 25 nm. The hermetic package of claim 1, wherein the above-mentioned glass contains V ₂ O ₅ as a main component. The hermetic package of claim 2, wherein the glass further comprises Bi ₂ O ₃ . The hermetic package of any one of claims 1 to 3, wherein the glass composition further comprises at least one of a low expansion filler and a laser absorbing substance. The hermetic package according to any one of claims 1 to 4, wherein at least one of the first substrate and the second substrate is a glass substrate. An organic electroluminescent element comprising: a first substrate; a second substrate disposed opposite to the first substrate; and a sealing layer disposed between the first substrate and the second substrate, The first substrate is connected to the second substrate; The above-mentioned sealing layer comprises a glass composition, The glass transition temperature of the glass constituting the above-mentioned glass composition is 350°C or lower, A reaction layer formed by reacting at least one of the first substrate and the second substrate with the sealing layer is formed, and The thickness of at least one of the above reaction layers is 4 nm˜25 nm. The organic electroluminescent element according to claim 6, wherein the above-mentioned glass contains V ₂ O ₅ as a main component. The organic electroluminescent element according to claim 7, wherein the glass further comprises Bi ₂ O ₃ . The organic electroluminescent element 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. 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.

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