CN104628252A - Rare earth doped lead-free frit and electrical component sealing method utilizing the same - Google Patents
Rare earth doped lead-free frit and electrical component sealing method utilizing the same Download PDFInfo
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- CN104628252A CN104628252A CN201310556965.4A CN201310556965A CN104628252A CN 104628252 A CN104628252 A CN 104628252A CN 201310556965 A CN201310556965 A CN 201310556965A CN 104628252 A CN104628252 A CN 104628252A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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Abstract
The invention describes a lead-free frit based on a rare earth oxide doped Bi2O3-SiO2-ZnO glass system and a sealing method utilizing the frit paste composition. The frit and the sealing method have excellent sealing effect on water vapor and gas, and are easy for electrical component processing at low temperature. At the same time, the invention provides a method for hermetic glass sealing of electrical components. The method provides a first glass substrate and a second glass substrate and fixes the frit onto the first glass substrate, and then utilizes a radiation source (laser or infrared ray) to heat the frit and make it fuse, and a hermetic type sealing dam can be formed between the first glass substrate and the second glass substrate.
Description
Technical field
The present invention relates to a kind of lead-less glasses material, and use the glass capsulation method of this frit paste composition gas-tight seal electrical element.Described electrical element, includes OLED (OLED), dye sensitization solar battery (DSSC), lighting (LED).The present invention adopts OLED display to set forth as an example.
Background technology
Organic electroluminescent LED (Organic light emitting diode, OLED) display of organic electroluminescence is also called, its structure belongs to sandwich type structure, usually being made up of anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and negative electrode etc., is a kind of total solids indicating meter utilizing current drives.Under the driving of impressed current, electronics and hole carrier are injected into leads organic luminous layer, then in luminescent layer, is compounded to form exciton, is sent out and luminous by exciton radiation de excitation.Due to OLED there is frivolous, power saving, wide viewing angle, image quality is even, speed of response is fast, can realize the features such as Flexible Displays, be acknowledged as " dreamlike indicating meter ".
But OLED is a kind of device to steam and oxygen extreme sensitivity, as long as OLED does not encapsulate, just easily cause stain at light-emitting zone, and stain can expand along with the time.On the one hand, penetrate into the steam of device and oxygen can with the low workfunction metal material of device cathodes, there is oxidizing reaction in such as Al, Mg, Ca etc., causes forming insulation layer at negative electrode and organic functions interlayer, causes device cannot be luminous.Meanwhile, during OLED work, the existence of steam can bring out the electrolysis venting that electrochemical reaction and water occur between anode and negative electrode, forms blackspot.On the other hand, also can there is irreversible chemical reaction with steam, oxygen in organic materials, destroys the stability of organic molecule, reduces device light emitting efficiency.Therefore, in order to protect OLED from steam and oxygen deterioration of device performance, above-mentioned OLED display being carried out gas-tight seal and will seem very important.
The prevailing method of above-mentioned OLED display being carried out to gas-tight seal is exactly by after UV treatment, uses epoxide, inorganic substance or the/organic substance that can form sealing.Such as, Vitex system company develops a kind of Barix encapsulation technology, adopts the alternating layer of inorganic materials and organic materials to seal OLED display.Although this sealing method can provide and good physical strength, their equipment costs are very expensive, and in a lot of occasion, these sealings fail anti-sealing Oxygen permeation in OLED display.
Another common method being used for sealing OLED display adopts metal solder or soft soldering exactly.But, owing to there is substantial difference between glass substrate and the CTE of metal in above-mentioned OLED display, so the OLED display adopting metal solder is non-resistant in wide temperature range.
Based on the hermetic sealing technology of frit, especially leaded frit, for the device of encapsulation provides excellent resistance to air loss.But these frits comprise toxic element mostly, as antimony (Sb) and plumbous (Pb), all environmental hazard can be caused.Therefore, developing the frit of a kind of Environment-friendlylow-temperature low-temperature welding, is very urgent.
Above-mentioned disclosed in background information be only used to strengthen understanding to background technology of the present invention, therefore, it may comprise the information not being formed in this domestic prior art well known by persons skilled in the art.
Summary of the invention
Main purpose of the present invention is to provide a kind of lead-less glasses material and the frit paste composition containing this frit, to solve the problem.
In the periodic table of elements, because lead and bismuth are two adjacent elements, they all belong to the P district in the 6th cycle, have very similar character.And containing the two glass in viscosity, transition temperature Tg, the aspects such as the coefficient of expansion must be similar.In addition, antimony and bismuth are again congenerss, and chemical property is comparatively close.So current bismuth glass material is the excellent substitute of lead glass material.With rare earth oxide, such as CeO2, La2O3, Er2O3, Y2O3, Pr6O11, Y2O3, the Bi2O3 of Lu2O3 or Nb2O5 Substitute For Partial, the mobility of glass system can be increased, increase the chemical stability of frit system, simultaneously, make the thermal expansivity scope of glass broader, expand the use range of frit.
To achieve these goals, the invention provides a kind of lead-less glasses material, it is characterized in that, it contains:
Bi2O3 (30-40 % by mole),
SiO2 (10-35 % by mole),
ZnO (5-35 % by mole),
CuO (5-15 % by mole),
Al2O3 (5-15 % by mole),
MnO2 (1-15 % by mole),
Fe2O3 (1-5 % by mole),
BaO (1-5 % by mole),
TiO2 (1-5 % by mole),
WO3 (1-5 % by mole),
RnOm (0.1-5 % by mole), and
Wherein Bi2O3+SiO2 is in the scope of 40 % by mole to 56 % by mole, and RnOm is rare-earth oxide, freely comprises CeO2, and La2O3, Er2O3, Y2O3, Pr6O11, Y2O3, Lu2O3, Nb2O5 are formed at the material of the group of interior a kind of or their compositions.
Second object of the present invention is just to provide a kind of frit paste composition, and it is characterized in that, it contains:
A) frit described in any one of the claims 1-5;
B) polymeric adhesive; With
C) organic solvent.
The feature of above-mentioned frit paste composition is, its viscosity is 500-100000cps, preferred 2000-80000cps.
3rd object of the present invention is just to provide a kind of gas-tight seal glass process using this frit paste composition, it is characterized in that, described frit is fixed on the predetermined position of the first glass substrate by screen printing process, utilize source of radiation (as laser or infrared rays) to carry out heated frit, make it be welded to by the first glass substrate on the second described glass substrate and also form gas-tight seal dam betwixt.
Frit of the present invention is excellent with the sealing effectiveness utilizing the sealing method of the OLED display element of this frit to steam and oxygen, and easily processes in low temperature process.
See accompanying drawing; the present invention can be easier to understand by following illustrative description; more clearly understand other objects of the present invention simultaneously, method, feature and advantage are all included within this description, comprise within the scope of the present invention, and be subject to the protection of appended claims.
Accompanying drawing explanation
Be described in detail exemplary embodiment in conjunction with the drawings, feature will become obvious to those skilled in the art, in accompanying drawing:
Fig. 1 illustrates the OLED element seal process schematic diagram utilizing frit paste composition of the present invention;
Fig. 2 illustrates the material loading and sintering process that utilize frit paste composition of the present invention;
Fig. 3 illustrates the process schematic utilizing frit paste composition LASER HEATING OLED element of the present invention;
Wherein, 100 shown in Fig. 3 is the upper surface of the first glass substrate;
Wherein, 200 shown in Fig. 3 is Environment-friendlylow-temperature low-temperature glass for bonding feed composition disclosed in the present invention;
Wherein, 300 shown in Fig. 3 is the upper surface of the second glass substrate.
Embodiment
The following detailed description of the present invention.
A kind of lead-less glasses material of the present invention, it is characterized in that, it contains:
Bi2O3 (30-40 % by mole),
SiO2 (10-35 % by mole),
ZnO (5-35 % by mole),
CuO (5-15 % by mole),
A12O3 (5-15 % by mole),
MnO2 (1-15 % by mole),
Fe2O3 (1-5 % by mole),
BaO (1-5 % by mole),
TiO2 (1-5 % by mole),
WO3 (1-5 % by mole),
RnOm (0.1-5 % by mole), and
Wherein Bi2O3+SiO2 is in the scope of 40 % by mole to 56 % by mole, and RnOm is rare-earth oxide, freely comprises CeO2, and La2O3, Er2O3, Y2O3, Pr6O11, Y2O3, Lu2O3, Nb2O5 are formed at the material of the group of interior a kind of or their compositions.。
When the content forming the composition of frit of the present invention is outside above-mentioned scope, sometimes can not form vitreum, water tolerance is obviously deteriorated sometimes, is also sometimes unfavorable for the absorption of frit to source of radiation.
Do not use lead glass material, first the basic components system of binary (Bi2O3-SiO2) is adopted to form the Network former of frit, then from all the other components to the water tolerance of gas-tight seal frit, sintering mobility, glass transition temp Tg, frit degree of absorption and thermal expansivity confirm that other material forms.Such as, when in above-mentioned frit, the content of ZnO component is less than 5 % by mole, frit paste composition often has more high softening temperature Tdsp.This is mainly because the ZnO component of high-content has part to provide the ability of free oxygen in frit Network former system, the fracture of the old key of glass network and the restructuring of new key is made to become relatively easy, thus there is the benefit of fluxing, the mobility of frit is also better, can Some substitute PbO, thus realize environmental protection object.Contrary, if when the ZnO component in above-mentioned glass frit compositions is higher than 35 % by mole, ZnO high-content causes the network contiguity in whole glass network former greatly to reduce, the weaken of frit, is unfavorable for obtaining the good frit of welding strength.Meanwhile, with rare earth oxide, such as CeO2, La2O3, Er2O3, the Bi2O3 of Y2O3, Pr6O11, Y2O3, Lu2O3 or Nb2O5 Substitute For Partial, the mobility of glass system can be increased, increase the chemical stability of frit system, meanwhile, make the thermal expansivity scope of glass broader.
Extinction component in frit freely comprises CuO, the transition metal oxides such as Fe2O3, V2O5, TiO2, the material of one or two or more kinds composition in the group that rare-earth oxide (lanthanide metal oxide) forms.
In the present invention, absorbancy can be expressed as:
β＝-log
10[T／(1-R)
2]／t
Wherein, β refers to specific absorbance, and T is exactly the ratio of the light of t after being transmitted through, and R is then the reflectivity of frit.Generally speaking, the specific absorbance adding the frit of transition metal or rare-earth oxide should be able to be greater than 2/mm.And include Fe2O3, the frit of V2O5 and TiO2 has the specific absorbance of more than 33/mm.
The lead-less glasses material that the present invention discloses, includes:
CuO (5-20 % by mole),
Al2O3 (5-15 % by mole),
MnO2 (1-15 % by mole),
Fe2O3 (1-5 % by mole),
BaO (0.1-5 % by mole),
TiO2 (0.1-5 % by mole), and
WO3 (0.1-5 % by mole).These components are very good to the receptivity of the Infrared at 810nm place.
Meanwhile, when the content of the Al2O3 in above-mentioned frit is less than 5 % by mole, the water resistance of glass frit compositions will reduce, and affects the effect of gas-tight seal.When the component of the Al203 in above-mentioned frit is greater than 15 % by mole, will reduce the content of Network former in frit, vitreum will become unstable.
In addition, when the content of the B component aO in above-mentioned frit is less than 0.1 % by mole, there is the problem that softening point temperature increases in described glass frit compositions, because the barium ion of divalence, be free on outside glass network former, have very strong polarizability, the Network former link level in frit is died down, softening temperature reduces.Contrary, when the content of the B component aO in above-mentioned frit is higher than 5 moles, is unfavorable for the stable of frit, sometimes devitrification occurs.
Preferably above-mentioned frit compositions, the glass transition temp Tdsp of a kind of Environment-friendlylow-temperature low-temperature glass for bonding material that the present invention discloses is 300 DEG C-400 DEG C, and glass transition temp Tg is 300-400 DEG C, is conducive to the low temperature seal technique of electrical element.
Except the number of component in glass frit compositions, outside having a great impact the gas-tight seal of OLED, in composition, the size of particle is also very important.The particle of the frit of the present invention containing such composition is preferably had to the size of 0.1um-20mn.When the particle diameter of frit components is less than 20um, because it has very little particle diameter, frit has very high specific surface area, and the surface energy of its system is very high, and therefore whole frit system has and reduces surface-area, reduce the demand of energy in frit system, just obtain enough outside abilities at reduced temperatures, the particle in glass powder will overcome migration activation energy, draws close mutually and forms new network body, thus comparatively speaking, the sintering process in frit is conducive to.Generally speaking, the size of frit particles, in above-mentioned scope, is applicable to low-temperature sintering, is applicable to the gas-tight seal of heat labile element, and can be used in follow-up radiation source heats, improves the fine ratio of product of OLED display.
Generally speaking, the invention provides the frit paste composition containing above-mentioned frit, described frit paste composition is characterised in that, it contains:
A) frit described in any one of the claims 1-5;
B) polymeric adhesive; With
C) organic solvent.
Specifically, a kind of frit paste composition that the present invention discloses, it is characterized in that, said composition contains:
A) the above-mentioned glass frit compositions of 60-90 weight part;
B) polymeric adhesive of 0.1-5 weight part; With
C) organic solvent of 5-35 weight part.
The feature of above-mentioned frit paste composition is, its viscosity is 500cps-100000cps, preferred 2000cps-100000cps.The viscosity of frit paste composition has impact to a certain extent for the yield of its gas-tight seal on the first glass substrate and the second glass substrate.When the viscosity of frit paste composition is lower than 500cps, frit paste composition, in silk screen printing process, extremely easily penetrates half tone and cannot reach the ideal thickness of frit.When the viscosity of frit paste composition is higher than 100000cps, caking agent just directly adheres on half tone, and returning in black technique in printing, sometimes can cause the plug-hole phenomenon of silk-screen half tone.Meanwhile, when the viscosity of frit paste composition is higher than 100000cps, the surface topography of frit on the first glass substrate also can be uneven, and the drop of high lower is very big, has a great impact the yield of follow-up gas-tight seal.
Polymeric adhesive of the present invention can be AC acrylic resin, EC ethyl cellulose prime system, or zinc-containing solid catalyst (Polyalkylene Carbonate).Organic solvent of the present invention can be acetate of butyl carbitol (BCA), terpinol (TPN), dibutyl phthalate (DBP), or 2,2,4-trimethylammonium-1.3 pentanediol mono isobutyrate (texanol alcohol ester), or triglyme (triglyme) or their composition group in one or two kinds.Caking agent/the organic solvent used in the present invention can be EC ethyl cellulose/BCA acetate of butyl carbitol, AC acrylic resin/2,2,4-trimethylammonium-1.3 pentanediol mono isobutyrate (texanol alcohol ester), or zinc-containing solid catalyst (Polyalkylene Carbonate)/triglyme.
In addition, frit paste composition of the present invention can use the filler of the thermal expansivity CTE regulating composition material further.First glass substrate and glass frit compositions, and the second glass substrate mates with the CTE between glass frit compositions, thus durable hermetically sealing dam is provided and prevents from breaking.Generally speaking, the CTE being used in the glass substrate of OLED display is roughly 30-90 × 10
-7/ DEG C, and the frit paste composition described in the present invention can well meet the matching degree between different glass substrate and frit.Use the first glass substrate in the present invention and the second glass substrate should be same glass material, the coupling of CTE can better be met.Better, frit paste composition of the present invention can use beta-eucryptite, β-triphane, Li2O-Al2O3-SiO4 material, pyrophosphate salt, and one or more materials in the group of cyanines green stone or their compositions are as filler.
As the concrete example of the gas-tight seal of OLED element of the present invention, composition graphs 1, will describe encapsulation process in detail below.
First, prepare the first glass substrate (S100), above-mentioned frit paste composition is fixed to preposition, normally used some glue coating method in industry can be adopted, or concrete silk-screen printing technology (S200) of setting forth in the present invention.The upper surface of the first glass substrate is positioned over the lower surface of silk-screen half tone, above-mentioned frit paste composition is coated with at the upper surface of silk-screen half tone, regulate corresponding volume under pressure, the spacing of half tone and the first glass substrate, and the parameter such as the angle of returning blade, by pressure and time black technique, frit paste composition is pressed into the upper surface to the first glass substrate, then, the first glass substrate being coated with frit paste composition is carried out drying and sintering process, so just glass frit compositions can be fixed on the predetermined position of the upper surface of the first glass substrate.Though specifically do not provide processing parameter, capable those skilled in the art should understand above-mentioned technique and know-why deeply.
Then, after the upper surface of the second glass substrate is carried out evaporation OLED material (S300 and S400), contraposition is carried out with the upper surface of the first glass substrate, laminating, by applying a source of radiation (such as laser) at the lower surface of the first glass substrate, the first glass substrate and the second glass substrate are directly formed a hermetically sealing dam (S400 and S500), described source of radiation can be laser apparatus, infrared lamp.It is understood that the illumination wavelength of source of radiation should be within the high-selenium corn bands of a spectrum of glass frit compositions of the present invention.Such as, ytterbium (900nm< λ <1200nm) can be used, Nd:YAG (λ=1064nm), Nd:YALO (λ=1.08um), or Ti: sapphire laser (λ=810nm), depend on concrete frit, the first glass substrate, and the optical characteristics of the second glass substrate.
In addition, the invention provides the electrical element of above-mentioned sealing method gas-tight seal, as the concrete example of above-mentioned electrical element, it can be the Organic Light Emitting Diode (OLED) enumerated, also can be dye sensitization solar battery (DSSC), even lighting (LED), sensor or other optics.Frit paste composition described in the application of the invention, be conducive to the machining at low temperature technique of electrical element, you enough can drop to the disadvantageous effect of element and minimize, and have increased substantially the resistivity of electric elements for steam and oxygen, have promoted its work-ing life.
In order to better understand benefit of the present invention, enumerate preferred embodiment below, following embodiment is only that example of the present invention is described, know that scope of the present invention is not restricted in following embodiment.
Embodiment 1. [manufacture of glass frit compositions]
Manufacture the frit of embodiment 1-4 with the material of following table 1 composition, the unit in table 1 is % by mole.
Table 1 (% by mole)
Frit blends in above-mentioned table 1 is carried out heating makes composition melt, as High Temperature Furnaces Heating Apparatus (1650 DEG C) mixing, then will melts to be discouraged or liquid nitrogen carries out quenching fracture, post-rift fragment, three-roller (three-mill) is adopted repeatedly to grind and batch mixing, required frit particle diameter 0.1-20um can be obtained, meet the size of 325 orders or 400 order half tones.The frit of embodiment 1-4 is characterised in that, softening temperature Tdsp is 300-400 DEG C, is suitable for the machining at low temperature operation of frit.
Embodiment 2 [manufacture of frit paste composition]
The frit blends of above-described embodiment 1-4 is utilized to manufacture frit paste composition.Frit blends in above-described embodiment 1-4 is claimed 70 weight parts respectively with the EC ethyl cellulose/BCA acetate of butyl carbitol of 30 weight parts, AC acrylic resin/2,2,4-trimethylammonium-1.3 pentanediol mono isobutyrate (texanol alcohol ester), or zinc-containing solid catalyst (Polyalkylene Carbonate)/triglyme manufactures 4 kinds of following frit paste compositions (numbering 1-4).Regulate the Different Weight ratio of polymeric adhesive and solvent, the different viscosity of frit paste composition can be obtained, with the operation of applicable silk screen printing process.
Further, frit paste composition is inverted in further the batch mixing that three-roller carries out once or several times, more preferably silk-screen effect can be reached.
Table 2.
Measure the frit paste composition of material number 1 in above-described embodiment 2 as follows, it the results are shown in following table 3.
1. glass transition temp Tg
Utilize DTA device (DTG-60H Shimatz), heat up with the speed of 10 DEG C/min, measure the glass transition temp of glass frit compositions.
2. softening temperature Tdsp
Utilize DTA device (DTG-60H Shimatz), heat up with the speed of 10 DEG C/min, measure the glass transition temperature of glass frit compositions.
3. thermal expansivity CTE
Utilize TMA device (TMA-Q400TA instrument), with the temperature rise rate of 5 DEG C/min, mensuration material is warmed up to the thermal expansivity 300 DEG C of processes from room temperature RT.
4. water tolerance
Above-mentioned glass frit compositions is sealed between the first glass substrate and the second glass substrate, form hermetically sealing dam, then this containment member is immersed in 24H in the pure water of 80 DEG C, measure the weight of this containment member, the gradient of weight is designated as "○" when being less than 0.5%, is denoted as "×" when the gradient of weight is more than 0.5%.
Table 3.
| Test subject | Tg(℃) | Tdsp(℃) | CTE(10 -7／℃) | Water tolerance |
| Numbering 1 | 330+10 | 360±10 | 75+1 | ○ |
In addition, the CTE improving frit paste composition in the present invention further can add corresponding filler in the mixture, to mate the CTE coefficient between the first glass substrate and the second glass substrate.
Embodiment 3 [hermetically sealing of OLED element]
The present invention discloses the predetermined position described frit being fixed on the first glass substrate by screen printing process or some glue coating process, utilize source of radiation to carry out heated frit, make it be welded to by the first glass substrate on the second described glass substrate and also form gas-tight seal dam betwixt.
Below by detailed method for hermetically sealing of setting forth OLED element with half tone silk screen printing process and laser radiation heating technique.It is to be understood that the frit paste composition of setting forth in the embodiment of the present invention and air hermetic packing technique, be not limited to half tone silk-screen or laser radiation heating.
Hermetically sealing technique, shown in Fig. 1 and Fig. 2, specific as follows:
A) preparation of frit paste composition
By above-mentioned frit paste composition uniform stirring batch mixing (S210) prepared, to reach desirable silk-screen condition.Generally speaking, first frit paste composition is carried out being stirred well to few more than 1H before silk-screen, scraper can be adopted to stir, or be positioned over the upper rotation number hour of roller machine (roller).
B) silk screen printing process
By frit paste composition good for abundant batch mixing, be applied in the upper surface of the half tone of silk-screen board, the order number of the half tone of described silk-screen board can be 325 orders, can be also 400 orders, depends on the particle diameter of particle in frit paste composition and silk-screen effect and determines.Regulate the corresponding scraper of silk-screen board or the angle of inclination of returning blade, the height of silk-screen half tone and the first glass substrate upper surface, and the pressure and other parameters pressing down half tone of returning blade or scraper, silk-screen is in the predetermined position (S220) of the first glass substrate upper surface, frit surface is now comparatively smooth, and edge is not crude.
C) sintering process of frit paste composition
Frit paste composition on above-mentioned first glass substrate predetermined position is carried out sintering process (S230).
First, at a lower temperature by complete for the organic solvent drying in frit paste composition.Generally speaking, frit paste composition, lower than 200 DEG C, therefore, can be carried out drying by these organic easy vaporization temperatures fast in low temperature environment.
Then, frit paste composition complete for drying is carried out carbonization treatment technique.Generally speaking, the polymeric adhesive (Binder) in carbonization treatment processing requirement frit paste composition as far as possible all within 300 DEG C smooth oxygenolysis become CO2, H2O, or other gases.Specifically, frit paste composition described in the present invention to the selection of polymeric adhesive based on the glass transition temp of frit blends higher than the complete decomposition temperature of polymeric adhesive, and the viscosity of polymeric adhesive will meet silk screen printing process requirement.
Finally, the frit paste composition after carbonization treatment is carried out sintering processes.Generally speaking, the grain fraction that in the frit paste composition that carbonization treatment is later, structure is comparatively loose, at 600 DEG C, preferably can complete sintering, shape on the predetermined position of the first glass substrate within 500 DEG C.Meanwhile, sintering temperature lower than near the glass transition temp of frit paste composition time, need slowly to heat up, to keep glass frit compositions, there is good surface topography.
D) air hermetic glass capsulation
The first glass substrate after sintering and the second glass substrate carry out air hermetic glass capsulation.
First, TFT (thin film transistor will be prepared, thin film transistor) upper surface of the second glass substrate of technique, carry out vacuum thermal evaporation art breading, form OLED unit, the upper surface of the second described glass substrate is defined as the one side (S300) of carrying out TFT technique.Described evaporation process forms OLED unit, namely on the upper surface of the second glass substrate, conventional hole input horizon HIL/ hole transmission layer HTL/ organic luminous layer EML/ electron transfer layer ETL/ electron injecting layer EIL/ negative electrode (S400) is completed, but, OLED unit described in the present invention is not limited to said structure, and theory is can by electroluminescent device architecture.Then, the upper surface of the upper surface of the second described glass substrate and the first described glass substrate is carried out exactitude position, contraposition and laminating (S500) are carried out in the predetermined position of the frit blends on the first glass substrate upper surface and the second glass substrate upper surface.Then, Ti: sapphire laser (λ=810nm) is passed into its upper surface by the lower surface 100 of the first glass substrate, frit blends 200 on its upper surface being heated, sealing forming hermetically sealing dam between the upper surface 100 and the upper surface 300 of the second glass substrate of the first glass substrate (S600).
Think the illustrative embodiments that can put into practice at present although combined the present invention is described in detail, but be understood that, the invention is not restricted to the embodiment announced, on the contrary, the present invention is intended to cover the various amendment and equivalents that comprise within the scope of the appended claims.
Claims (10)
1. a lead-free frit, is characterized in that, it contains
Bi2O3 (30-40 % by mole),
SiO2 (10-35 % by mole),
ZnO (5-35 % by mole),
CuO (5-15 % by mole),
Al2O3 (5-15 % by mole),
MnO2 (1-15 % by mole),
Fe2O3 (1-5 % by mole),
BaO (1-5 % by mole),
TiO2 (1-5 % by mole),
WO3 (1-5 % by mole),
RnOm (0.1-5 % by mole), and
Wherein Bi2O3+SiO2 is in the scope of 40 % by mole to 56 % by mole, and RnOm is rare-earth oxide.
2. the lead-free frit of one according to claim 1, it is characterized in that, it contains:
Bi2O3 (30-35 % by mole),
SiO2 (15-30 % by mole),
ZnO (5-25 % by mole),
CuO (5-20 % by mole),
Al2O3 (5-15 % by mole),
MnO2 (1-15 % by mole),
Fe2O3 (1-3 % by mole),
BaO (1-5 % by mole),
TiO2 (1-5 % by mole),
WO3 (1-5 % by mole),
RnOm (0.1-5 % by mole), and
Wherein Bi2O3+SiO2 is in the scope of 40 % by mole to 56 % by mole, and RnOm freely comprises CeO2, and La2O3, Er2O3, Y2O3, Pr6O11, Y2O3, Lu2O3, Nb2O5 are formed at the material of the group of interior a kind of or their compositions.
3. one according to claim 1 not flint glass material, is characterized in that, the softening temperature (Tdsp) of described frit is 300-400 DEG C, and glass transition temp Tg is 300-400 DEG C.
4. one according to claim 1 not flint glass material, is characterized in that, the thermal expansivity CTE of described frit is in 50-80 × 10
-7/ DEG C scope in.
5. one according to claim 4 not flint glass material, is characterized in that, described frit also comprises the filler reducing CTE further, described filler freely comprises beta-eucryptite, β-triphane, Li-Al-SiO4 material, pyrophosphate salt, cyanines green stone is at interior a kind of material composition.
6. a frit paste composition, is characterized in that, it comprises:
A) frit described in any one of the claims 1-5;
B) polymeric adhesive; With
C) organic solvent.
7. a kind of frit paste composition according to claim 6, it is characterized in that, said composition contains:
A) frit described in any one of the claims 1-5 of 60-90 weight parts;
B) polymeric adhesive of 0.1-5 weight part; With
C) organic solvent of 5-35 weight parts.
8. a kind of frit paste composition according to claim 6, is characterized in that, the viscosity of described paste composition is 500-100000cps.
9. a sealing method for electrical element, it comprises:
First glass substrate;
Second glass substrate; With
The frit described in any one of 1-8 of described claim, the predetermined position of the first glass substrate is fixed on by coating process, utilize source of radiation (as laser or infrared rays) to carry out heated frit, make it be welded to by the first glass substrate on the second described glass substrate and also form gas-tight seal dam betwixt.
10. electrical element sealing method according to claim 9, is characterized in that, described electrical element includes OLED (OLED) element, dye sensitization solar battery (DSSC) or lighting (LED).
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