WO2017016461A1 - 封装材料、有机发光二极管器件及其封装方法 - Google Patents

封装材料、有机发光二极管器件及其封装方法 Download PDF

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WO2017016461A1
WO2017016461A1 PCT/CN2016/091581 CN2016091581W WO2017016461A1 WO 2017016461 A1 WO2017016461 A1 WO 2017016461A1 CN 2016091581 W CN2016091581 W CN 2016091581W WO 2017016461 A1 WO2017016461 A1 WO 2017016461A1
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emitting diode
organic light
substrate
light emitting
rare earth
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PCT/CN2016/091581
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English (en)
French (fr)
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李娜
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京东方科技集团股份有限公司
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Priority to EP16829224.1A priority Critical patent/EP3331042B1/en
Priority to US15/502,577 priority patent/US10217959B2/en
Publication of WO2017016461A1 publication Critical patent/WO2017016461A1/zh

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/842Containers
    • H10K50/8426Peripheral sealing arrangements, e.g. adhesives, sealants
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/421Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing

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  • the present disclosure belongs to the field of packaging technologies, and in particular, to a packaging material, an organic light emitting diode device, and a packaging method thereof.
  • organic light-emitting diode (OLED) display has attracted people's attention because of its good color contrast, active illumination, wide viewing angle, thinness, fast response and low energy consumption.
  • organic light-emitting diodes, especially the electrodes and organic layers therein are prone to performance degradation due to oxygen and moisture in the surrounding environment entering the organic light-emitting diode device, which seriously affects the service life. If the electrodes and organic layers in the organic light emitting diode are hermetically sealed (encapsulated) from the surrounding environment, their lifetime will increase significantly.
  • the package structure is mainly used to enclose the organic light emitting diode between the two substrates, and the packaging performance requirements are as follows: blocking ability of oxygen: 10 -3 cm 3 /m 2 /day, blocking the water capacity: 10 -6 g / m 2 / day.
  • the width of the package structure should be as small as possible (eg, 1 mm) to reduce its effect on the size of the organic light emitting diode device.
  • the temperature required during the packaging process should be as low as possible to reduce the influence on the electrodes, organic layers, and the like of the organic light emitting diode.
  • the temperature of the pixel at 1 to 2 mm from the package structure is not higher than 1000 ° C.
  • the package structure should be insulated so that electrical connection components, such as external thin film electrodes, can pass through the package structure into the organic light emitting diode.
  • the main packaging methods currently used are laser packaging, such as laser scanning packaging, laser spot heating packaging, matrix laser packaging, and the like.
  • the laser scanning package is to project a laser beam onto the packaging material (glass frit) of the surface of the organic light emitting diode device to be packaged, and then the laser beam is scanned one week along the outline of the packaging material to melt the packaging material to complete the packaging.
  • Laser point heating package is not in the packaging material The laser spot is packaged in the same position to finally meet the packaging requirements.
  • the encapsulating material glass frit
  • a metal oxide such as cerium oxide or vanadium oxide
  • these metal oxide materials are black after being melt-solidified by laser, when When applied to transparent display devices (including other devices such as transparent light sources, of course), it will be visible to the outside world, which will seriously affect the aesthetics of the product.
  • the present disclosure has been made in view of the above circumstances, and provides an encapsulating material, an organic light emitting diode device, and a packaging method thereof that can form a transparent package structure and can be used for a transparent device.
  • An embodiment of the present disclosure provides an encapsulating material for a transparent device, comprising: a main component comprising: a rare earth metal oxide, zinc oxide, aluminum oxide, and silicon dioxide; and a binder The binder is configured to bond the principal component; wherein the primary absorption wavelength of the rare earth metal oxide is in the range of infrared light or ultraviolet light.
  • the rare earth metal oxide is an oxide of a lanthanide rare earth metal.
  • the oxide of the lanthanide rare earth metal includes any one or more of antimony trioxide, antimony trioxide, antimony trioxide, antimony trioxide, and antimony trioxide.
  • the weight percentage of each component in the main component is: rare earth metal oxide: 40 to 80% by weight; zinc oxide: 1 to 20% by weight; aluminum oxide: 2 to 20% by weight; Silicon: 5 to 20% by weight.
  • the components of the primary component are in the form of a powder.
  • the second substrate is disposed opposite to the first substrate
  • An organic light emitting diode between the first substrate and the second substrate;
  • a package structure between the two substrates and configured to surround the organic light emitting diode
  • the package structure is formed by curing of the above-mentioned packaging material.
  • the organic light emitting diode device is a transparent organic light emitting diode device.
  • Another embodiment of the present disclosure further provides an organic light emitting diode device packaging method, including The following steps:
  • the first substrate comprising at least one organic light emitting diode
  • the encapsulating material is cured to form a package structure.
  • curing the encapsulating material includes: melting and curing the encapsulating material.
  • melting the encapsulating material includes illuminating the encapsulating material with a laser to melt it.
  • the laser has a wavelength of 200 to 1200 nm.
  • the laser may be, for example, an infrared laser or an ultraviolet laser.
  • the laser light source used in packaging may be, for example, a semiconductor laser.
  • the device to be packaged can be, for example, an organic light emitting diode device.
  • the OLED device packaging method may be, for example, providing two glass substrates, screen printing the prepared packaging material (glass frit) onto the upper substrate, and performing pre-sintering to deposit the packaging material on the upper substrate. And then, the upper substrate is paired with another glass substrate on which the organic light emitting diode is formed, to form a sealed organic light emitting diode device (such as a transparent organic light emitting diode display device), and then a radiation source (such as an infrared laser or an ultraviolet laser) Heating the encapsulating material to melt and solidify to form a package structure and bond the two substrates together to form a complete sealing structure.
  • the sealing structure can protect the organic light emitting diode and the external film electrode from being damaged, and effectively prevent the entry of oxygen and moisture.
  • the encapsulating material according to the present disclosure can be used for packaging, especially packaging of organic light emitting diode devices.
  • FIG. 1 is a cross-sectional structural view of an organic light emitting diode device according to an embodiment of the present disclosure
  • an encapsulation material for a transparent device comprising:
  • a main component comprising: a rare earth metal oxide, zinc oxide, aluminum oxide, and silicon dioxide;
  • the main absorption wavelength of the rare earth metal oxide is in the range of infrared light or ultraviolet light.
  • the “main absorption wavelength” means that a substance is selective for absorption of light waves, for example, when absorbing white light or a broad-spectrum light source, the substance absorbs light for a certain wavelength range. Strong, therefore, the “primary absorption wavelength” here is the wavelength corresponding to the light that the substance absorbs the most light waves.
  • the rare earth metal oxide described above may be, for example, an oxide of a lanthanide rare earth metal.
  • the oxide of the lanthanide rare earth metal includes, for example, antimony trioxide (Yb 2 O 3 ), antimony trioxide (Ce 2 O 3 ), antimony trioxide (Eu 2 O 3 ), antimony trioxide (Tb). Any one or more of 2 O 3 ), antimony trioxide (Gd 2 O 3 ).
  • the main absorption wavelengths of the above five rare earth metal oxides are 975 nm, 210 to 251 nm, 375 to 394 nm, 284 to 477 nm, and 272 to 275 nm, respectively.
  • the package structure formed by the encapsulating material of the present embodiment is also colorless and transparent.
  • the encapsulating material of the present embodiment is used for transparent display, the display effect is not affected, and the product can be made beautiful.
  • the package structure formed by the above package material is colorless and transparent, the appearance is relatively good, and thus it can be used in a colorless transparent organic light emitting diode device.
  • the various components in the main component can be well matched to each other, thereby ensuring a low melting point of the encapsulating material, and having little influence on the organic light emitting diode during the packaging process, and the encapsulating material is The thermal expansion coefficient is matched with the glass substrate, the packaging material is evenly distributed during the packaging process, and the pores are not generated due to the displacement deformation of the packaging material during heating, which can achieve good sealing performance and effectively isolate moisture and oxygen from damage to the organic light emitting diode. And can make two substrates very Good bonding together.
  • the encapsulating material of the present embodiment is non-conductive and can protect the external thin film electrode.
  • the weight percent of each component of the main component of the encapsulating material is:
  • Rare earth metal oxide 40 to 80% by weight
  • Zinc oxide 1 to 20% by weight
  • Aluminum oxide 2 to 20% by weight
  • each component of the above main component is in the form of a powder.
  • the main component of the encapsulating material can be, for example, a "glass frit" composed of powders of the respective components, so that the preparation is convenient and the components can be uniformly mixed.
  • the powder of each of the above components may have a particle diameter of 0.1 ⁇ m to 10 ⁇ m, respectively.
  • the binder is configured to bond the powders of the components of the above main components together to form a solid product in the form of a bar.
  • the strip-shaped packaging materials can be used by being placed on the substrate, and the operation is simple and convenient.
  • the binder for example, nitrocellulose, ethylcellulose or the like can be used.
  • the amount of the binder is such that the powder of each component in the main component is bonded together, and there is no particular requirement, and generally 0.5 ml/g frit, that is, 0.5 ml of binder per gram of glass powder is used.
  • an organic light emitting diode device including:
  • the second substrate is disposed opposite to the first substrate
  • An organic light emitting diode disposed between the first substrate and the second substrate;
  • a package structure between the two substrates and configured to surround the organic light emitting diode
  • the package structure is formed by curing of the above-mentioned packaging material.
  • the organic light emitting diode device includes two substrates: an array substrate 1 and a package substrate 2.
  • the array substrate 1 is provided with an organic light emitting diode 11 .
  • a package structure 3 glass frit seal
  • surrounding the organic light emitting diode 11 is disposed between the two substrates 1 and 2, so that the organic light emitting diode 11 can be enclosed in a space composed of the two substrates and the package structure 3. 3 is formed by curing of the above encapsulating material.
  • the organic light emitting diode device may be an organic light emitting diode display device for display, or may be another device including an organic light emitting diode such as a light source.
  • the organic light emitting diode device is a transparent organic light emitting diode device, such as a transparent organic light emitting diode display device.
  • an organic light emitting diode device packaging method including:
  • the first substrate comprising at least one organic light emitting diode
  • the encapsulating material is cured to form a package structure.
  • curing the encapsulating material includes: melting and curing the encapsulating material.
  • the foregoing packaging material may be disposed on a predetermined area of any one of the two substrates (such as the package substrate 2), and then the two substrates (such as the package substrate 2 and the array substrate 1) are paired with the package, and then the packaging material is used. After melting (e.g., with a laser), it is post-cured to form a package structure, thereby bonding the two substrates together and enclosing the organic light emitting diode.
  • melting e.g., with a laser
  • the device to be packaged may also be an organic light emitting diode device, that is, a glass casing encapsulating the organic light emitting diode device may be formed by a packaging material.
  • melting the encapsulating material includes irradiating the encapsulating material with a laser to melt it.
  • the wavelength of the laser light is, for example, 200 to 1200 nm.
  • the laser may be an infrared laser or an ultraviolet laser.
  • the OLED device packaging method is, for example, preparing two glass substrates, wherein the array substrate 1 is provided with an organic light emitting diode 11; then the prepared packaging material is screen printed onto the package substrate 2, Performing pre-sintering to deposit the encapsulation material on the package substrate 2; encapsulating the package substrate 2 and the array substrate 1 to enclose the organic light emitting diode 11; then heating the encapsulation material with a radiation source (such as an infrared laser or an ultraviolet laser), After it is melted and solidified, the package structure 3 is formed and the two substrates are bonded together to form a complete sealing structure (for example, an organic light emitting diode display device).
  • the sealing structure can protect the thin film electrode externally connected to the organic light emitting diode It is not destroyed and effectively prevents the ingress of oxygen and moisture.
  • the wavelength of the laser for encapsulation may be in the above range. Since the main absorption wavelength of the rare earth metal oxide in the present embodiment is in the range of invisible light, the laser should also be an infrared laser or an ultraviolet laser. As an example, the laser wavelength may be 200 to 400 nm or 760 to 1200 nm. The specific laser wavelength may be determined according to the kind of the rare earth metal oxide.
  • the rare earth metal oxide includes bismuth trioxide (Yb 2 O 3 )
  • a laser having a wavelength of 760 to 1200 nm may be selected, and when the rare earth metal oxide includes three
  • cerium oxide (Ce 2 O 3 ), antimony trioxide (Eu 2 O 3 ), antimony trioxide (Tb 2 O 3 ), or antimony trioxide (Gd 2 O 3 ) the wavelength can be selected from 200 to ⁇ . 400nm laser.
  • encapsulating materials are prepared and used to form a package structure to verify the performance of the encapsulating material.
  • the following methods are used to prepare the encapsulating material and form the encapsulating structure.
  • the binder dissolved by the solvent is added to adjust the paste material.
  • the solvent was 2 g of amyl acetate
  • the binder was 5 g of ethyl cellulose (or nitrocellulose or the like).
  • S07 scanning the encapsulating material with a laser having a wavelength of 200 to 1200 nm, melting and solidifying to form a package structure.
  • the laser output power is 37.5W
  • the scanning speed is 2mm/s
  • the diameter of the laser beam should be smaller than the width of the strip-shaped packaging material, and a certain pressure can be applied to the two substrates during scanning.
  • the packaging material of the embodiment of the present disclosure has a small deformation amount at the time of packaging and a low thermal stress, the requirements for the laser and the laser operation mode are not very high, and a semiconductor laser can be used, and Laser scanning package, laser spot heating package, matrix laser package, etc. can be applied.
  • the laser scanning package is selected for practical convenience.
  • the thermal expansion coefficient of the sample was measured using a heat engine analyzer (XYW-500B).
  • the water oxygen transmission rate is determined by forming a metal electrode pattern on the back sheet to be detected, forming a calcium film on the back sheet on which the metal electrode pattern is formed, and forming a back sheet on which the metal electrode pattern and the calcium film are formed as a partition.
  • the plate blocks the drying chamber and the humid chamber, and the change in the conductivity of the calcium film is measured by the metal electrode pattern, and the water oxygen transmission rate of the back sheet is calculated based on the change value.
  • the main components of the encapsulating material used in the specific embodiments, and the performance of the corresponding package structure are as follows.
  • Antimony trioxide (rare earth metal oxide): 40% by weight;
  • Zinc oxide 20wt%
  • Aluminum oxide 20% by weight
  • the laser wavelength used for the package is 975 nm.
  • the performance of the package structure formed by the encapsulation material is:
  • Oxygen barrier capacity 0.8 ⁇ 10 -3 cm 3 / m 2 / day;
  • Antimony trioxide (rare earth metal oxide): 80% by weight;
  • Zinc oxide 1wt%
  • Aluminum oxide 14% by weight
  • the laser wavelength used for the package is: 244 nm.
  • the performance of the package structure formed by the encapsulation material is:
  • Oxygen barrier capacity 0.77 ⁇ 10 -3 cm 3 / m 2 / day;
  • Antimony trioxide and antimony trioxide (rare earth metal oxide): 75 wt%, wherein the mass ratio of antimony trioxide and antimony trioxide is 1:1;
  • Zinc oxide 13wt%
  • Aluminum oxide 2wt%
  • the laser wavelength used for the package was 364 nm.
  • the performance of the package structure formed by the encapsulation material is:
  • Oxygen barrier capacity 0.88 ⁇ 10 -3 cm 3 / m 2 / day;
  • Antimony trioxide (rare earth metal oxide): 60% by weight;
  • Zinc oxide 12wt%
  • Aluminum oxide 13% by weight
  • the laser used for the package has a wavelength of 257 nm.
  • the performance of the package structure formed by the encapsulation material is:
  • Oxygen barrier capacity 0.91 ⁇ 10 -3 cm 3 / m 2 / day;
  • the package structure formed by the package material according to the present disclosure is colorless and transparent, and is used for a transparent organic light emitting diode display device (or a transparent organic light emitting diode light source) without affecting the display effect, and the product can be made.
  • the encapsulation material of the present disclosure has a low coefficient of thermal expansion and is matched with the glass substrate, so that deformation and displacement do not occur during the laser heating process, so that no bubbles are formed in the package structure, and the two substrates can be well bonded together, and The package performance is also very good.

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Abstract

一种封装材料、有机发光二极管(11)器件及其封装方法,属于封装技术领域,其可解决相关技术中的封装材料形成的封装结构(3)为黑色,从而影响如透明显示器件美观的问题。一种用于透明器件的封装材料,其包括:主成分,主成分包括:稀土金属氧化物、氧化锌、三氧化二铝和二氧化硅;和粘结剂,粘结剂被配置为粘结主成分;其中,稀土金属氧化物的主要吸收波长处于红外光或紫外光的范围。该封装材料可用于封装,尤其是有机发光二极管器件的封装。

Description

封装材料、有机发光二极管器件及其封装方法
相关申请的交叉参考
本申请主张2015年7月27日在中国提交的中国专利申请号No.201510446094.X的优先权,其全部内容通过引用包含于此。
技术领域
本公开属于封装技术领域,具体涉及一种封装材料、有机发光二极管器件及其封装方法。
背景技术
有机发光二极管(OLED)显示作为一种新兴的显示技术,因其具有良好的色彩对比度、主动发光、宽视角、能薄型化、响应速度快和低能耗等优点,因而特别吸引人们的关注。然而,有机发光二极管,特别是其中的电极和有机层,容易因周围环境中的氧气和湿气进入有机发光二极管器件中而导致性能下降,严重影响其使用寿命。如果有机发光二极管内的电极和有机层与周围环境气密式隔绝开(封装),则其寿命将显著增加。
然而,以上隔绝的要求很难达到。现有技术中,主要采用封装结构将有机发光二极管封闭在两个基板之间,对其封装性能的要求如下:对氧的阻挡能力:10-3厘米3/米2/天,对水的阻挡能力:10-6克/米2/天。而且,封装结构的宽度应尽可能小(如1mm),以减少其对有机发光二极管器件的尺寸的影响。同时,在封装过程中所需的温度应该尽可能低,以减少对有机发光二极管的电极、有机层等的影响。在封装过程中,一般要求距封装结构1~2mm处的像素的温度不高于1000℃。另外,封装结构应当是绝缘的,以便电连接部件(如外接薄膜电极)能够穿过封装结构而进入有机发光二极管中。
目前主要应用的封装手段为激光封装,例如激光扫描封装、激光点加热封装、矩阵激光封装等。激光扫描封装是将一束激光投射到待封装的有机发光二极管器件表面的封装材料(玻璃料)上,然后激光束沿着封装材料轮廓扫描一周,使封装材料熔融从而完成封装。激光点加热封装是在封装材料的不 同位置进行激光点封装,最终达到封装要求。
但是,目前为了增加封装材料(玻璃料)对激光的吸收,通常需要向封装材料中加入氧化铋或者氧化钒等金属氧化物,而这些金属氧化物材料经激光熔融固化后是黑色的,当其应用于透明显示器件(当然也包括透明光源等其他器件)中时,会在外界可见,从而严重影响产品的美观。
发明内容
本公开鉴于上述情况,提供一种可形成透明封装结构并可用于透明器件的封装材料、有机发光二极管器件及其封装方法。
本公开的一个实施例提供一种用于透明器件的封装材料,其包括:主成分,所述主成分包括:稀土金属氧化物、氧化锌、三氧化二铝和二氧化硅;和粘结剂,所述粘结剂被配置为粘结所述主成分;其中,所述稀土金属氧化物的主要吸收波长处于红外光或紫外光的范围。
在一个示例中,所述稀土金属氧化物为镧系稀土金属的氧化物。
在一个示例中,所述镧系稀土金属的氧化物包括三氧化二镱、三氧化二铈、三氧化二铕、三氧化二铽、三氧化二钆中的任意一种或多种。
在一个示例中,所述主成分中各组分的重量百分含量为:稀土金属氧化物:40~80wt%;氧化锌:1~20wt%;三氧化二铝:2~20wt%;二氧化硅:5~20wt%。
在一个示例中,所述主成分的各组分为粉末状。
本公开的另一实施例提供一种有机发光二极管器件,其包括:
第一基板;
第二基板,所述第二基板与第一基板相对设置;
有机发光二极管,所述有机发光二极管在所述第一基板和第二基板之间;和
封装结构,在两基板间且被配置为围绕所述有机发光二极管;
其中,所述封装结构由上述的封装材料固化形成。
在一个示例中,所述有机发光二极管器件为透明有机发光二极管器件。
本公开的另一实施例还提供一种有机发光二极管器件封装方法,其包括 如下步骤:
提供第一基板,所述第一基板包括至少一个有机发光二极管;
提供第二基板,在所述第一基板或第二基板上形成上述的封装材料;
将第一基板与第二基板对盒,其中,所述封装材料被配置为围绕所述有机发光二极管;
将所述封装材料固化,形成封装结构。
在一个示例中,将所述封装材料固化包括:将所述封装材料熔融后固化。
在一个示例中,将所述封装材料熔融包括:用激光照射所述封装材料以使其熔融。
在一个示例中,所述激光的波长为200~1200nm。
在一个示例中,所述激光例如可以为红外激光或紫外激光。
本实施例中,在封装时所用的激光光源例如可以是半导体激光器。此外,待封装的器件例如可以为有机发光二极管器件。
具体地,所述有机发光二极管器件封装方法例如可以为:提供两块玻璃基板,将配制好的封装材料(玻璃料)丝网印刷到上基板上,进行预烧结以将封装材料沉积在上基板上,之后将上基板与另一块形成有有机发光二极管的玻璃基板对盒,用以形成密封的有机发光二极管器件(如透明有机发光二极管显示器件),然后用辐射源(如红外激光、紫外激光)加热封装材料,使其熔融、固化后形成封装结构并将两块基板粘接在一起,从而形成一个完整的密封结构。该密封结构能够保护有机发光二极管和外接薄膜电极不被破坏,并有效防止氧气和湿气的进入。
根据本公开的封装材料,其可用于进行封装,尤其是有机发光二极管器件的封装。
附图说明
图1为本公开的实施例的有机发光二极管器件的剖面结构示意图;
其中,1、阵列基板;11、有机发光二极管;2、封装基板;3、封装结构。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案,下面结合附图和具体实施方式对本发明作进一步详细描述。但应当理解,以下描述并不构成对本发明保护范围和作用原理的限定。
根据一个实施例,提供一种用于透明器件的封装材料,其包括:
主成分,所述主成分包括:稀土金属氧化物、氧化锌、三氧化二铝和二氧化硅;
和粘合剂,所述粘结剂被配置为粘结所述主成分;
其中,稀土金属氧化物的主要吸收波长处于红外光或紫外光的范围。
需要说明的是,“主要吸收波长”是指:一种物质对光波的吸收是有选择性的,例如在吸收白光或者是宽光谱的光源发光时,该物质对于某个波长范围的光吸收非常强烈,因此,这里的“主要吸收波长”即为该物质对光波吸收最多的那种光所对应的波长。
本实施例中,上述这样的稀土金属氧化物例如可以为镧系稀土金属的氧化物。所述镧系稀土金属的氧化物例如包括三氧化二镱(Yb2O3)、三氧化二铈(Ce2O3)、三氧化二铕(Eu2O3)、三氧化二铽(Tb2O3)、三氧化二钆(Gd2O3)中的任意一种或多种。上述五种稀土金属氧化物的主要吸收波长分别为975nm、210~251nm、375~394nm、284~477nm、272~275nm,由于以上的吸收波长基本处于红外光或紫外光的范围内,是不可见的,故由本实施例的封装材料形成的封装结构也是无色透明的。当将本实施例的封装材料用于透明显示时,不会影响显示效果,并可使产品美观。并且,由于由上述封装材料形成的封装结构是无色透明的,外观比较好看,故可以用于无色透明有机发光二极管器件中。
此外,本实施例的封装材料中,主成分中的各种组分可很好的相互配合,从而保证该封装材料的熔点低,封装过程中对有机发光二极管的影响小,且该封装材料的热膨胀系数与玻璃基板匹配,封装过程中封装材料分布均匀,不会由于封装材料在加热时发生位移形变而出现气孔,能达到很好的密封性能,有效隔绝水分和氧气对有机发光二极管的损伤,并可将两基板很 好的粘接在一起。而且,本实施例的封装材料不导电,可保护外接薄膜电极。
在一个示例中,封装材料的主成分中各组分的重量百分含量为:
稀土金属氧化物:40~80wt%;
氧化锌:1~20wt%;
三氧化二铝:2~20wt%;
二氧化硅:5~20wt%。
经研究发现,各组分处于以上的含量范围内对封装材料的性能最有利。
在一个示例中,以上主成分的各组分为粉末状。也就是说,封装材料的主成分例如可为各组分的粉末混合组成的“玻璃粉”,从而制备方便且各组分能够混合均匀。通常而言,以上各组分的粉末的粒径分别可为0.1μm~10μm。
在一个示例中,所述粘结剂被配置为将以上主成分中各组分的粉末粘结在一起,从而形成条块状的固体产品。这样,只要将这些条块状的封装材料摆放在基板上即可使用,操作简单,比较方便。
作为所述粘结剂,例如可以为硝基纤维素、乙基纤维素等。粘结剂的用量以可将主成分中各组分的粉末粘结在一起为准,无特别要求,一般在0.5ml/g frit,即每克玻璃粉使用0.5ml的粘结剂。
根据另一实施例,还提供一种有机发光二极管器件,其包括:
第一基板;
第二基板,所述第二基板与第一基板相对设置;
有机发光二极管,所述有机发光二极管被配置在所述第一基板和第二基板之间;和
封装结构,在两基板间且被配置为围绕所述有机发光二极管;
其中,所述封装结构由上述的封装材料固化形成。
在一个实施例中,如图1所示,有机发光二极管器件包括两个基板:阵列基板1和封装基板2。其中,阵列基板1上设有有机发光二极管11。两基板1、2间设有围绕有机发光二极管11的封装结构3(玻璃料封条),从而可将有机发光二极管11封闭在由两基板和封装结构3组成的空间中,该封装结构 3是由上述封装材料固化形成的。
有机发光二极管器件可以为用于进行显示的有机发光二极管显示器件,也可以为光源等其他含有有机发光二极管的器件。
在一个示例中,有机发光二极管器件为透明有机发光二极管器件,例如可以为透明的有机发光二极管显示器件。
根据另一实施例,还提供一种有机发光二极管器件封装方法,其包括:
提供第一基板,所述第一基板包括至少一个有机发光二极管;
提供第二基板,在所述第一基板或第二基板上形成上述的封装材料;
将第一基板与第二基板对盒,其中,所述封装材料被配置为围绕所述有机发光二极管;
将封装材料固化,形成封装结构。
在一个示例中,将所述封装材料固化包括:将封装材料熔融后固化。
具体的,可先将上述封装材料布置在两基板中的任一个基板上(如封装基板2)的预定区域,之后将两基板(如封装基板2和阵列基板1)对盒,再使封装材料熔融(如用激光)后固化,形成封装结构,从而将两基板粘接在一起,并将有机发光二极管封闭。
此外,待封装的器件也可以为有机发光二极管器件,即可通过封装材料形成封装有机发光二极管器件的玻璃外壳。
在一个示例中,将封装材料熔融包括:用激光照射所述封装材料以使其熔融。
在一个示例中,上述激光的波长例如为200~1200nm。具体的,上述激光可以为红外激光或紫外激光。
本实施例中,所述有机发光二极管器件封装方法例如为:准备两块玻璃基板,其中阵列基板1上设有有机发光二极管11;之后将配制好的封装材料丝网印刷到封装基板2上,进行预烧结以将封装材料沉积在封装基板2上;在将封装基板2与阵列基板1对盒,将有机发光二极管11封闭起来;然后用辐射源(如红外激光、紫外激光)加热封装材料,使其熔融、固化后形成封装结构3并将两基板粘接在一起,从而形成一个完整的密封结构(例如,有机发光二极管显示器件)。该密封结构能够保护有机发光二极管外接的薄膜电极 不被破坏,有效地防止氧气和湿气的进入。
也就是说,封装用激光的波长可以处于以上的范围内。由于本实施例中的稀土金属氧化物的主要吸收波长处于不可见光的范围,故此时激光也应为红外激光或紫外激光。作为一个示例,激光波长可以为200~400nm或760~1200nm。具体的激光波长可根据稀土金属氧化物的种类而定,当稀土金属氧化物包括三氧化二镱(Yb2O3)时,可选择波长760~1200nm的激光,而当稀土金属氧化物包括三氧化二铈(Ce2O3)、三氧化二铕(Eu2O3)、三氧化二铽(Tb2O3)、三氧化二钆(Gd2O3)时,则可选择波长200~400nm的激光。
实施例:
下而列举的各具体实施例中制备不同的封装材料,并用其形成封装结构,进而验证封装材料的性能。
此外,在各具体实施例中,均采用以下的方法制备封装材料和形成封装结构。
S01、按照各实施例的比例,将封装材料的主成分的各组分的粉末共10g加入玛瑙研钵中,加入2ml的酒精,充分研磨混合10分钟。
S02、待酒精完全挥发后加入被溶剂溶解的粘结剂,调出糊状材料。其中,溶剂为2g的乙酸戊酯,粘结剂为5g的乙基纤维素(或硝基纤维素等)。
S03、真空放置10分钟,使糊状材料内的气体完全排除。
S04、用丝网印刷方式将糊状材料印刷在玻璃基板上,形成带状的封装材料。
S05、在150~200℃的温度预烧结60分钟,之后在350℃保温20分钟,完全除去粘结剂,在基板上形成固化的条状封装材料。
S06、将封装材料的上表面打磨平,将该基板与另一基板对盒在一起。
S07、用波长200~1200nm的激光沿封装材料扫描一次,使其熔融后固化,形成封装结构。其中,激光输出功率为37.5W,扫描速度为2mm/s,且激光束的直径应比条状封装材料的宽度小,在扫描时还可对两基板施加一定的压力。
其中,由于本公开实施例的封装材料在封装时的形变量小,热应力低,故其对激光器和激光运行方式的要求不是很高,可使用半导体激光器,并且 激光扫描封装、激光点加热封装、矩阵激光封装等方式均可适用。此处,由于实用简便而选择使用激光扫描封装。
S08、对所得的封装结构进行性能测试。其中:
(1)热膨胀系数
使用热机分析仪(XYW-500B)对试样的热膨胀系数进行测定。
(2)水氧透过率
水氧透过率通过如下方法测定:在待检测的背板上形成金属电极图形,在形成有金属电极图形的背板上形成钙膜,将形成有金属电极图形和钙膜的背板作为隔板阻隔干燥室和潮湿室,通过所述金属电极图形测量钙膜的电导率的变化值,根据该变化值算出背板的水氧透过率。
具体的,各具体实施例中所用的封装材料的主成分,以及相应的封装结构的性能如下。
实施例1:
本实施例的封装材料主成分的组成为:
三氧化二镱(稀土金属氧化物):40wt%;
氧化锌:20wt%;
三氧化二铝:20wt%;
二氧化硅:20wt%。
封装所用的激光波长为:975nm。
由该封装材料形成的封装结构的性能为:
颜色:无色透明;
热膨胀系数:-85×10-7/℃;
氧阻挡能力:0.8×10-3厘米3/米2/天;
水阻挡能力:0.75×10-6克/米2/天。
实施例2:
本实施例的封装材料主成分的组成为:
三氧化二铈(稀土金属氧化物):80wt%;
氧化锌:1wt%;
三氧化二铝:14wt%;
二氧化硅:5wt%。
封装所用的激光波长为:244nm。
由该封装材料形成的封装结构的性能为:
颜色:无色透明;
热膨胀系数:-75×10-7/℃;
氧阻挡能力:0.77×10-3厘米3/米2/天;
水阻挡能力:0.7×10-6克/米2/天。
实施例3:
本实施例的封装材料主成分的组成为:
三氧化二铕和三氧化二铽(稀土金属氧化物):75wt%,其中三氧化二铕和三氧化二铽的质量比为1∶1;
氧化锌:13wt%;
三氧化二铝:2wt%;
二氧化硅:10wt%。
封装所用的激光波长为:364nm。
由该封装材料形成的封装结构的性能为:
颜色:无色透明;
热膨胀系数:-91×10-7/℃;
氧阻挡能力:0.88×10-3厘米3/米2/天;
水阻挡能力:0.9×10-6克/米2/天。
实施例4:
本实施例的封装材料主成分的组成为:
三氧化二钆(稀土金属氧化物):60wt%;
氧化锌:12wt%;
三氧化二铝:13wt%;
二氧化硅:15wt%。
封装所用的激光波长为:257nm。
由该封装材料形成的封装结构的性能为:
颜色:无色透明;
热膨胀系数:-101×10-7/℃;
氧阻挡能力:0.91×10-3厘米3/米2/天;
水阻挡能力:0.88×10-6克/米2/天。
由以上具体实施例可以看出,根据本公开的封装材料形成的封装结构为无色透明,用于透明有机发光二极管显示器件(或透明有机发光二极管光源)时不会影响显示效果,可使产品美观。同时,本公开的封装材料的热膨胀系数低,与玻璃基板匹配,故在激光加热过程中不会出现变形和位移,从而封装结构中无气泡,可将两基板很好的粘接在一起,并且封装性能也很好。
可以理解的是,以上所述仅仅是为了说明本发明的原理而采用的示例性实施方式,然而本发明并不局限于此。对于本领域内的普通技术人员而言,在不脱离本发明的精神和实质的情况下,可以做出各种变型和改进,这些变型和改进也应视为本发明的保护范围。

Claims (16)

  1. 一种用于透明器件的封装材料,包括:
    主成分,所述主成分包括:稀土金属氧化物、氧化锌、三氧化二铝和二氧化硅;和
    粘结剂,所述粘结剂被配置为粘结所述主成分;
    其中,所述稀土金属氧化物的主要吸收波长处于红外光或紫外光的范围。
  2. 根据权利要求1所述的封装材料,其中,所述稀土金属氧化物为镧系稀土金属的氧化物。
  3. 根据权利要求2所述的封装材料,其中,所述镧系稀土金属的氧化物包括三氧化二镱、三氧化二铈、三氧化二铕、三氧化二铽、三氧化二钆中的任意一种或多种。
  4. 根据权利要求1~3中任意一项所述的封装材料,其中,所述主成分中各组分的重量百分含量为:
    稀土金属氧化物:40~80wt%;
    氧化锌:1~20wt%;
    三氧化二铝:2~20wt%;
    二氧化硅:5~20wt%。
  5. 根据权利要求1~4中任意一项所述的封装材料,其中,所述主成分的各组分为粉末状。
  6. 一种有机发光二极管器件,包括:
    第一基板;
    第二基板,所述第二基板与第一基板相对设置;
    有机发光二极管,所述有机发光二极管在所述第一基板和第二基板之间;和
    封装结构,在两基板间且被配置为围绕所述有机发光二极管;其中,
    所述封装结构由封装材料固化形成;
    所述封装材料包括:
    主成分,所述主成分包括:稀土金属氧化物、氧化锌、三氧化二铝和二氧化硅;和
    粘结剂,所述粘结剂被配置为粘结所述主成分;
    其中,所述稀土金属氧化物的主要吸收波长处于红外光或紫外光的范围。
  7. 根据权利要求6所述的有机发光二极管器件,其中,所述稀土金属氧化物为镧系稀土金属的氧化物。
  8. 根据权利要求7所述的有机发光二极管器件,其中,所述镧系稀土金属的氧化物包括三氧化二镱、三氧化二铈、三氧化二铕、三氧化二铽、三氧化二钆中的任意一种或多种。
  9. 根据权利要求6~8中任意一项所述的有机发光二极管器件,其中,所述主成分中各组分的重量百分含量为:
    稀土金属氧化物:40~80wt%;
    氧化锌:1~20wt%;
    三氧化二铝:2~20wt%;
    二氧化硅:5~20wt%。
  10. 根据权利要求6所述的有机发光二极管器件,其中,所述有机发光二极管器件为透明有机发光二极管器件。
  11. 一种有机发光二极管器件封装方法,包括:
    提供第一基板,所述第一基板包括至少一个有机发光二极管;
    提供第二基板,在所述第一基板或第二基板上形成权利要求1~5中任意一项所述的封装材料;
    将第一基板与第二基板对盒,其中,所述封装材料被配置为围绕所述有机发光二极管;
    将所述封装材料固化,形成封装结构。
  12. 根据权利要求11所述的有机发光二极管器件封装方法,将所述封装材料固化包括:将所述封装材料熔融后固化。
  13. 根据权利要求12所述的有机发光二极管器件封装方法,其中,将所述封装材料熔融包括:用激光照射所述封装材料以使其熔融。
  14. 根据权利要求13所述的有机发光二极管器件封装方法,其中,所述激光的波长为200~1200nm。
  15. 根据权利要求14所述的有机发光二极管器件封装方法,其中,所述激光为红外激光。
  16. 根据权利要求14所述的有机发光二极管器件封装方法,其中,所述激光为紫外激光。
PCT/CN2016/091581 2015-07-27 2016-07-25 封装材料、有机发光二极管器件及其封装方法 WO2017016461A1 (zh)

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