CN109071325A - Sealing device comprising transparent laser welding region - Google Patents

Abstract

Disclosed herein is sealing devices comprising first base material, the second substrate, the inoranic membrane between first base material and the second substrate and include the combination between first base material and the second substrate at least one welding region.Welding region may include the Chemical composition that different from inoranic membrane and first or second substrate.Sealing device can also include the stress area at least surrounding welding region, and in the stress area, stress locating for a part of device is greater than stress locating for the device of remainder.There is disclosed herein displays and electronic component comprising the sealing device.

Description

Sealing device comprising transparent laser welding region

Cross reference to related applications

This application claims the benefit of priority of following patent application: the entitled " Sealed that on March 10th, 2016 submits Devices Comprising Transparent Laser Weld Regions " [" includes the close of transparent laser welding region Seal apparatus "] No. 15/066704 U.S. Patent application；Entitled " the Laser Welding that on May 7th, 2014 submits Transparent Glass Sheets Using Low Melting Glass Or Thin Absorbing Films " [" makes Laser welding is carried out to transparent glass sheet with low-melting glass or thin absorbing film "] the 14/271st, No. 797 U.S. Patent application, The U.S. Patent application requires the benefit of priority of following U.S. Provisional Application: the entitled " Laser that on May 10th, 2013 submits Welding Transparent Glass Sheet Using Low Melting Glass Film " [" uses low-melting glass Film to transparent glass sheet carry out laser welding "] No. 61/822,048 U.S. Provisional Application；What on October 4th, 2013 submitted Entitled " Laser Welding Transparent Glass Sheets Using Ultraviolet Absorbing Film " No. 61/886,928 U.S. Provisional Application of [" laser welding is carried out to transparent glass sheet using UVR absorbing film "]；With 2013 Entitled " the Laser Sealing Using Low Melting Temperature Glass for that on May 31, in submits The 61/829,379th of Hermetic Devices " [" package sealing with laser is carried out to air-tightness device using low melting temperature glass "] It based on content herein above for stating every application, and is included in this by number U.S. Provisional Application in full by reference Text.

Technical field

Electronic component and display unit the present disclosure relates generally to sealing device and comprising the sealing device, more specifically For, it is related to the seal glass device comprising Vitreous solder region.

Background technique

Many modem devices require sealed environment to be operated, and many is to need " active " dress of electrical bias It sets.Display, such as translucency and the Organic Light Emitting Diode of optical biasing (OLED) are needed, due to using electron injection material to need Absolutely gas-tight is wanted, therefore is the application of high request.In addition to this, these materials can generally decompose in an atmosphere in several seconds, Therefore corresponding device should keep vacuum or inert atmosphere for a long time.In addition, the temperature due to organic material to be encapsulated is sensitive Property it is high, therefore airtight sealing should carry out at a temperature of near-ambient.

Sealant based on frit includes the glass material for being for example ground to partial size usually in about 2 to 150 micron ranges Material.For frit-sealed application, usually frit material is mixed with negative CTE material similar in partial size, and uses Obtained mixture is blended into thickener by organic solvent or adhesive.Illustrative negative CTE inorganic filler includes cordierite Grain (such as Mg₂Al₃[AlSi₅O₁₈]), barium silicate, beta-eucryptite, vanadic acid zirconium (ZrV₂O₇) or tungsten wire array (ZrW₂O₈), they are added It is added in frit and forms thickener to reduce the thermal expansion coefficient mispairing between substrate and frit.Solvent merges for adjusting Powder and organic bond thickener rheology viscosity, and these solvents need to be suitable for controlled distribution purpose.In order to make two Substrate combines, and glass frit layers can be applied on the sealing surfaces of one or two substrate by spin coating or silk-screen printing.Through The substrate for crossing frit coating is initially subjected to organic burn-out steps (for example, carrying out 30 at 250 DEG C at relatively low temperature Minute), to remove organic carrier.Then, along corresponding sealing surfaces, two substrates to be combined assemble/match, And this is put into chip bonder substrate.Hot compression circulation is executed under the temperature and pressure clearly limited, is thus melted Frit is to form compact glass seal.It removes outside certain leaded compositions, the glass transition temperature of frit material Typically larger than 450 DEG C, it is therefore desirable to processed at high temperature to form barrier layer.Such temperature sensitive type of elevated-temperature seal technique It may be unfavorable for workpiece.In addition, being used to reduce the thermal expansion coefficient mispairing between common substrate and frit Negative CTE inorganic filler, these negative CTE inorganic fillers will be incorporated into conjunction in connector, and lead to the barrier layer based on frit It is substantially opaque.Based on above-mentioned, it is expected that it is close to form transparent and airtight glass-glass sealing element, glass-metal at low temperature Sealing, glass-ceramic seal and other sealing elements.

Although super high power laser aid can be used in conventional glass baseplate laser welding, this in nearly laser ablation Under operation usually damage and glass baseplate and obtain second-rate gastight seal.Furthermore this conventional method makes to obtain The opacity of device increase, and additionally provide low-quality sealing element.

In some cases, sealing element may not be optically transparent, for instance it can be possible that coloring.For being carried out to light Transmitting, conversion, is extracted, in the situation of the sealed package of diffusion and/or scattering at transmission, these defects are particularly disadvantageous.For example, Opaque sealing element can stop light transmission, and optically opaque sealing element may be such that light sends out when light passes through sealing area Raw undesirable distortion.For these reasons, sealant usually is applied around substrate periphery, such as be applied in around object to be sealed It in the frame of body, or is only applied in edge, even if unsealing object in packaging part.Nevertheless, in some constructions, side Material at edge can still make light that undesirable distortion occur or reduce light transmission.

It is therefore advantageous that providing the method for carrying out package sealing with laser to substrate, this method among other advantages, is gone back The transparency, intensity and/or air-tightness of sealing element can be increased, reduce manufacturing cost and/or complexity, and/or improve Productivity and/or yield.It also will be advantageous that, the sealing device for display and other electronic devices be provided, light can be made Transmittance is improved and/or reduces distortion.Obtained sealing device itself can be used as in display or other electronic devices Component, or can be used for protecting various electronic devices and other component, such as light emitting structure or color conversion device, such as swash Optical diode (LD), LED, OLED and/or QD.

Summary of the invention

Embodiment of the present disclosure relates generally to hermetic barrier, seals more particularly, to absorbing membrane is used The method and composition of solid structure.Embodiment of the present disclosure, which provides, uses film as interfacial initiation agent, to sheet glass The method for carrying out laser welding or sealing with other materials piece, the film have absorption characteristic in seal process.According to one A little embodiments, illustrative Laser Welding Condition may be adapted on conductive interface film be welded, and under electric conductivity Drop is negligible.Therefore, the embodiment can be used to form the air-tightness of active device (such as OLED or other devices) Packaging part, and suitable glass or semiconductor package part can be manufactured extensively, in large quantity.It should be noted that term sealing, In conjunction with, engagement and welding be used interchangeably and be used interchangeably in the disclosure.This usage should not limit this paper institute The range of attached claims.It should also be noted that in the disclosure, when term glass and inorganic it is related to carrying out noun film When modification, they are used interchangeably, and this usage should not limit the scope of the claims by the appended claims herein.

Embodiment of the present disclosure provides a kind of package sealing with laser method, such as laser welding, diffusion welding etc., the side Method can provide absorbing film in the interface between two glass.In stable state, absorption can be greater than or up to about 70%, or Person can be less than or down to about 10%.It is less than or is depended under laser wavelength of incidence down to 10% absorption, in glass baseplate In colour center form and combine illustrative laser absorption film, and the colour center is formed as external colour center and (such as impurity or mixes Miscellaneous dose) or the intrinsic inherent colour center of glass caused by.Some non-limiting examples of film include Tg < 600 DEG C SnO2, ZnO, TiO2, ITO, UV heat absorbing glass film and low-melting glass (LMG) or low liquidus temperature (LLT) film (no glass transition temperature The material of degree), they can be used for the interface of glass baseplate.For example, LLT material can include but is not limited to ceramics, glass pottery Porcelain and glass material.For example, LLT glass may include tin fluorphosphate glass, tin fluorphosphate glass, the chalcogen compound for mixing tungsten Glass, tellurite glasses, borate glass and phosphate glass.In another non-limiting embodiment, sealing material It can be for containing Sn²⁺Inorganic oxide material, for example, SnO, SnO+P₂O₅And SnO+BPO₄.Other non-limiting examples can wrap Include near-infrared (NIR) the heat absorbing glass film of absorption peak at > 800nm wavelength.It can provide visible light using the welding of these materials Transmission, and there is enough UV or NIR to absorb to cause mild stable state Diffusion Welding.These materials can also be provided with office Portion's seal temperature, and the temperature is adapted for the transparent laser weldment of Diffusion Welding.This Diffusion Welding makes corresponding glass Glass substrate carries out low-power and low temperature laser welding, and excellent transparent weldering can be generated with effective and quick speed of welding Fitting.The Exemplary laser welding procedure according to embodiment of the present disclosure may also rely on the glass after colour center is formed Photoinduction hydrophilicity characteristic, to include temperature-induced absorption.

This document describes use inorganic (LMG) material of low melting point or UV absorption (UVA) or infrared absorption (IRA) material Interfacial film, the phenomenon that being welded together each transparent glass sheet to cause sealing using laser.In the exemplary embodiment, Describe three standards for realizing and combining formed by force: (1) illustrative LMG or UVA or IRA film can transparency window (such as It is fully absorbed under incident wavelength other than about 420nm to about 750nm), by enough heat propagations into glass baseplate, and glass Therefore glass substrate can show (2) temperature-induced absorption and (3) and form transient state colour center under incident wavelength.Measurement shows to be formed Hot compression Diffusion Welding mechanism, qualitatively results in extremely strong combination.There is also described herein relevant to welding procedure The obvious generality of colour center forming process in the differentiation and laser welding of temperature event.Also discuss LMG or UVA material with Eagle Deposited strength after CTE mispairing irrelevance and thermal cycle to 600 DEG C between material enhances situation.Also It discusses about the embodiment for being welded together the different each sheet glass of thickness by using heat-conducting plate.Therefore, this paper institute The embodiment stated can have the ability to form the air-tight packaging part with passive and active device, may include and use The relevant package sealing with laser attribute of LMG or UVA boundary material.Illustrative attribute includes but is not limited in the visible spectrum saturating CTE mispairing irrelevance between bright, strong, thin, high transmittance, " green " composition, LMG or UVA film and glass baseplate, and Low melting temperature.

It is close that the other embodiment of the disclosure provides the laser with low temperature bond formation and " direct glass capsulation " Encapsulation method, wherein transparent glass can be sealed to absorption glass (absorbing glass) under incident wavelength, to be formed Opaque sealing element at visible wavelength 400-700nm.In the exemplary embodiment, two blocks of glass are in laser wavelength of incidence It down and is transparent or almost transparent in visible wavelength region.Obtained sealing element is in visible wavelength region Be it is transparent, to illumination application for be attracting because not absorbing light at sealing station, will not generate with it is close Seal relevant hot stack.In addition, there is no need to accurately distribute sealing glass due to that can be applied to film above entire cover-plate glass Glass thickener come be sealed operation, thus provide very big freedom degree for device manufacturing quotient change they seal pattern and It does not need to carry out sealing area special patterning or processing.It in other embodiments, can also be in the certain of glassy zone It is sealed on point to form the non-airtight combination for mechanical stability.In addition, can be carried out on curved conformal surfaces The sealing.

Embodiment of the present disclosure provides low melting temperature material, can be used for sheet glass laser welding one It rises, this is related to welding CTE differential of the arbitrary glass without considering glass.Other embodiment can provide pair of glass baseplate Claim welding (that is, welding of heavy sheet glass and heavy sheet glass), such as welding, the welding of Lotus and Lotus of Eagle and Eagle etc.. Heat-conducting plate can be used to provide the asymmetric welding (that is, welding of thin glass and heavy sheet glass) of glass baseplate in some embodiments, Such as Willow and EagleWelding, Eagle and Lotus welding (that is, welding of thin glass and thin glass), The welding of Eagle and fusion silica, the welding of Willow and Willow, fusion silica and the weldering for fusing silica It connects.Other embodiments can provide the welding (glass and ceramics, glass and metal etc.) of different substrate materials, and can provide transparent And/or translucent sealing wire.Some embodiments can weld thin, impermeable, " green " material, and can be CTE differential big two kinds provide strong welding between substrate or material.

Embodiment further provides the material for glass-encapsulated part to be laser welded, so as to to oxygen and The sensitive passive and active device of degradation caused by moisture invasion carries out permanent air tight work.Illustrative LMG or other suctions Receiving diaphragm seal can use laser absorption by thermal activation after by the assembling of each mating surface, and can have higher system Make efficiency because sealing the rate of each equipment by thermal activation and combining to be formed and determine, rather than by by vacuum or Online (inline) film deposition in inert gas assembly line determines the rate that device is packaged.It is close in UV or NIR-IR Illustrative LMG, LLT and other absorbing membranes in sealing can also be sealed large stretch of multiple device, then delineation or It is cut into each device (individualized), and due to mechanical integrity height, individualized yield can be higher.

It in some embodiments, include forming inoranic membrane in the top on first base material surface in conjunction with the method for workpiece；It will Workpiece to be protected is arranged between first base material and the second substrate, wherein contacts the film with the second substrate；And it is logical It crosses and local heating is carried out to film and workpiece is incorporated in first base material and the second substrate using the laser emission with predetermined wavelength Between.Inoranic membrane, first base material or the second substrate can have transmittance at about 420nm to about 750nm.

In other embodiments, a kind of coupling apparatus is provided comprising in the nothing that first base material surface is formed Machine film, and the shielded device between first base material and the second substrate, wherein inoranic membrane is contacted with the second substrate.? In such embodiment, described device include and with the laser emission with predetermined wavelength come local heating inoranic membrane The combination formed between first base material and the second substrate changes according to the impurity composition variation in first or second substrate, And is changed according to the composition of inoranic membrane and changed.In addition, inoranic membrane, first base material or the second substrate are in about 420nm to about There can be transmittance under 750nm.

In other embodiment, the method that a kind of pair of device is protected is provided, the method includes first The first part surface of substrate forms inorganic film；By device to be protected be arranged in first base material and the second substrate it Between, wherein contacting sealant with the second substrate；And use laser emission local heating inorganic film and first and second base Material is so that sealant and substrate melt and form sealing between each substrate.First base material may include glass or glass ceramics, and Second substrate may include glass, metal, glass ceramics or ceramics.

In each embodiment, present disclosure also relates to sealing devices comprising be formed in first base material surface Inoranic membrane；The second substrate contacted with inoranic membrane；And welding region, the welding region are included in first base material and the second substrate Between the combination that is formed, and the welding region extended to from the first depth in first base material it is second deep in the second substrate Degree.According to other embodiment, inoranic membrane includes at least one inoranic membrane element, and in first base material and the second substrate One or two include at least one inorganic substrate element.In other embodiment, first in welding region or First inoranic membrane concentration of element of two substrates is higher than the second inoranic membrane concentration of element of the first or second substrate outside welding region. According to other embodiment, the first base material concentration of element in welding region is higher than second of the inoranic membrane outside welding region Substrate concentration of element.In other embodiment, the second inoranic membrane can be formed above the second substrate surface.

In some embodiments, inoranic membrane and optionally at least one of first or second substrate about 420nm extremely There is transmittance under wavelength within the scope of about 750nm.In other embodiment, first base material, the second substrate and inoranic membrane In each can have transmittance under the wavelength within the scope of about 420nm to about 750nm.In other embodiments, Welding region can be transparent.One of first base material or the second substrate or both can be selected from glass or glass ceramics, Such as soda lime glass, sillico aluminate glass, alkali metal aluminosilicate glass, borosilicate glass, alkali metal borosilicic acid Salt glass, aluminium borosilicate glass, composite alkali aluminum borosilicate glass and alkaline-earth metal aluminium borosilicate glass.According to certain realities Mode is applied, first base material or the second substrate may include polymer, ceramics or metal.

Inoranic membrane can have the composition comprising following substance: 20-100 moles of %SnO；0-50 moles of %SnF₂；With 0-30 moles of %P₂O₅Or B₂O₃.Inoranic membrane can also have the composition comprising following substance: 10-80 moles of %B₂O₃；5-60 Mole %Bi₂O₃；With 0-70 moles of %ZnO.According to each embodiment, the thickness of inoranic membrane can be micro- at about 0.1 micron to about 10 In the range of rice.In other embodiment, the thickness of welding region can be in about 0.3 micron to about 14 microns of range It is interior.

In some embodiments, sealing device may also include the stress area at least surrounding welding region, wherein stress The first stress in region is greater than the second stress outside stress area.For example, the first stress can be in greater than about 1MPa to about 25MPa In the range of.In other embodiment, the first stress is relative to the ratio of the second stress in about 1.1:1 to the model of about 25:1 In enclosing.According to certain embodiments, the thickness of stress area can be in the range of about 20 microns to about 500 microns.

There is disclosed herein sealing devices comprising in the inoranic membrane that first base material surface is formed；It is connect with inoranic membrane Second substrate of touching；And welding region, the welding region include the combination formed between first base material and the second substrate. According to other embodiment, one or both of first base material and the second substrate include at least one inorganic substrate element. In other embodiment, welding region compared to welding region outside a part of inoranic membrane rich in at least one it is inorganic Substrate element.There is disclosed herein sealing devices comprising in the inoranic membrane that first base material surface is formed；It is connect with inoranic membrane Second substrate of touching；And welding region, the welding region include the combination formed between first base material and the second substrate. According to other embodiment, inoranic membrane includes at least one inoranic membrane element.In other embodiment, the first or second Substrate includes the first part in welding region and the second part outside welding region.According to other embodiment, phase Than in second part, first part is rich at least one inoranic membrane element.It in other embodiment, can be second The second inoranic membrane is formed above substrate surface.

The other feature and advantage of claimed theme are proposed in the following detailed description, part therein is special Advantage of seeking peace is readily appreciated that according to being described to those skilled in the art, or by implementing to include in detail below Claimed theme as described herein including embodiment, claims and attached drawing and be realized.

It should be understood that foregoing general description and specific embodiment below all describe the implementation of the disclosure Mode and be intended to offer for understanding the property of theme claimed and the overview or frame of characteristic.Included For further understanding the disclosure, attached drawing is incorporated in the present specification and constitutes part of specification attached drawing.Attached drawing instantiates Each embodiment, and together with specification it is used to explain the principle and operation of theme claimed.

Detailed description of the invention

These attached drawings are provided for purposes of illustration, it should be appreciated that the embodiment for being disclosed herein and discussing is not Arrangement and mechanism shown in being limited to.

Fig. 1 is an exemplary process diagram of the laser welding described in accordance with one embodiment of the present disclosure.

Fig. 2 is to instantiate the schematic diagram that airtight sealing device is formed by the package sealing with laser of an embodiment.

Fig. 3 is the figure of the another embodiment of this theme.

Fig. 4 is the experimental arrangement schematic diagram for estimating the physical extent of laser welding combined area.

Fig. 5 is the micro-image of fracture specimens.

Fig. 6 is the modeling scheme schematic diagram according to some embodiments of the disclosure.

Fig. 7 is another modeling scheme according to embodiment of the present disclosure.

Fig. 8 is surveyed for %T relative to the time by the 355nm laser transmissivity (%T) of Eagle 0.7mm glass baseplate The experimental arrangement figure of amount.

Fig. 9 is the figure described in accordance with one embodiment of the present disclosure.

Figure 10 is analyzed at glass interface, enters Eagle from LMG film layerDiffusion in glass baseplate A series of figures.

Figure 11 is the schematic diagram of the laser weldability between the sheet glass of different-thickness.

Figure 12 is the experiment schematic diagram of laser welding range of the estimation above ITO lead (leads).

Figure 13 provides the photo of the package sealing with laser line formed above ITO pattern film.

Figure 14 is the photo of the other package sealing with laser line formed above patterned film.

Figure 15 is the simplification figure of another method according to some embodiments.

Figure 16 is two layers of laser heating surface absorbing model of some embodiments.

Figure 17 is the series of temperature variation diagram of some embodiments.

Figure 18 is for some embodiments, a series of average energies for depositing within the residence time for scanning laser Figure.

Figure 19 is with the Eagle during IR radiation source heats, at 355nmAnd LotusGlass is saturating Penetrating property figure.

Figure 20 is glass transmittance figure of some embodiments during heating at 355nm.

Figure 21 is some embodiments during and after UV radiation, to the radioparent influence diagram of film and substrate.

Figure 22 is figure of the absorption relative to wavelength of some embodiments.

Figure 23 is in EagleThe package sealing with laser of exemplary low-melting glass film on glass combines exograph X.

Figure 24 is in EagleThe intersecting laser of exemplary low-melting glass film on glass seals exograph X.

Figure 25 is the interfacial contact geometric ranges schematic diagram that some embodiments are observed in laser welding.

Figure 26 is the constant pressure P in application_OutsideUnder, it is opposite to contact during carrying out laser welding to interfacial gap region Region A_c/A₀Differentiation schematic diagram.

Figure 27 instantiates the wheel using common Laser Welding Condition above the laser sweeping area of an embodiment Wide instrument trace.

There is provided a series of figures of the bonding speed comparable situation for the estimation of some embodiments by Figure 28.

Figure 29 is the polarimetry of some embodiments and the schematic diagram of image.

Figure 30 is to provide the figure of stress position according to exemplary weld line.

Figure 31 is according to some embodiments by a series of photos of the soda-lime glass of laser welding.

Figure 32 is the schematic diagram of some embodiments.

Figure 33-34 is the photo of the sealing wire in some embodiments.

Figure 35 A is the side view of the product comprising two substrates and inoranic membrane.

Figure 35 B is the top view for being subjected to a kind of a kind of product of example seal technique.

Figure 35 C is the sectional view of the sealing device according to each embodiment of the disclosure.

Figure 36 A-36B is the SEM image for being respectively seal interface before and after package sealing with laser.

Figure 37 instantiates the product and exemplary area by welding for elemental analysis.

Figure 38 A-38C instantiate in the welding region and non-solder region of sealing article element depth distribution (F, P, Sn each figure).

Figure 39 A-39C instantiate in the welding region and non-solder region of sealing article element depth distribution (Al, B, Si each figure).

Figure 40 instantiates each embodiment according to the disclosure, and the stress distribution of sealing device becomes with change in depth The each figure changed.

Although this specification may include many specific conditions, these do not constitute the limitation of the scope of the present disclosure, but retouch State feature specific for specific embodiment.

Specific embodiment

Each embodiment of encapsulating method and sealing device is described with reference to the drawings, wherein in order to make it easy to understand, identical Element is provided with identical appended drawing reference.

It should also be understood that unless otherwise stated, otherwise, term such as " top ", " bottom ", " outside ", " inside " etc. be for Term for the sake of convenience, is not construed as restricted term.In addition, being described as whenever by a group comprising one group of element and they At least one of combination when, described group can be in the form of individual element or intercombination comprising any amount of listed by these Element is perhaps mainly made of these any amount of column elements or is made of these any amount of column elements.

Similarly, whenever by a group be described as by one group of element at least one element or their combination form When, described group can be made of in the form of individual element or intercombination these any amount of column elements.Unless otherwise saying Bright, otherwise, cited numberical range includes the upper and lower bound of the range simultaneously.Unless otherwise stated, otherwise, this paper institute "one" and "an" of indefinite article and its corresponding definite article " should/described " expression " an at least (pcs/species) ", or " (pcs/species) or more (pcs/species) ".

It will be appreciated by those of skill in the art that many changes can be made to the embodiment, while remaining to obtain Obtain beneficial effects of the present invention.Also it should be apparent that a part of can pass through in the expectation benefit of the disclosure selects one A little features using other features without being obtained.Therefore, those skilled in the art will appreciate that many change and modify all Be it is possible, it is even desired in some cases, and be a part of this disclosure.Therefore it provides conduct is described below To the explanation of disclosure principle without constituting the limitation to the disclosure.

It will be understood by those skilled in the art that without departing from the spirit and scope of the present invention, it can be to described herein Illustrative embodiments carry out many modifications.Therefore, description of the invention is not intended to be limited to given example, also not It is interpreted as being limited to given example, and whole protections by the appended claims and its equivalents offer should be endowed Range.Furthermore, it is possible to using some characteristics of the disclosure without accordingly with other characteristics.Therefore, provided above to example The principle for being intended to indicate that the disclosure of the description of property or illustrated embodiment rather than it is limited, and can wrap Include its modification and variation.

Fig. 1 is an exemplary process diagram of the laser welding according to some embodiments of the disclosure.With reference to figure 1, this figure provides use suitable UV laser by two panels Eagle(EXG) sheet glass or substrate are laser welded Process.Although illustrating and describing two panels EXG sheet glass, the claims by the appended claims herein should not necessarily be limited by this, because Embodiment of the present disclosure to can be used to carry out laser welding to the glass baseplate of any type and composition.That is, herein The method can be suitable for soda-lime glass, strengthen and non-strengthened glass, sillico aluminate glass etc..

Figure 35 A similarly describes the side view of stack 100 comprising the first base material 110 with first surface 115 With the second substrate 120 with second surface 125.It can be arranged between the first glass baseplate 110 and the second substrate 120 inorganic Film 130, to form seal interface 135.Herein, seal interface 135 refers to the first surface 115 and of first base material 110 The point contacted with inoranic membrane 130 between the second surface 125 of two substrates 120, for example, each to be combined by welding or sealing The place that meets on surface.

It in some embodiments, can be in whole, substantially all or a part of first surface 115 and/or the second table Inoranic membrane 130 is formed above face 125.It, can on first surface 115 or second surface 125 although being not shown in Figure 35 A Device, layer or other elements are provided, and it can be contacted (such as abut or covered by inoranic membrane 130) with inoranic membrane 130, or In other embodiments, inoranic membrane 130 can be arranged in device, layer or component ambient (such as around device periphery Frame or other construction settings).In other embodiment, one or both of first and second substrates 110,120 can Comprising it is one or more wherein can apparatus for placing or element cavity (not shown).

It continues to refer to figure 1, this figure provides a series of illustrative steps for being laser welded two glass baseplates, Thus one or two coated substrate can be made to have low-melting glass (LMG) or UV absorption (UVA) membrane material or NIR to absorb (IRA) membrane material.In step A into B, top glass substrate can be pressed into coated with the another of exemplary UVA, IRA or LMG film On one substrate.It should be noted that it is as described herein it is many experiment and example may relate to certain types of inoranic membrane (such as LMG, UVA etc.).But this should not limit the scope of the claims by the appended claims herein, because the inoranic membrane of many types is suitable For the welding procedure.In step C, the interface of two sheets, and suitably selection ginseng can be directed a laser to Number is to cause the welding procedure as illustrated in step D.It was found that weld size is slightly less than the size (about 500 μm) of incident beam.

Fig. 2 is to instantiate the schematic diagram that airtight sealing device is formed by the package sealing with laser of an embodiment.With reference to Fig. 2 can be formed (i.e. low comprising low melting temperature in the initial step along the sealing surfaces of the first flat glass substrates 302 Tg) the patterned glass layer 380 of glass.Glassy layer 380 can be deposited via physical vapor deposition, such as by coming from sputtering target 180 sputtering is deposited.In one embodiment, which can form along periphery sealing surfaces, periphery sealing Surface is adjusted and engages with the sealing surfaces of the second glass or other materials substrate 304.In embodiment illustrated, when When making the first and second substrates using matching construction, they and glassy layer cooperate to limit containing workpiece 330 to be protected Internal volume 342.In the illustrated example of decomposition image for showing component, the second substrate includes that workpiece 330 is located therein Depressed section.

It, can be in first base material and/or the as the substitution for forming patterned glass layer in an alternative embodiment The substantially all of surface of two substrates forms the coating (blanket layer) of sealing (low melting temperature) glass. It can assemble as described above comprising first base material/sealing glass layer/second substrate package assembly, and laser part can be used Limit the seal interface between two substrates.

In a non-limiting embodiment, inoranic membrane can be deposited on the surface of first base material and the surface of the second substrate On, and the contact of these films can be made to form seal interface.Think on two surfaces in seal interface comprising inoranic membrane It can make that there is stronger combination between first base material and the second substrate.By the inclusion of two films, (such as first and second is inorganic Film), the heating of interface substrate can be started simultaneously on both surfaces, rather than (such as inoranic membrane is deposited thereon in side Substrate) on begin to warm up and spread to second side (such as the substrate contacted with inoranic membrane) again.Furthermore it is possible to need less energy Come induce substrate and film viscoplasticity expand or swelling, this can enable in welding region have less residual stress.It can Bond strength is improved with the reduction by this residual stress, otherwise may cause cohesional failure.In such embodiment In, the thickness of the first inoranic membrane can be identical or different with the thickness of the second inoranic membrane.In other embodiment, the first He The thickness for the single inoranic membrane that the merging overall thickness of second inoranic membrane approximate can limit herein, such as in about 100nm to about 10 In the range of micron.

Focusing laser beam 501 from laser 500 can be used for local melting low melting temperature glass and adjacent glass Substrate material is to form seal interface.In one approach, laser can be focused and then in sealing surfaces by first base material 302 Upper translation (scanning) is with local heating glass sealing material.In order to influence the local melting of glassy layer, which preferably exists Laser machine absorbing at wavelengths.Glass baseplate can be in the case where laser machining wavelength initial transparent (for example, at least transparent 50%, 70%, 80% or 90%).

Laser 500 can have any suitable output for influencing to seal.Illustrative laser can be UV laser, example Such as, but not limited to, 355nm laser is in the transparent range of common display glass.Suitable laser power can be in about 1W To about 10W.The width of sealing area can be proportional to laser spot size, can be about 0.06 to 2mm, example Such as 0.06,0.1,0.2,0.5,1,1.5 or 2mm.The rate of translation (i.e. sealing rate) of laser can be at about 1mm/ seconds extremely In 400mm/ seconds or even about 1mm/ seconds to 1m/ seconds or bigger ranges, for example, 1,2,5,10,20,50,100,200 or 400mm/ seconds, 600mm/ seconds, 800mm/ seconds, 1m/ seconds.Laser spot size (diameter) can be about 0.02 to 2mm.

With reference to Figure 35 B, stack 100 can be sealed, such as using being directed to and focus on seal interface, close The laser 500 below interface or above seal interface is sealed, the beam spot diameter, D on interface is allowed to be less than about 2mm.For example, beam Spot diameter can be less than about 1mm, for example, less than about 500 microns, be less than about 400 microns, be less than about 300 microns or be less than about 200 Micron, be less than about 100 microns, less than 50 microns or less than 20 microns, including therebetween all ranges and subrange.Some In embodiment, beam spot diameter, D can be in the range of about 20 microns to about 500 microns, and for example, about 50 microns to about 250 micro- Rice, about 75 microns to about 200 microns or about 100 microns to about 150 microns, including therebetween all ranges and subrange.

Using any predefined paths, laser 500 can be scanned or translate relative to substrate or substrate can be opposite In laser translation (as shown by arrows), to generate any pattern, such as square, rectangle, circle, oval or any other are suitable Pattern or shape, thus one or more cavitys of such as air-tightness or the non-airtight ground in sealing device.Laser beam (or base Material) along the translational velocity V of Interface Moving_sAccording to application variation and it can depend on such as the first and second substrates Composition and/or focusing construction and/or laser power, frequency and/or wavelength.In some embodiments, the translation of laser Speed can be in the range of about 1mm/s (mm/second) to about 1000mm/s, for example, about 10mm/s to about 500mm/s or about 50mm/s to about 700mm/s is greater than about 100mm/s, greater than about 200mm/s, greater than about 300mm/s, greater than about 400mm/ S, be greater than about 500mm/s or greater than about 600mm/s, including therebetween all ranges and subrange.

The mean time area of a room that laser is spent on single pad is also referred to as " residence time ", can be with beam spot diameter, D and translational velocity V_sCorrelation, for example, residence time=(D/V_s).For example, the illustrative residence time can about 1 microsecond (ms) extremely In the range of about 10ms, for example, about 2ms to about 9ms, about 3ms to about 8ms, about 4ms to about 7ms or about 5ms to about 6ms, including All ranges and subrange therebetween.

Translational velocity V of the laser beam at seal interface_sIntensity, the pattern of laser welding can be influenced with beam spot diameter, D And/or form.In addition, repetition rate (the r of pulse laser_p) or continuous wave (CW) laser modulation rate (r_m) can influence to obtain Laser weld lines.In some embodiments, pulse laser can be with a certain translational velocity V_sWork, according to the following formula (1), this is flat Move speed V_sGreater than laser beam at seal interface beam spot diameter, D multiplied by laser beam repetition rate (r_p) product, the formula (1) are as follows:

V_s/(D*r_p)>1 (1)

Similarly, modulation CW laser can be with a certain translational velocity V_sWork, according to the following formula (1 '), translational velocity V_sIt is greater than At seal interface the beam spot diameter, D of laser beam multiplied by laser beam modulation rate (r_m) product, the formula (1 ') are as follows:

V_s/(D*r_m)>1 (1’)

Certainly, for given translational velocity, also changeable beam spot diameter, repetition rate and/or modulating speed are to meet Formula (1) or (1 ').The laser to work under these parameters can produce the non-overlap laser welding comprising each " point ".For example, each Time (1/r between laser pulse_pOr 1/r_m) residence time (D/V can be greater than_s).In some embodiments, V_s/(D*r_p) Or V_s/(D*r_m) can in the range of about 1.05 to about 10, for example, about 1.1 to about 8, about 1.2 to about 7, about 1.3 to about 6, about 1.4 To about 5, about 1.5 to about 4, about 1.6 to about 3, about 1.7 to about 2 or about 1.8 to about 1.9, including therebetween all ranges and sub- model It encloses.For example, according to each embodiment of the disclosure, this welded pattern can be used for being formed non-airtight sealing element.

In other embodiments, pulse laser can be with a certain translational velocity V_sWork, according to the following formula (2), translation speed Spend V_sLess than or equal to beam spot diameter, D multiplied by repetition rate (r_p) product, the formula (2) are as follows:

V_s/(D*r_p)≤1 (2)

Similarly, modulation CW laser can be with a certain translational velocity V_sWork, according to the following formula (2 '), translational velocity V_sIt is less than Or equal to laser beam at seal interface beam spot diameter, D multiplied by laser beam modulating speed (r_m) product, the formula (2 ') are as follows:

V_s/(D*r_m)≤1 (2’)

Certainly, for given translational velocity, also changeable beam spot diameter, repetition rate and/or modulation rate are to meet Formula (2) or (2 ').The overlapping laser welding comprising continuous " point " can be formed by working under the parameter, which, which is close to, connects Continuous line (such as work as r_mOr r_pWhen increasing to infinity).For example, time (the 1/r between each laser pulse_pOr 1/r_m) can be less than Or it is equal to residence time (D/V_s).In some embodiments, V_s/(D*r_p) or V/ (D*r_m) can be in the range of about 0.01 to about 1 It is interior, for example, about 0.05 to about 0.9, about 0.1 to about 0.8, about 0.2 to about 0.7, about 0.3 to about 0.6 or about 0.4 to about 0.5, packet Include all ranges and subrange therebetween.For example, according to each embodiment of the disclosure, these welded patterns can be used for shape At gastight seal.

Suitable glass baseplate, which shows significantly to induce during sealing, to be absorbed.In some embodiments, the first base Material 302 can be transparency glass plate, such as Corning Inc with EagleTrade name manufacture and sale Those or other glass.Alternatively, first base material 302 can be any transparency glass plate, such as is manufactured and sold by following company Those of sell: Asahi Glass glass Co., Ltd. (Asahi Glass Co.) (such as AN100 glass), Japan Electric glass company (Nippon Electric Glass Co.) (such as OA-100 glass or OA-21 glass) or healthy and free from worry precise materials company (Corning Precision Materials).Second substrate 304 can be glass material identical with the first glass baseplate, Or second substrate 304 can be opaque substrate, such as, but not limited to ceramic base material or metal base.Illustrative glass base The thermal expansion coefficient of material can be less than about 150x10^-7/ DEG C, it is, for example, less than 50x10^-7/℃、20x10^-7/ DEG C or 10x10^-7/℃.When So, in other embodiments, first base material 302 can be ceramics, ITO, metal or other materials of patterning or conitnuous forms Expect substrate.

Fig. 3 is the figure of the another embodiment of this theme.With reference to Fig. 3, the picture left above, which instantiates, can be used for two Eagle(EXG) glass baseplate carries out some exemplary parameters of laser welding.Can with time monitoring transmissivity (%T), and The transmissivity under three kinds of different laser powers is instantiated in the figure of lower-left.At lower laser power profile (curve of rightmost) In be easily observe that LMG, IRA or UVA film fusing beginning, be the inflection of " inflection point " equally, be followed by the fast of glass baseplate Speed absorbs and heating, this is because the high local temperature of glass has been more than EagleStrain point caused by.Higher Inflection (leftmost curve) can be eliminated under laser power and can induce the nothing that formation of glass sheets is absorbed into from LMG, IRA or UVA Stitch transition.Illustrative laser welding may include scanning the area along interface boundary to be combined.In list shown in the lower right corner It describes three conditions and is specifically described below, for example, low melting point film absorption/fusing under incident wavelength, in glass Middle formation colour center and/or temperature-induced absorption occurs in glass in some embodiments.The absorption of individual film is It is enough, without will affect colour center formation or even temperature assimilation effect.It should be noted that the event sequence indicated in Fig. 3 is answered The scope of the claims by the appended claims herein is not limited or indicates the relative importance for other events listed.

In some embodiments, the UV laser that initiation event can be low-melting glass (such as LMG or UVA) film is inhaled It receives.This can be compares Eagle based on film at 355nmFusing with bigger absorption, and based on Fig. 3 is bent Line.Considering the experimental arrangement that the upper left of Fig. 3 illustrates, the laser is Spectra Physics HIPPO 355nm, with 30kHz generation 8-10ns pulse, up to 6.5 watts of mean power.By laser beam focus at the with a tight waist of 500 micron diameters, monitoring The light beam of transmission is simultaneously sampled, obtain the percent transmissions (%T) of different laser powers (5.0W, 5.5W, 6.0W) with when Between figure.The bottom left section of Fig. 3 shows these figures.Under lower laser power (bottom and intermediate curve), it is easy in Fig. 3 Observe the beginning of UVA, IRA or LMG film fusing, be the same inflection of inflection point, be followed by the rapid absorption of glass baseplate with Heating, this is because the high local temperature of glass has been more than EagleStrain point caused by.The glass just welded Part is possible unfused and is only softening, therefore when they are in close contact with the power moderately applied, they become flexible.This property Matter can be similar to solid-state diffusion and combine, and especially lower between the 50-80% of the fusion temperature of substrate can form strong knot For conjunction.The birefringent optical cross section figure of solid phase binding instantiates the apparent interface between two parts being soldered Line (for example, see Fig. 4).

Another embodiment includes the welding carried out with 355nm pulse laser, thus with 1MHz, 2MHz or 5MHz repetition Frequency generates a series of 1ns pulses.When the light beam on inoranic membrane is focused into diameter in 0.02mm to the hot spot between 0.15mm And when speed of welding is in the range of 50mm/s to 400mm/s, about 60 μm to about 200 μm of flawless combination is formd Line.Required laser power can be in the range of about 1W to about 10W.

With reference to Fig. 4, which instantiates the experimental arrangement for estimating the physical extent of laser welding combined area.With continued reference to Fig. 4, laser welding two panels Eagle as previously describedPiece is installed in glass sandwich structure and with diamond sawing It cuts.This is illustrated in the left figure of Fig. 4.Obtained section is mounted in polarimeter to measure the light generated by local stress area It learns birefringent.This shows in the right figure of Fig. 4.Brighter region indicates bigger stress in the right figure.Such as the right figure institute of Fig. 4 Show, bond area shows the physical extent with about 50 microns.In addition, though it is molten not occur any substrate or substrate glass Change, but the combination formed between two glass baseplates is but very strong.For example, the diagram in the center in birefringence images section Go out the extension of solid phase binding region and is deep into EagleIn substrate (50 microns), this demonstrate high sealing intensities.Laser Welding will include scanning the area along interface boundary to be combined.

Fig. 5 is the micro-image of fracture specimens.With reference to Fig. 5, shown in the three-dimensional confocal microscopy view pictures of fracture specimens say The sealing intensity of bright embodiment of the present disclosure is sufficiently strong, so that by tearing following substrate (such as EagleBase Material) material as deep as 44 μm just occur failure (i.e. cohesional failure).Sample did not carried out annealing.Fig. 5, which is also illustrated, is subjected to shaver Piece crackle opens the fracture specimens of the unannealed laser welding embodiment of technology.A series of burnt measurements of three-dimensional copolymerization are carried out, And representative example is shown on the right side of Fig. 5.One feature of these Confocal Images shows that interfacial seal intensity can be with It is sufficiently strong, so that the failure in most of substrate material occurs for example, in the described situation far from interface as deep as 44 μm, And as deep as about 200 μm in other experiments.In other experiment, polarimeter measurement show newly formed laser welding (with The condition studied in Fig. 5 is identical) in generate residual stress, the laser welding newly formed is annealed 1 hour at 600 DEG C, is obtained To firm connection no measurable stress is shown by polarimetry.Attempt to destroy this combination, as a result cause except weldering It connects outside the seal line of substrate, remaining place ruptures.

As noticed in Fig. 3, using embodiment of the present disclosure, using illustrative low melting point film or in incidence wave Another film of long lower absorption/fusing, forms colour center in film and glass and temperature-induced suction occurs in film and glass It receives and strong, air-tightness transparent combination can be achieved.About first criterion, such as low-melting glass absorption events, have enough The laser irradiation of the glass-LMG/UVA- glass structure of high powerperunitarea can be in film LMG/UVA circle of sputtering Cause in face and absorb, so as to cause fusing.This case is easily observe that in the bottom curve in the lower left corner Fig. 3.Bottom curve First slope tracks LMG/UVA fusion process about 15 seconds, another process occurs at this time, this process is the glass in corresponding substrate Glass-laser interaction (that is, colour center is formed).After about 17 seconds, it can show that the deep camber of lower curve due to glass among this Colour center is formed in glass and big absorption has occurred.These colour centers can generally change according to the elemental impurity levels in substrate and be become Change, the element impurity such as As, Fe, Ga, K, Mn, Na, P, Sb, Ti, Zn, Sn etc..Transmission curve is more bent, then the color formed The heart is more.This is second criterion mentioned in Fig. 3.The fusing point of LMG/UVA film can be, but be not limited to about 450 DEG C, still Based on the laser irradiation experiment for using the EXG glass baseplate coated with aluminium of substitution to be carried out under similar Laser Welding Condition Observation situation, interface temperature could possibly be higher than 660 DEG C.In this experiment, aluminium fusing (fusion temperature: 660 DEG C), and use warp It is about 250 DEG C that the thermal imaging camera (FLIR video camera) for crossing calibration, which is measured using the surface temperature of Laser Welding Condition,.

Fig. 6 is the modeling scheme schematic diagram according to some embodiments of the disclosure.With reference to Fig. 6, LMG/UVA is utilized 355nm laser is simulated with the heat transfer characteristic of EXG material with 0.8-3kW/cm²Hitting includes 1 μm of+700 μm of thin inoranic membrane Two layers of stack of EXG.The phase transformation in inorganic thin film (for example, LMG, IRA, UVA film etc.) is not considered in a model.With continued reference to Fig. 6, the estimation of transient thermal profile show to can get the interface temperature greater than 660 DEG C.It is higher than 660 DEG C really regardless of whether having reached The presence of the interface temperature cut, the LMG/UVA interfacial film of heat fusing increases glass and being transferred to band gap compared with low energy Absorption in glass substrate.The change of these band gap is generally understood that it is due to caused by the thermal expansion of substrate lattice, with electronics energy Change it is related, and with due to electron-photon interaction caused by with the direct renormalization of energy it is related.The lower right corner of Fig. 3 Show the figure of this property in fusion silica.Net effect is the LMG/UVA film of heat by reducing band gap at interface More absorptions are promoted in neighbouring EXG substrate, this produces more heats from internal conversion process in turn, or even makes band Gap further decreases.This process may be collectively referred to as thermal induction absorption, indicate the third criterion of Fig. 3 instruction.Certainly, at this Other inoranic membranes can be used in a little embodiments, and these examples should not limit the scope of the appended claims.

As described above, the laser welding that colour center is formed in disclosure embodiment formed in play an important role.Use Fig. 8 Shown in experimental arrangement instantiated in Fig. 7 process model building be formed centrally with based on three-level to Essential colour under the conditions of non-multi-photon Scheme (three level diagram) and exports fitting function.Fig. 7 is that another is modeled according to embodiment of the present disclosure Scheme.In the left figure of Fig. 7, three electronic band states of glass absorb 355nm photon, in ground state n_g[t], conduction band n_e[t] and colour center n_ccAccumulation or consumption i on population (population) in [t].It should be noted that single headed arrow expression laser absorption, and double end arrow Head indicates excited absorption and transmitting.In the right figure of Fig. 7, rate equation is provided, predicts the smooth list of electron energy level population Accumulation and consumption are adjusted, and the beam interference drive part of system shows the quick oscillation of identical populationThe right figure of Fig. 7 Most downlink provide the primary condition of three energy levels.Fig. 8 is transmitted by the 355nm laser of Eagle 0.7mm glass baseplate Rate (%T) is used for the experimental arrangement figure that %T is measured relative to the time.With reference to Fig. 8, feature encapsulates (diagnostic Packaging) fusion silica window and Eagle can passed throughThe integral energy of UV pulse is measured after sheet glass Amount and time waveform, wherein mean power is about 5 to 6W.

Following equation (1) describes the relationship for testing observable absorbance (Abs) and time, for example, with transmission Rate (trans) is related to the relationship of time data: (1 ≈ Abs+Trans).Solution can be the summation of rising and damped expoential, but It can simplify as following formula:

Wherein α indicates linear absorption coefficient (cm^-1), I indicates laser flux (photon/cm²Second), σ_gIndicate ground state absorption Section (cm²), σ_esa(σ_Excitation) indicate excited-state absorption cross section (cm2), σ_ccIndicate colour center (color-enter) absorption cross-section (cm²), k_ecIndicate transient state colour center rate, and k_fIndicate fluorescence decay rate.Reference equation (1) and Fig. 8, can be observed colour center and are formed Effect in disclosure embodiment.Fig. 9 is the figure described in accordance with one embodiment of the present disclosure.With reference to Fig. 9, to Mr. Yu A little non-limiting laser-glass interaction parameters, provided there are colour center formation equation (1) figure (diagram Camber line), and the figure (straight line of diagram) of equation (1), the laser-glass phase are provided there is no colour center formation Interaction parameter is α=0.01cm^-1, I=4.610^-21Photon/cm²Second, σ_g=1.2010^-17cm², σ_esa=1.21 10^-17cm₂, σ_cc=2.2010^-13cm², k_ec≈kf≈1.0·10⁷Second^-1.σ is set_cc=0, linear correlation can be carried out.Then Pass through following relationship: % transmissivity=100-% absorbance relationship obtains % transmissivity.As illustrated in Fig. 9, it can be seen that, make With the parameter value of reasonable selection, colour center is simply formed into item zero (that is, setting σ_cc=0) camber line is transformed to straight line.Experiment This curvature is typically exhibited with laser welding glass baseplate, the glass baseplate includes but is not limited to Eagle Lotus The combination of Willow and Willow and Willow, Willow and Lotus and Willow and Eagle.

Figure 10 provides analysis at glass interface, enters Eagle from exemplary L MG film layerIn glass baseplate Diffusion figure.With reference to Figure 10, using TOF-SIMS analysis under suitable Laser Welding Condition, from LMG at glass interface Film layer possibly into arrive EagleThe diffusion of glass baseplate, the LMG film layer have illustrative non-limiting composition (38%SnO, 40%SnF₂, 20%P₂O₅, 2%Nb₂O₅) and with a thickness of about 0.8 μm.(a, b) and process above original interface F the and Sn line scanning of (c, d) shows to leave the diffusion very little at interface above the interface of laser welding, and fluorine is from interfacial migration About 0.5 micron, on average, tin does not move significantly.Therefore, although Figure 10 seems to indicate that lacking significant LMG material expands It is scattered in exemplary substrate, but it is true to carry out further effort research and quantization to the mutual mixed degree between inoranic membrane and substrate Various inoranic membrane migration of element of accepting have arrived in substrate, and substrate element has entered in inoranic membrane (for example, see Figure 38 A- 38C and 39A-39C, is hereafter discussed in more detail).

Figure 35 C shows the sectional view (such as intercepting along the line C in Figure 35 B) of sealing device 200.As shown, can To form welding region 250 after the sealing, which extends to the second base from the first depth d1 in first base material 210 The second depth d2 in material 220.Without being bound by theory, it is believed that welding region 250 can indicate composition and the first and second bases Any one of material 210,220 and/or the different region of inoranic membrane 230.For example, since the viscoplasticity of substrate and/or film is swollen Swollen or swelling, can migrate out from their own each layer from every layer of various elements and enter in welding region 250, As discussed in more detail about Figure 38 A-C.For example, inoranic membrane 230 may include one or more inoranic membrane elements, such as F, P, Sn, B, Bi, Zn, Ti, W, Ce, Nb, Pb, Fe, Va, Cr, Mn, Mg or Ge, they may exist or be not present in first and/or In second substrate 210,220.Similarly, the first and/or second substrate 210,220 may include one or more inorganic substrate members Element, such as Al, B, Si, Na, Li, K, Mg, Ca or Ba, they may exist or be not present in inoranic membrane 230.These films and base Material migration of elements and mixing can produce the chemical composition welding region different from each layer.

For example, in some embodiments, during package sealing with laser, substrate and/or inoranic membrane may be due to absorbing laser Can and expand and deformation, and due to it is this absorption and generate local heating.Thermal expansion can make one or more inoranic membranes and Substrate migration of element (is different from diffusion), to form the chemical composition welding region 250 different from all parts, the chemistry Form such as element mixture from first base material 210, inoranic membrane 230 and/or the second substrate 220.Welding region 250 can be with It is present in the welding portion W of sealing device, for example, laser beam is incident on the place on seal interface, thus in two substrates Between formed combine.Welding portion W may be constructed continuous single line, or in other embodiments, one or more weldering Socket part divides W that can separate (for example, as shown in Figure 35 C) by non-solder part I.

According to each embodiment, inoranic membrane and substrate migration of element into migrate out seal interface and can produce thickness t_W Greater than the welding region 250 of the original depth of inoranic membrane.For example, one or more membrane element elements can be on either side from inoranic membrane Depth d1 or d2 are moved to, to form thickness t_W=t_iThe welding region 250 of+d1+d2, wherein t_iIt is that inorganic film thickness (is not marked Note).In this region, the chemical composition of welding region can be different from inoranic membrane and first or second substrate, for example, due to one Kind or multiple film migration of element are into substrate and/or caused by one or more substrate migration of element are into inoranic membrane.According to each Embodiment, depth d1 and d2 can be identical or different, and for example, can be about 0.1 μm to about 2 μm, for example, about 0.2 μm extremely About 1.8 μm, about 0.3 μm to about 1.6 μm, about 0.4 μm to about 1.5 μm, about 0.5 μm to about 1.4 μm, about 0.6 μm to about 1.2 μm, Or about 0.8 μm to about 1 μm, including therebetween all ranges and subrange.The thickness t of welding region 250_WCan similarly it become Change, this depends on the original depth of inoranic membrane 130 and film and/or substrate migration of elements degree (for example, the amount of d1 and d2 Value).Illustrative throat thickness t_WIt may include but be not limited to 0.3 μm to about 14 μm, for example, about 0.5 μm to about 12 μm, about 0.8 μm To about 10 μm, about 1 μm to about 8 μm, about 2 μm to about 7 μm, about 3 μm to about 6 μm or about 4 μm to about 5 μm, including owning therebetween Range and subrange.

In some embodiments, the chemical composition of welding region 250 can be with the inoranic membrane 230 in the I of non-solder part And/or the chemical composition of first or second substrate 210,220 is different.For example, welding region 250 can have the first inorganic substrate Concentration of element is greater than in the I of non-solder part (for example, see region I_i) the second inorganic substrate element in inoranic membrane 230 is dense Degree.In other embodiments, welding region 250 can have the first inoranic membrane concentration of element, be greater than in the I of non-solder part (for example, see region S_1iAnd S_2i) the first and/or second substrate 210,220 in the second inoranic membrane concentration of element.According to another Outer embodiment, welding region 250 can have the first inoranic membrane concentration of element, be greater than in welding portion W, but fall in weldering It is outer (for example, see region S to connect region 250₁And S₂) the first and/or second substrate 210,220 in third inoranic membrane element it is dense Degree.In other embodiment, a part of the first and/or second substrate in welding region 250 is (for example, see region S_1W And S_2W) it can have the 4th inoranic membrane concentration of element, it is greater than in the I of non-solder and/or the part W of welding (for example, see area Domain S_1iAnd S_2iAnd/or S₁And S₂) the first and/or second substrate in second and/or third inoranic membrane concentration of element.

Figure 36 A-B is the SEM image for being respectively seal interface before and after laser welding.The embodiment party shown in In formula, the first and second substrates 210,220 include EAGLE Glass, and inoranic membrane 230 includes LMG. In Figure 36 A (before welding), inoranic membrane 230 with a thickness of 1.05 μm, and in Figure 36 B (after welding), the thickness of welding region 250 Degree is 2.80 μm.It is clearly visible the viscoplasticity expansion or swelling of substrate and film and the mutual mixed of these layers in Figure 36 B and is formed Welding region 250.(for example, see region S in welding region_1WAnd S_2W) the first and/or second substrate part chemical group At can be with the difference of the substrate 210,220 in Figure 36 A (before welding).For example, one or more inorganic membrane elements from film 230 Element can move in the substrate in welding region 250.Similarly, the chemical composition of welding region 250 can be with Figure 36 A (weldering Before connecing) in inoranic membrane 230 in chemical composition it is different.For example, one or more inorganic bases from substrate 210 and/or 220 Material element can move in welding region 250.

For example, depend on material and laser processing parameter used, above-mentioned zone respectively between concentration difference can be alone Variation, and in some embodiments, it can be in the range of about 5 moles of % to about 80 moles of %, for example, about 10 moles of % are extremely About 75 moles of %, about 15 moles of % to about 70 moles of %, about 20 moles of % to about 65 moles of %, about 25 moles of % to about 60 rub You are %, about 30 moles of % to about 55 moles of %, about 35 moles % to about 50 moles % or about 40 mole % to about 45 moles of %, Including therebetween all ranges and subrange.In some embodiments, the first film concentration of element can be denseer than the second membrane element element Degree up at least about 5 moles of % (such as up at least about 10,20,30,40,50,60,70 or 80 moles of %) and/or the first base Material concentration of element can than the second substrate concentration of element (such as up at least about 40,50,60,70 or 80 up at least about 30 moles of % Mole %).Can be measured in various modes known in the art it is this form difference, for example, such as secondary ion beam matter Compose (SIMS), element probe microscopic analysis (EPMA) and intermediate electronic microtechnic (TEM).

During or after sealing, stress area or heat-affected zone (HAZ) 260 can also be formed in a device, this is answered Power region extends to the 4th depth d4 in the second substrate 220 from the third depth d3 in first base material 210.As shown in Figure 35 C, Stress area 260 can be covered or the region including welding region 250 and surrounding is (for example, region S_1SAnd S_2S).It welds as a result, The part for connecing the first outside region 250 and/or second substrate still can be fallen into stress area 260, either in device In the part W of welding or the part I of non-solder.In some embodiments, the thickness t of stress area 260_SIt can be micro- tens In the range of rice to several hundred microns, for example, about 20 μm to about 500 μm, for example, about 30 μm to about 400 μm, about 40 μm to about 300 μ M, about 50 μm to about 200 μm, about 60 μm to about 150 μm, about 70 μm to about 120 μm or about 80 μm to about 100 μm, including its Between all ranges and subrange.According to other embodiment, depth d3 and d4 can be identical or different.

Without being bound by theory, but think that the residual stress in region 260 may be sharp because in welding region or nearby having Light is exposed, so that substrate is heated rapidly and cooled down and exists.Although it is straight that laser can focus on specific beam spot at seal interface Diameter, but the heat from laser can distribute and influence larger portion of sealing device, which extends beyond welding Region 250, for example, greatly to welding region outer tens or several hundred microns.For example, when depending on the stop of welding temperature and laser Between, the size of stress area can change.But even under high translational velocity (such as residence time < 2-3ms), heat Spread (1.4x10^-6m²/ s) it can lead to stressed zone greatly to tens microns.Can influence stressed zone other factors may include due to Substrate directly heats caused by the UV edge dislocation of color center model and/or glass in glass baseplate.

In some embodiments, the stress in region 260 can be with the stress in the sealing device outside region 260 not Together.For example, (for example, see region S in region 260_1S) a part of first base material 210 can have the first stress, be greater than area Domain 260 is outer (for example, see region S₁) first base material 210 in the second stress.In other embodiments, in region 260 (for example, see region S_2S) the second substrate of a part 220 can have tertiary stress, be greater than region 260 it is outer (for example, see Region S₂) the second substrate 220 in the 4th stress.Although being not easy to see in the SEM image of Figure 36 A-36B, have can allergic effect These regions of power, but following any means can be used to be quantified and compared for the stress in each region.

For example, depend on material and laser processing parameter used, above-mentioned zone respectively between stress difference can be independent Variation, and in some embodiments can be in about 1MPa to about 25MPa or higher range, for example, about 2MPa is to about 20MPa, about 3MPa to about 15MPa, about 4MPa to about 10MPa, about 5MPa to about 8MPa or about 6MPa to about 7MPa, including its Between all ranges and subrange.According to other embodiment, the stress in region 260 is relative to the stress outside region 260 Ratio can be in the range of about 1.1:1 to about 25:1, for example, about 1.2:1 to about 20:1, about 1.3:1 to about 15:1, about 1.4:1 to about 10:1, about 1.5:1 to about 9:1, about 1.6:1 to about 8:1, about 1.7:1 to about 7:1, about 1.8:1 to about 6:1, about 1.9:1 to about 5:1, about 2:1 to about 4:1 or about 2.5:1 to about 3:1, including therebetween all ranges and subrange.

Stress in these regions can be measured and/or be estimated by various technologies, including but not limited to stress birfringence (stress test), Raman spectroscopy (variation of fictive temperature and stress), Brillouin (Brilluoin) spectroscopic methodology (fictive temperature With the variation of stress), refractometry (variations in refractive index due to caused by fictive temperature and stress), polarization microtechnic and/ Or thermal capacitance measurement.According to each embodiment, if it is desired, after sealing, sealing device can be made to carry out one or more steps Subsequent annealing steps with reduce and/or estimation area 260 in stress.

Although based on big CTE mispairing --- CTE obvious between each material in interface_870CHM=18ppm/ DEG C compared to CTE_EXG =3.1ppm/ DEG C, it may expect that moveable atom species used in disclosure embodiment have significant bigger diffusion, But removing is not observed.On the contrary, the temperature that iterative cycles are up to 600 DEG C seems to eliminate any residual stress, thus Generate stronger combination.Obtained inorganic thin film is sufficiently thin, so that being removed as caused by the CTE mispairing of each glass baseplate Power is much smaller than binding force.This, which meets, carrys out the cube proportional of the laminar structure combined stress of self-adhesive film deposition stress and film thickness Knowledge.

Figure 11 is the schematic diagram of the laser weldability between the sheet glass of different-thickness.With reference to Figure 11, discovery will surpass Thin Willow glass (0.1mm) is welded to EagleIt the case where glass (0.7mm), i.e. " asymmetry ", can be obtained of poor quality Welding.In " symmetrical " Eagle and Eagle situation (left side of Figure 11), along glass interface scan the hot-zone of heat with into The excellent welding of row.Corresponding Temperature Distribution is instantiated below each diagram.However, when the sheet glass for using different-thickness When, there is asymmetric hot-zone, in some cases, such as when welding Willow and Eagle, will lead to ropy weldering Connect (middle illustration of Figure 11).However, illustrative embodiments can provide the solution of this asymmetric Welding Problems, It is shown on the right side of Figure 11, wherein any hot and cooling thin glass sheet can be dissipated using heat-conducting plate with the hot-zone of effectively recovery heat And form firm solder bond.Therefore, some embodiments as described herein can using the use of heat-conducting plate come to thickness not Same sheet glass carries out laser welding.

Although description before this, which has been described, is welded to glass baseplate (with similar or different ruler for glass laser Very little, geometry and/or thickness), but this should in no way limit the range of appended claims, because embodiment exists In the case where with or without conductive interface film, the substrate or sheet material of non-glass materials may be equally applied to, such as but not It is limited to ceramics, glass ceramics, metal etc..For example, Figure 12 is the experiment signal for estimating the laser welding range above ITO lead Figure.With reference to Figure 12, the Eagle coated through LMG is instantiated in the left figure of Figure 12Piece is laser-welded to be coated through ITO EaglePiece.In this experiment, 100nm ito film is deposited into Eagle by passing through the reactive sputtering of maskOn substrate.Alternative condition makes ito film have relatively high average sheet resistance --- about 126 Ω/ (Ω/sq), mark Quasi- deviation is 23 Ω/sq, this, which reflects, does not carry out hot type heating to substrate before, during or after reactive sputter-deposition. The ito film occurred in Figure 12 is obvious jaundice or dimmed band, in diagonal distribution in photo.Before laser welding, 350 Ω that record is measured with multimeter in the distance of instruction.Then it is coated with LMG'sPiece is laser-welded to Eagle coated with ITOOn piece, it is thus found that laser weld lines are very clear, firm, transparent and in diagonal point Cloth, but it is inverted (inverted).In the right figure of Figure 12, in previously used same distance, observe across ITO lead It is measured after the laser welding of resistance, resistance is increased into 1200 Ω from 350 Ω.Conductivity decline is the absorption due to ito film 355nm makes caused by ito film partial destruction when radiating.But in order to avoid due to ito film damage, embodiment party caused by overheating Laser parameter can be changed in formula, so that the temperature of interface will not go to ito film substrate from blank glass substrate or will not be from ito film Substrate go to blank substrates (for example variable peak power of laser parameter, variable repetition rate, variable mean power, can The beam translational velocity of change, electrode pattern, LMG film thickness etc.).

Figure 13 provides the other photo of the package sealing with laser line formed above ITO pattern film.With reference to a left side of Figure 13 Figure, obtains another electrode type from separate sources, is equally made of ITO and with a thickness of about 250nm.Ito film is continuous , sealing is formed on using method described herein.Measuring the initial resistance in about 10mm distance is 220 ohm.When from When transparent glass goes to electrode zone, package sealing with laser is carried out with constant speed and power.After being sealed, in transparent glass and ITO overlying regions observe firm sealing, and the slightly wide about 10-15% of the sealing above ITO.This increasing of sealed width Adding may prompt the heat generated in this region to be more than the heat generated in transparent region.Since laser emission makes electrode material Absorb or due to the different thermal diffusion properties of film can also cause it is additional be thermally generated, and under any circumstance, measure Resistance increase about 10% reaches 240 Ω, this is inappreciable.This may also indicate that, when temperature is increased relative to blank glass When, the ITO of better quality and thicker film do not show electric conductivity decline.It should be noted that when being converted to electrode from transparent glass When region, the additional resistivity reduction reduction for being thermally generated and therefore making ITO can be reduced by reducing package sealing with laser power.Experiment knot Fruit also prompts, and when the electrode width used is between the 1/2-1/3 of beam width, and spacing is in the 1/2-1/ of beam diameter When between 3, it can be in sealing station punishment at the single electrode of electrod-array (with overall width identical with original electrodes) It is optimal.Shown after sealing with the experiment that the high sealing speed higher than 20mm/s carries out later, resistance decline < 1-2%, Middle initial resistance is about 200 Ω.

Figure 14 is a series of photos of the other package sealing with laser line formed above patterned film.With reference to Figure 14, with not Transparent molybdenum electrode carries out similar experiment.Figure 14 provides a series of photos of continuous and patterned molybdenum interfacial film, It, which shows, forms package sealing with laser line on the molybdenum interfacial film.In left figure, the photo of continuous molybdenum film is illustrated with crackle Or the molybdenum electrode part of rupture forms more uneven combination.Even in this case, under constant package sealing with laser power, Uniform molybdenum electrode is not also damaged completely.However, due to the absorption of uniform electrode or reflection laser radiation, electrode zone adds Heat is apparently higher than transparent glass region.This can be observed by the width increase of the sealing area of molybdenum overlying regions.It should It is noted that a unspoiled region is located at the transitional region between transparent and uniform molybdenum region, to prompt power tune All the combination of three factors can overcome any overheat pair during whole, laser power density, laser spot velocity or sealing event The influence of uniform molybdenum electrode.In the right figure of Figure 14, the photo of the molybdenum film of patterning or perforation, which instantiates, to be formd more evenly Combination so that, that is, 14 Ωs 16 Ωs to weld after weld before minimum to the level of disruption of its electric conductivity.In the punch block Sealing above domain shows significant less heat, thus provides the alternative solution of power modulation method.It should also be noted that Electrode metal should be carefully selected, because it has been found that, other high metal phase ratios, low with fusion temperature with molybdenum or fusion temperature Metal (Al) (650 DEG C compare 1200 DEG C) be less likely to remain intact under air-proof condition to seal.Therefore, it as a result prompts, When the electrode width used is between the 1/2-1/3 of beam width, and spacing is between the 1/2-1/3 of beam diameter, It can be in sealing station punishment at the single electrode of electrod-array (with overall width identical with original electrodes) optimal.Cause This, embodiment of the present disclosure be applicable to glass and glass, metal, glass ceramics, ceramics and have identical or different size, The package sealing with laser of other of geometry and thickness substrate.

It is effectively formed that bond strength is high, weldering of transparent, glass and glass using the application of embodiment described herein It connects, there are many such application, including but not limited to solid-state lighting, display and transparent vacuum insulation technology.Particularly, glass Laser welding can provide many traditional welding methods (such as electron beam, electric arc, plasma or torch) and cannot provide at all Some efficiency and feature, such as small heat affected area (HAZ).It in some embodiments, is opaque for many glass The case where, laser glass welding generally can in the case where no preheating or rear heating using infrared (IR) laser into Row；Or in the case of many glass are transparent, laser glass welding can be in the case where no preheating or rear heating It is carried out using ultrashort pulse laser (USPL).In some embodiments, glass baseplate composition and distribution are correctly selected Available airtight " sandwich type " glass laser sealed package of IR heat absorbing glass material in interface.In some embodiments In, ultra-short pulse laser can focus at the surface in exemplary glass substrates or internal point, and can be by non-linear Process (such as multi-photon or avalanche ionization) induction absorbs.

So far, it has been described that low power laser welding procedure depends on the absorption of low-melting glass interfacial film, and Due to its be low temperature bond formed (down to the half of fusion temperature) and to contact and pressure condition requirement, can return Because in Diffusion Welding.As described above, laser welding sheet glass and strong combination, which are formed, has some remarkable results, for example, Low-melting glass film absorbs under laser wavelength of incidence, and the colour center of induced with laser is formed in glass baseplate, and sends out in the substrate It has given birth to thermal induction and has absorbed the raising for effectively accelerating temperature.

But in some embodiments, many films highly absorbed at incident wavelength (such as 355nm) are enough to induce Form the laser welding of high bond strength.Other films, such as ZnO or SnO₂It is different from some examples as described herein in chemistry Property low-melting glass composition, but the same laser weldability having the same under relatively low luminous flux.Therefore, with Some low-melting glass compositions (~450 DEG C) are compared, and in view of the fusion temperature (1975 DEG C) of ZnO, find in some embodiment party Eutectic feature may not be required in formula.However it has been found that the common trait of these films is that they are substantially inhaled at 355nm Receive radiation: ZnO absorbance~45% (film of 200nm thickness), low-melting glass~15% (film of 200nm thickness).It is also determined that Illustrative methods as described herein can be to quartz or pure fusion silica substrate --- and i.e. the substrate of colour center does not carry out Laser welding.Accordingly, it is determined that colour center was not necessarily required, but in some embodiments, when illustrative (for example,~Abs < 20%) may need colour center when the absorption of film is lower.

Figure 15 is the simplification figure of another method according to some embodiments.With reference to Figure 15, there is the light limited The defocused laser 15 of beam width or diameter D are incident on the sandwich shape structure 16 formed by the contact of two sheet glass 17,18, wherein one The internal interface of piece is coated with thin absorbing film 19.Although light beam shown in is cylinder, and this description should not limit herein The scope of the appended claims, because light beam can be cone or other suitable geometries.It can swash for incident Absorbance under optical wavelength selects membrane material.Laser 15 can be with V at a predetermined rate_sTranslation, and when the translation of laser beam Between can effectively irradiate set point, and residence time D/V can be passed through_sTo characterize.In some embodiments, Ke Yi Apply appropriate pressure during welding or binding events, to ensure continuous contact between clean surface, while adjusting any one Or multiple parameters are to optimize welding.Illustrative non-limiting parameter includes laser power, speed V_s, repetition rate and/or beam Spot diameter D.

As described in above for Fig. 3, it is found that best welding can be the function of three kinds of mechanism, that is, by exemplary film and/ Or substrate absorbs laser emission and the heating effect based on the absorption process；Increase since (band gap is to compared with long wave for heating effect Long displacement) caused by film and substrate absorb, can be transient state and depend on processing conditions；And generated by UV radiation Defect or Impurity Absorption or color center model.Heat distribution can be the importance of the process, and following discussion can be used for helping Understand the Temperature Distribution of the interface between two substrates, it is assumed that interface is static absorption.

El-Adawi develops a kind of analysis model, be used for analyze on large-scale semi-infinite slab substrate laser heating by The double stacked part formed with a thickness of the absorbing film of Z.Using the thermic vibrating screen in every kind of material of matched Boundary Condition for Solving, Obtain the temperature expression of the function of the time and position as film and substrate: T_f(t,z),T_s(t,z).The model of El-Adawi is false It is fixed for determining the thermal property (diffusivity D, thermal conductivity k, thermal capacity Cp) of film and substrate, so that only occurring to absorb simultaneously in surface And there is no phase transformations.Being generated using Laplace transform (Laplace transforms) has index and error (complementation) letter Several summations:

Wherein Af indicates the surface absorbance of film, and Io indicates laser flux (photon/cm²Second), n expression integer (0≤ N≤∞), all subscript f indicate film parameters, and subscript s indicates substrate parameter.B and ε are related with material properties: B=1- ε/1+ ε < 1, ε=(k_s/k_f) √ Df/Ds), while L_fFurther include time t:The time of film layer and spatial dimension can respectively such as Get off to provide: 0 < t, 0≤z_f≤ Z, wherein Z indicates film thickness.The time of substrate layer and spatial dimension can such as get off respectively to be mentioned For: t_s< t, Z≤z_s≤ ∞, wherein t_sIt indicates after initial laser film is incident, the temperature of back of the membrane is begun to deviate from needed for room temperature Time (t_s=Z²/6D_f).The coefficient of expansion is related with independent variable and material properties by following formula:

Figure 16 is two layers of laser heating surface absorbing model of identical embodiment.With reference to Figure 16, the figure shows pulses UV (355nm) laser 20 hits the double stacked part 22 with 1 μm of UV absorbing film 23 and 700 μm Eagle-XG substrate 24.Far Figure can be calculated and be drawn to spatial temperature distribution from the weld interface in Eagle-XG stack 22 from equation (2), Assuming that the mean power of pulse (30kHz, 10ns pulse width, 500 μm wide laser beam waist diameter) 355nm laser is 6 watts.So Different laser sweep speeds (2mm/s, 5mm/s, 10mm/2 and 20mm/s) is used afterwards.Using 15% UV film absorbance come into Row calculates, the value be tin fluorophosphate LMG material at 355nm and with a thickness of about 200nm when typical absorbance.Because with Mobile faster light beam is compared, and mobile slow laser beam stops more long above given laser welding site, therefore, is drawn Eagle processedTemperature Distribution in substrate or stack 22 hereby is observed that due to using different laser sweep speeds Caused Temperature Distribution variation.For example, when giving effective stop above solder joint with 500 μm of 2mm/s mobile wide laser beams Between be 0.25 second, and the laser beam scanned with 20mm/s only stops 0.025 second.

As shown in figure 17, it is investigated due to using different laser powers, or drawn using the different film of absorbance The temperature change risen.Figure 17 is the series of temperature variation diagram of some embodiments.With reference to Figure 17, the double-deck laser heated mould is used Type [equation (2)] draws glass baseplate Temperature Distribution to the dependence of laser power and film absorbance.Figure 17 use and Figure 16 phase Same laser parameter.More specifically, using the pulse UV laser with following parameter: λ=355nm girdles the waist=500 μm, weight Complex frequency=30,000Hz and pulse width=10ns.Right figure as being observed that in the left figure of Figure 17, with Figure 17 In the high-order property of absorbance compare, laser power seems more linear to the influence that base material temperature is distributed.This property exists Power I_oAnd absorbance A_fOccur unobvious in the equation (2) coupled.Absorbance can influence effective film thickness z indirectly_f, absorbance To a certain extent with coefficient of expansion b_nAnd g_nIt is related.On the contrary, I_oBe it is independent, be not present and coefficient of expansion b_nAnd g_nIt is relevant Functional relation.

Figure 18 is for some embodiments, a series of average energies for depositing within the residence time for scanning laser Figure.With reference to Figure 18, it can be observed that the residence time depends on laser sweep speed and laser pulse repetition frequency, numerical value simultaneously It is represented in independent variable x-y plane with unit.These, which are calculated, assumes that film absorbance is 25%, and beam width is 500 micro- Rice and and laser pulse width be 10ns --- the welding of fruitful laser glass can be obtained in some embodiments.Figure 18 are indicated with shown plane and have estimated threshold power (11a 6W, 12a 20W) by rule of thumb according to experiment, are higher than and are generated The power of fruitful laser welding.The amount of laser power that the curve graph or figure of top and bottom use is different: 6 watts of comparisons 20 Watt.The comparison of two figures in Figure 18 shows that under low incidence laser power (for example, 6 watts), laser speed and repetition are frequently The slight change of rate can produce incident power significantly more higher than incident power needed for causing enough laser weldings.Even if Repetition rate it is higher and need not with initial laser welding condition (30kHz, 2mm/s laser sweep speed) slightly different also result in The incident power densities wanted.Higher laser sweep speed is rapidly resulted in energy needed for glass baseplate progress laser welding not Foot, this is the linear relationship of inverse relation the comparison laser residence time and laser repetition rate of laser residence time and speed As a result.Under higher incident laser power (such as 20 watts), can get biggish land regions or process window 11b, 12b, wherein the minor shifts of speed and repetition rate maintain sufficient Laser Welding Condition without generating excessive energy. Process window 11b, 12b of two figures can be conducive to laser welding or combine optimization.

Figure 19 is with the Eagle during IR radiation source heats, at 355nmAnd LotusGlass is saturating Penetrate rate figure.With reference to Figure 19, when with 10.6 μm of infrared CO₂Laser irradiation EagleAnd LotusWhen substrate, lead to Cross influence of the experiment temperature variation to the absorbent properties of glass interface.It is observed that at 355nm, these substrates Gained transmissivity is according to CO₂Laser emission generate temperature and significant changes.Therefore, in some embodiments, interface is heated It can generate in the interface of film and glass baseplate and more effectively absorb.

Figure 20 is glass transmission figure of some embodiments during heating at 355nm.With reference to Figure 20, discovery can be with Occur to be formed by the radiation-induced colour center of UV in film and glass baseplate, this can lead to have additional inhale in radiation areas It receives.Since result elevates the temperature, it can be observed that 355nm transmission is to Eagle in Figure 20And LotusGlass The influence of glass substrate.Temperature increases the combination for being attributable to that heating effect shown in Figure 19 and colour center are formed.

Figure 21 is some embodiments during and after UV radiation, to the transmissivity influence diagram of film and substrate.With reference to figure 21, the first curve 30 indicates the Eagle with 200nm ZnO filmThe transmissivity of 0.6mm substrate.Second curve 31 indicates Due to utilizing 355nm laser source, the 3W/mm of 30kHz repetition rate²Transient absorption caused by radiation is (that is, in existing absorption On absorption).Second curve 31 includes inducing to absorb due to caused by colour center and temperature.Third curve 32 indicates laser emission Induction after closing absorbs, i.e. temperature has been restored to environmental condition, and colour center partial disappearance.It should be noted that in these implementations There are some permanent Change of absorption in mode, have high transmissivity in the case where being greater than or equal to 420nm.This effect be due to Caused by the presence of film, and compared with the blank substrates of not film, this effect is significantly enlarged.Such as seen in third curve 32 It observes, some variations of film and substrate can be permanent, but this will not influence visible transmission.In addition to these are based on UV Radiation effect except, increased and fusing it is observed that required temperature can occur for the absorption based on individual film, and This effect can also use the realization of IR absorbing film, as discussed below.Therefore, as shown in figure 21, some exemplary films can be with It shows temperature and colour center forms and changes as the UV temperature radiated and power density change.

Figure 22 is figure of the absorption relative to wavelength relationship of some embodiments.With reference to Figure 22, an embodiment includes The film made of the glass based on FeO, according to processing conditions, which may be at two different oxidation state --- 2+ and 3+. The illustrative non-limiting glass-film based on silica has the FeO of greater than about 10-15 weight %, and equal proportion is FeO and Fe2O3.As illustrated in Figure 22, Fe is found₂O₃It shows to absorb by force under NIR wavelength, and in the wavelength of 1064nm Under YAG laser irradiation also can be used.In this case, it is seen that light transmission is less than about 0.02 and will not damage in about 420nm Decaying to about 700nm.It was found that the absorption at 1064nm is about 0.1, and can be with higher than exemplary film fusing point Enough laser powers heat exemplary film and carry out laser welding.Certainly, appended claims should not necessarily be limited by this, because To also contemplate other examples of IR absorbing film He other IR laser.

Figure 23 is in EagleThe package sealing with laser of exemplary low-melting glass film on glass combines exograph X.

Figure 24 is in EagleThe intersecting laser of exemplary low-melting glass film on glass seals exograph X.Figure 33-34 is the photo of the sealing wire in some embodiments.With reference to Figure 23,24,33 and 34, these figures, which instantiate, utilizes UV laser The exemplary weld formed at different conditions.More specifically, Figure 23 is instantiated in Eagle1 μ m-thick is used on glass Low-melting glass film 200 μm of package sealing with laser lines, and Figure 24 instantiates EagleThe low of 1 μ m-thick is used on glass The intersection of two 400 μm of lines of melting point glass film.The width of sealing wire, seal line or bonding wire can be by changing each substrate The spot size of interface change.It is also noted that in either case that (single welding intersects weldering during the experiment Connect), flawless is formed in film or substrate.With reference to Figure 33, there can be 1 μm of low-melting glass film among two substrates Lotus Laser weld lines are observed in glass stack.Welding condition includes the repetition rate of 1MHz, the laser of 10W Thus the translational velocity of power and 100mm/s obtains 190 μm of line width.With reference to Figure 34, there can be 1 μm of low melting point glass The Eagle of glass filmIntersecting laser sealing wire is observed in glass stack.Welding condition includes the repetition rate of 1MHz, The laser power of 4W and the translational velocity of 200mm/s, thus obtain 80 μm of line width.

Figure 25 is the interfacial contact geometric ranges schematic diagram that some embodiments are observed in laser welding.With reference to figure 25, left figure indicates the boundary condition occurred in " Ra " range, wherein clearance t_GapThickness determined by local surfaces roughness, Its statistical nature is Ra number, and in the face of asperities spatial distribution characterized by the correlation length of part.The right figure table of Figure 25 Show the boundary condition occurred in " dirt " range, wherein clearance t_GapThickness by main dirt particle diameter distribution statistics It determines, and spatial distribution is determined by dirt Density Distribution in face.Thus, it can be observed that the gap thickness within the scope of Ra depends on In glass substrate surface statistics, range is from the ultra-smooth numerical value down to several nanometers of zero point (for example, crystallization range) to expression quotient Purchase tens nanometers of exemplary value of the upper limit of glass (for example, soda-lime glass, borosilicate glass).

The potential mechanism of laser welding dynamics, Diffusion Welding creep flowage is explored, it can be observed that down to glass base The combination that relative low temperature occurs at a temperature of the half of the fusion temperature of material is formed, and may be needed in some embodiments Contact and pressure condition.Mode of most of substrate material mass transport into gap and the temperature by being higher than substrate strain point It is consistent come the swollen expanded glass of thermosol that activates.As discussed in more detail below, the viscoplasticity expansion and swelling of substrate can lead to weldering Region is connect rich in one or more inorganic substrate elements (for example, see Figure 39 A-C).

The movement of this material can pass through various forms of creep flowages (i.e. sticky mistake common in Diffusion Welding model Journey, plasticity process or diffusion transport process) one of describe.Although these models are usually used in describing metal welding, Use opposite contact area A_c/A₀Concept, the case where they can be used for the disclosure, Figure 26 instantiates its dynamics development. Figure 26 is the constant pressure P in application_OutsideUnder, during carrying out laser welding to interfacial gap region, opposite contact area A_c/A₀ Differentiation schematic diagram.With reference to Figure 26, in the figure at top, time=0 and opposite contact area A_c/A₀Primary condition be equal to 0.In the figure in the middle, the time is greater than 0, it illustrates the intermediate state in interfacial gap region, wherein A_c/A₀>0.Figure in bottom In, the time is predetermined point (t ≈ terminal), has been substantially finished welding or combination at this time and gap not actually exists, A_c/ A₀≈1.It forms the Diffusion Welding interface as representated by Figure 26 and assumes relative contact product A_c/A₀Differentiation converge to chemical key-shaped At distance.These dynamics can be described with approximation method:

Wherein k indicates that constant, p indicate pressure, and n indicates that pressure index, Q indicate the creep flowage mechanism of special speed control Activation energy.N value can be related to rate control mechanism as follows: adhesive quality being transmitted, n=1；For Plastic Flow, n=2； Evaporation/condensation is transmitted, n=3；And for diffusion transport, n > 3.

Equation (4) can be used for instructing to derive the certain mechanical forces to work, because expression formula is it is assumed that isothermy.For Beginning this mechanical investigations, and due to low softening point borosilicate glass and EagleSimilitude (softening point: 971 DEG C), therefore may be used within the scope of 800 DEG C -950 DEG C, to the height of low softening point borosilicate glass (700 DEG C -750 DEG C) The document parameter for the three-point bending test research that warm creep is carried out, wherein finding, for all creep stages, deformational behavior table Reveal linear viscoelasticity, the linear viscoelasticity is by quickly and at a slow speed the VISCOUS FLOW of creep behavior is controlled.Use fast creep shape Condition data (n=1, Q=160kJ/mol, and k=0.00048Pa-1s), condition are similar to certain laser weldings experiment (950 DEG C), it is assumed that EagleNominal modulus and CTE value be 73.6GPa and 3.1ppm/ DEG C, can be evaluated whether welding region apply Total effective pressure P_AlwaysIt is 600MPa at 950 DEG C, has been more than the nominal application pressure of about 0.1MPa.Upper limit estimation is based on The experimental data of measurement, and indicate that substrate glass and membrane material are swollen and expand in planar interface overlying regions, such as Figure 27 institute Show.Figure 27 instantiates the contourgraph mark using common Laser Welding Condition above the laser sweeping area of an embodiment Line.With reference to Figure 27, bottom schematic view indicates to carry out that continuous laser twice scans is coated with single low melting point under the following conditions The Eagle of glass (film of 1 μ m-thick)Substrate, the condition are as follows: 355nm, 30kHz, 4mm/ seconds rate of translation.Figure 27 Top image be single line contourgraph trace above the two welding regions, show raised form.

Even if assuming for temperature to be fixed on 950 DEG C, still it may be noted that whether VISCOUS FLOW mechanism under this condition is sufficient To be formed and be promoted Diffusion Welding to complete (A_c/A₀≈1).Figure 28 provides some opinions to such case.Figure 28 there is provided For a series of figures of the bonding speed comparable situation of some embodiments estimation.With reference to Figure 28, equation (4) can be based on, made With effective welding pressure of low strain dynamic and low softening point borosilicate glass creep flowage parameter and 600MPa come to bonding speed Estimated value is compared.The difference of the two figures is only that it is assumed that VISCOUS FLOW (left figure) or Plastic Flow (right figure). Recalling about 0.25 second residence time produces firm laser welding under the conditions of about 6 watts and 30kHz laser repetition rate, VISCOUS FLOW explanation may be under suspicion, and the left figure in Figure 28 shows other mechanism, such as Plastic Flow, this is also likely to be jail Solid welding the reason of being formed.

Figure 29 is the polarimetry of some embodiments and the schematic diagram of image.With reference to Figure 29, can check by interface The residual stress field that the Exemplary laser welding procedure that solder bond nearby carries out generates.For example, the top graph of Figure 29 instantiates In two 0.7mm EagleThe polarimetry of the stress field near laser welding between glass baseplate, one of them Inner surface is coated with the low-melting glass film of 1 μ m-thick.The picture left above provides to be obtained by scanning 355nm UV laser under the following conditions Laser welding residual stress field polarization image, the condition are as follows: 20mm/ seconds, 14 watts, 200 μm of beamwidths and 150kHz Repetition rate, and top right plot provides the three-dimensional rendering of the residual stress field.In the following figure of Figure 29, provides and show sprawling (propagating) stress field and sought according to Laser Welding Condition its position analysis dependence diagram.Then can estimate Counting influences the position of sprawling stress field under universal Laser Welding Condition.However, analysis model often regards simple structure For semo-infinite entity or plate.Equation (2) illustrates the complexity of the solution for two-layer system, with related with the time Fusing or stress forward position introducing, this solution may become difficult to rapidly handle.A kind of melting model consideration company It is connected to the plate of radiator, and incidenting laser radiation is completely absorbed on surface.The model considers two kinds of time situations: Yi Zhongzhuan Condition be fusing time be less than transit time (for example, plate rear end from room temperature increase temperature needed for the time) and second of situation It is greater than transit time for fusing time.The model also contemplates the thermal balance side suitable for the sprawling interface between liquid and solid Journey:

Wherein, in addition to Z represents fusing advanced position, Q_LThe latent heat of fusion is represented, and hot-fluid is one absorbed at surface Dimension, optical radiation and thermal material properties keep temperature independent outer, and each term is identical as used in equation (2).Then may be used To export quadratic equation with Z and dZ/dt, the Z and dZ/dt have the coefficient as ermal physics and the function of laser parameter.For The dependence for understanding sprawling stress field, can pass through byFusing (fusion) latent heat replace with from before Eagle The activation energy of the creep stream of substitute melts frontal analysis model, the Eagle to change the laser of sprawlingSubstitute is low strain dynamic point borosilicate glass, and activation energy is normalized effective molecular weight to (160kJ/ rubs You)/(0.266kg/ moles).In view of the case where plate substrate backside does not radiate in welding process, obtained expression formula is showed There is interesting dependence to laser and material properties out:

Wherein Z indicates that creep advanced position, l indicate that base material thickness, Cp indicate substrate thermal capacitance, and A indicates substrate absorbance, R Indicate substrate reflectivity, Δ T_mIndicate sprawling temperature needed for maintaining creep stream from environment temperature rising condition (for example, Δ T_m= T_Strain–T_Environment), ρ indicates that matrix density, λ indicate substrate thermal conductivity, I_oIndicate laser radiation rate (W/m²) and the t expression time.

Figure 30 instantiates power dependent, it is possible thereby to observe, laser power is simply increased during welding can be with Bigger stress is generated except interface zone, wherein excessive energy results in bigger stress.Figure 30 is that basis is shown Example property sealing wire provides the figure of stress position.With reference to Figure 30, it can use equation (6) and determine the stress from exemplary weld line Position is girdled the waist=500 μm wherein used parameter is similar to previously used parameter: wavelength=355nm, and repetition rate= 30,000Hz, pulse width=10ns, V_s=2mm/ seconds, residence time=0.25 second,Thickness=0.7mm, T_Strain =669 DEG C.Figure 30 and equation (6) additionally provide why the higher glass baseplate of strain point can obtain higher stress distribution Opinion.For example, stress distribution position Z is with Δ T_mThe square root of item is scale, and Δ T_mItem and T_StrainIt is linearly related.From these expression Other trials of formula prognostic experiment observation result can not only be limited by used hypothesis, but also can be by that can count The information of calculation limits, for example, if carrying out laser welding to CTE higher material.It has been found that low CTE glass baseplate is (small In about 5ppm/ DEG C) more higher than CTE glass (such as soda-lime glass) be easier to weld.These low CTE substrates include quartz, fusion Silica, EagleWillow and Lotus glass baseplate.By many experiments, it was found that suitable condition, thus The welding of high quality can be carried out in the higher glass of CTE.For example, it was discovered that embodiment as described herein can be used 1 μm LMG film without carrying out any preheating to substrate, is less used for welding soda-lime glass (CTE be about 9ppm/ DEG C or higher) Say strain or annealing point.Figure 31 is a series of photographs according to some embodiments by the soda-lime glass of laser welding Piece.With reference to Figure 31, the combination shape of high quality is realized using extremely low laser power and Nanosecond Pulse Width UV (355nm) laser At.Laser Welding Condition for these non-limiting and illustrative welding includes pulse width=1ns, and repetition rate= 5MHz, power=1 watt, about 20 μm of beam spot obtain 67 μm of sealing wire and V_s=50mm/s.With continued reference to Figure 31, make With the soda-lime glass plate of two 0.7mm thickness of pulse 355nm laser welding, they have the low melting point of 1 μ m-thick of sputtering with one The substrate of glass-film is compressed together.Examples detailed above and experiment should not limit Claims scope as described herein, because being There is the laser of the 2MHz to 5MHz of 1ns pulse width to repeat for research under 50mm/s -400mm/ seconds laser beam rate of translation Frequency range.In addition, being investigated about 20 μm -70 μm at low-melting glass membrane interface of laser beam spot for exemplary weldering It connects.In some embodiments, it can be observed that illustratively welding line mass, wherein focal spot size is about 20 μm and translates Rate is 50mm/s.After these welding substrates are continued 4 hours to be formed without any crackle at 100 DEG C, it is also noted that To the robustness of these welding substrates.

Figure 32 is the schematic diagram of some embodiments.With reference to Figure 32, which, which instantiates, realizes Laser Welding using absorbing membrane A kind of exemplary, non-limitative method connect, wherein laser thermal energy can be sent in substrate/substrate interface 40 to be expanded Dissipating bind closes opposite contact area, in the given time as close possible to unification, while farthest reducing any subsidiary damage, Such as the spatial dimension and magnitude of residual-tensile stress.Weld interface synthesis speed ratio CTE misfit stress interface is formed The effect of the higher substrate of faster CTE, this method may be more significant.It therefore, in some embodiments, can be on welding circle Using the saccadic speed of focus on light beam and higher speed at face, formed with implementation example welding without any crackle.

In some embodiments, laser welding may be used at absorption (preferably A% > about 20%) under laser wavelength of incidence λ Film realize.In other embodiments, substrate and film can express at λ is formed centrally remarkably.In other embodiment In, temperature influence can be used for increasing the absorption of one or both of film and substrate at λ.This exemplary temperature influence may be used also To help to improve sealing or speed of welding, and heat affected area (HAZ) can be reduced and the work of creep flowage can be reduced Change energy, such as form eutectic system, alloy etc..In some embodiments, it if necessary to transparency, then can be provided in UV Band gap, or high-selenium corn is provided in NIR, IR.Other embodiment can provide interface surface energy γ_{Weld interface}> > remnants γ_{Stress field} And/or total mark bond strengthWelding.Other embodiment may include low sharp Luminous intensity requirement, laser peak photon flux is less than about 1025 photons/seconds/cm accordingly²It and does not include multi-photon attribute, ablation Or plasma generates.

Although it have been described that some embodiments use low-melting glass or inoranic membrane, but this paper appended claims Book should not necessarily be limited by this because embodiment can be used UV absorbing film, IRA film and/or between two substrates other are inorganic Film.As described above, in some embodiments, the colour center formation in exemplary substrate glass is not required, and with film UV absorb (for example, less than about 20%) variation and change.Therefore, in other embodiments, if the UV absorption of film is greater than about 20%, then alternative substrate, such as quartz, low CTE substrate etc. are easily formed welding.In addition, when using high CTE substrate, this A little substrates are easy to using illustrative high repetition frequency laser (for example, greater than about 300kHz is to about 5MHz) and/or low peak function Rate is welded.In addition, film absorption be influence factor embodiment in, exemplary IR laser system can be used to weld IR absorbs (visible transparent film).

In each embodiment of the disclosure, glass sealing material and obtained each layer be it is transparent and/or translucent, Thin, impermeable, " green ", and be configured to form airtight sealing at low temperature, and have enough close Sealing strength is to adapt to the big CTE difference between sealing material and adjacent substrate.In some embodiments, sealant can be free of Filler and/or adhesive.The inorganic material for being used to form sealant can not be based on frit, or in some embodiment party In formula, the powder (such as UVA, LMG etc.) formed by the glass ground can be.In other embodiments, layer material is sealed It is the low Tg glass under predetermined wavelength with basic optical absorption cross-section, the predetermined wavelength and the laser for being used for sealing technology Operation wavelength matching or substantially match.In other embodiment, at room temperature, low Tg glassy layer is to laser processing wave Long absorption is at least 15%.

In general, suitable sealant material includes the oxidation of low Tg glass and copper or tin with appropriate reaction Object.Glass sealing material can be formed by low Tg material, such as phosphate glass, borate glass, tellurite glasses and sulphur Belong to compound glass.As defined herein, the glass transition temperature of low Tg glass material is lower than 400 DEG C, such as less than 350 DEG C, 300 DEG C, 250 DEG C or 200 DEG C.Exemplary borate glass and phosphate glass include tin phosphate glass, tin fluorophosphate Glass and tin fluor borate glass.Sputtering target may include such glass material, alternatively, its precursor.Illustrative copper and tin oxygen Compound is CuO and SnO, can be formed by the sputtering target of the pressed powder including these materials.Optionally, glass capsulation combines Object may include one or more dopants, including but not limited to tungsten, cerium and niobium.If they can be right comprising these dopants Such as the optical property of glassy layer has an impact, and can be used for controlling absorption of the glassy layer to laser emission.For example, doping two Cerium oxide can increase absorption of the low Tg glass barriers in the case where laser machining wavelength.Other suitable sealant materials include liquid phase Line temperature has laser absorption less than or equal to about 1000 DEG C, less than or equal to about 600 DEG C or less than or equal to about 400 DEG C Low liquidus temperature (LLT) material.In other embodiments, the composition of inoranic membrane can be selected to reduce in induction State the activation energy of first base material, the second substrate or the first and second substrate creep flowages.

Illustrative tin fluorphosphate glass composition can be in corresponding ternary phase diagrams with SnO, SnF₂And P₂O₅It is each It is indicated from composition.Suitable UVA glass-film may include SnO₂、ZnO、TiO₂, ITO and other low-melting glass compositions.It closes Suitable tin fluorphosphate glass includes 20-100 moles of %SnO, 0-50 mole %SnF₂With 0-30 moles of %P₂O₅.Optionally, this A little tin fluorphosphate glass compositions may include 0-10 moles of %WO₃, 0-10 moles of %CeO₂And/or 0-5 moles of %Nb₂O₅.Example Such as, suitably form the tin fluorophosphate starting material of the doping of glass seal layer composition include 35 to 50 moles of %SnO, 30 to 40 moles of %SnF₂, 15 to 25 moles of %P₂O₅With the dopant oxygen compound of 1.5 to 3 moles of %, such as WO₃、CeO₂And/or Nb₂O₅.According to tin fluorphosphate glass composition described in a specific embodiment can be niobium doping tin-oxide/ Tin fluorophosphate/phosphorus pentoxide glass, it includes about 38.7 moles of %SnO, 39.6 moles of %SnF₂, 19.9 moles of %P₂O₅ With 1.8 moles of %Nb₂O₅.The sputtering target that can be used to form such glassy layer may include 23.04%Sn, 15.36%F, 12.16% P, 48.38%O and 1.06%Nb (being indicated in the form of atomic molar percentage).

The tin phosphate glass composition includes about 27%Sn, 13%P and 60%O according to another embodiment, It may originate from sputtering target, and the sputtering target includes about 27%Sn, 13%P and 60%O (in the form of atomic molar percentage table Show).It should be understood that various glass compositions disclosed herein can be related to the combination of the composition or source sputtering target of sedimentary Object.As tin fluorphosphate glass composition, illustrative tin fluor borate glass composition can be expressed as SnO, SnF₂ And B₂O₃Respective ternary phase diagrams composition.Suitable tin fluor borate glass composition includes that 20-100 moles of %SnO, 0-50 rub You are %SnF₂With 0-30 moles of %B₂O₃.These tin fluor borate glass compositions are optionally including 0-10 moles of %WO₃、0- 10 moles of %CeO₂And/or 0-5 moles of %Nb₂O₅.For forming the suitable low Tg glass group of glass seal layer from these materials The other aspects for closing object and method are disclosed in following file: No. 5,089,446 commonly assigned United States Patent (USP) and series number It is 11/207,691,11/544,262,11/820,855,12/072,784,12/362,063,12/763,541,12/879, 578 and 13/841, the full content of 391 U.S. Patent application, these files is totally incorporated herein by reference.

In some embodiments, inoranic membrane may include B₂O₃-ZnO-Bi₂O₃TERNARY GLASS.In some embodiments, Suitable glass can include about 10-80 moles of %B₂O₃, about 5-60 moles %Bi₂O₃About 0-70 moles %ZnO.Unrestricted In property embodiment, glass composition can include about 40-75 moles of %B₂O₃, about 20-45 moles %Bi₂O₃About 0-40 rubs You are %ZnO.Such glass can have relatively low Tg, and for example, less than about 600 DEG C, less than about 500 DEG C or be less than about 400 DEG C, such as in the range of about 300 DEG C to about 500 DEG C.

Illustrative substrate (glass or other) can have any appropriate size.Substrate can have area (length and width Degree) size, independently in the range of 1cm to 5m (such as 0.1,1,2,3,4 or 5m), and there is thickness, it can In the range of about 0.5mm to 2mm (such as 0.5,0.6,0.7,0.8,0.9,1.0,1.2,1.5 or 2mm).In other implementation In mode, base material thickness can in the range of about 0.05mm to 0.5mm (such as 0.05,0.1,0.2,0.3,0.4 or 0.5mm).In other embodiment, the thickness of glass baseplate can in the range of about 2mm to 10mm (such as 2,3,4, 5,6,7,8,9 or 10mm).The overall thickness of exemplary glass sealant can be in the range of about 100nm to 10 microns.Each In embodiment, the thickness of the layer can be, for example, less than 10,5,2,1,0.5 or 0.2 microns less than 10 microns.Illustratively Glass seal layer thickness includes 0.1,0.2,0.5,1,2,5 or 10 micron.The width of sealing area can be with laser spot size It is proportional, it can be about 0.05 to 2mm, such as 0.05,0.1,0.2,0.5,1,1.5 or 2mm.The rate of translation of laser is (i.e. Seal rate) can in the range of about 1mm/ seconds to 1000mm/ seconds, such as 1,2,5,10,20,50,100,200,400 or 1000mm/ seconds.Laser spot size (diameter) can be about 0.02 to 1mm.

It has therefore been discovered that when local glass temperature in spatial dimension (such as " welding volume ") be more than its strain or When annealing temperature (for example, being respectively 669 DEG C and 772 DEG C for EXG), it can be produced in some embodiments of the disclosure Raw suitable laser welding glass baseplate interface.The volume can depend on incident laser power, the composition of UVA or LMG melt, And colour center forms (due to caused by the impurity in corresponding substrate).Once reaching, then the volume can be scanned on interface zone, from And it generates between two substrates (glass or other substrates) and quickly and firmly seals.Can get is more than the close of 5-1000mm/s Seal speed.Exemplary laser welding can be in the substrate regions of the swept concern of laser, from high temperature relevant to melt volume It is converted to relatively cold environment temperature suddenly.The integrality of gastight seal and its corresponding intensity can be by as described below To maintain: the thinness of Slow cooling (self annealing) hot radical glass colour center (relaxation) region and UVA or the thin membrane regions LMG or NIR is (logical Chang Wei¹/₂- 1 μm), so that any influence of the CTE mispairing between two corresponding substrates (glass or other substrates) be made not act as With.

Choosing according to each embodiment, for the rectangular processing conditions at sealant on the glass substrate and sealing layer material It is sufficiently flexible for selecting, so that substrate is not adversely affected because of the formation of glassy layer.The glass of low melting temperature can be used for Seal or bond different types of substrate.Salable and/or combinative substrate includes glass, glass-glass laminate, glass Glass-polymer laminates, glass ceramics or ceramics, including gallium nitride, quartz, silica, calcirm-fluoride, magnesium fluoride or sapphire Substrate.Other substrate can be, but be not limited to metal base, including tungsten, molybdenum, copper or other kinds of suitable metal substrate.

For example, the non-limiting example of glass baseplate may include soda lime glass, sillico aluminate glass, alkali metal silicon Aluminate glass, borosilicate glass, alkali-metal borosilicates glass, aluminium borosilicate glass, composite alkali aluminum borosilicate glass Glass, alkaline-earth metal aluminium borosilicate glass and other suitable glass, optionally, they can be by chemical strengthening and/or Heat tempering.According to some non-limiting embodiments, can be fitted by the glass that ion exchange obtains chemical strengthening Cooperation is substrate.In each embodiment, the first and/or second substrate may include chemically reinforced glass, compression stress Greater than about 100MPa, and compression stress layer depth (DOL) is greater than about 10 microns.According to other embodiment, first and/or The compression stress of second glass baseplate can be greater than about 500MPa and DOL can be greater than about 20 microns or compression stress can To be greater than about 700MPa and DOL can be greater than about 40 microns.For example, the non-limiting reality of suitable commercially available glass baseplate Example includes the EAGLE of Corning Inc (Corning Incorporated)Lotus^TM、 Iris^TMWithGlass.According to some embodiments, at least one of first or second substrate includes glass or glass Ceramics.In other embodiment, the first and second substrates include glass or glass ceramics.

In some embodiments, a kind of substrate can be phosphor-containing glass plate, can be used for for example, light emitting device group In part.For example, including one of metal sulfide, metal silicate, metal aluminate or other suitable phosphors or a variety of Phosphor-containing glass plate can be used as the wavelength-conversion sheet in the white lamp of LED.The white lamp of LED generally includes the blue for emitting blue light LED chip is to be formed using III-th family based on the compound semiconductor of nitride.For example, the white lamp of LED can be used for shining Bright system, or the backlight as liquid crystal display.Low melting temperature glass disclosed herein and relevant encapsulating method can For sealing or encapsulating LED chip.

Since substrate can enhance to form colour center using universal laser irradiation condition and generated temperature, by The illustrative methods according to embodiment of the present disclosure can be made in the property of base substrate (glass or other substrates) It is possibly realized.In some embodiments, if it is desired to which transparent sealing, then colour center formation are reversible.If each substrate has Different thickness then can be used thermal conductivity substrate to repair weld integrity in some embodiments.

Therefore, illustrative embodiments can be used low melting temperature material and low laser pulse peaks power to glass or Other materials substrate carry out laser welding, with minimally formed shock wave and ensure be not in can be to tensile break strength Hurtful micro-crack.Illustrative embodiment can also provide Diffusion Welding in the case where no molten bath is spread, to permit Temperature sealing technology lower enough is provided perhaps.Due to the thinness of diaphragm area, embodiment of the present disclosure can eliminate two phases Any influence of the CTE mispairing between substrate is answered, and may be used to provide the welding of adjoining dimensions or different substrates.This Outside, in embodiment of the present disclosure, sealing is not needed to pattern film for frit or coloring material, because This manufacturer need not disclose its exclusive design.

The disclosure is taught that low melting temperature material how can be used to be laser welded glass-encapsulated part, thus Permanent air tight work can be carried out to the passive and active device sensitive to degradation caused by oxygen and moisture invasion.Institute as above It states, embodiment as described herein provides UVA, LMG or other sealing elements, after by the assembling of each mating surface, can use These sealing elements of laser absorption thermal activation, and these sealing elements can have higher manufacture efficiency, because sealing each work The rate for making device by thermal activation and can combine and be formed and determine, rather than by by vacuum or inert gas assembly line Line (inline) film deposition determines the rate that device is packaged.This can be sealed large stretch of multiple device, then It delineates into each device (individualized), and due to mechanical integrity height, individualized yield can be higher.

Embodiment of the present disclosure additionally provide a kind of package sealing with laser method (such as laser welding, Diffusion Welding etc.) and Illustrative laser absorption film, the method depend under laser wavelength of incidence, and the colour center in glass baseplate is formed, and is somebody's turn to do Colour center is formed as caused by the inherent colour center of external colour center (such as impurity or dopant) or glass inherently.Some non-limits of film Property example processed includes SnO₂、ZnO、TiO₂, ITO and the low-melting glass film workable for glass baseplate interface.Use these materials The welding of material can provide visible transmission, and there is enough UV to absorb to cause mild stable state Diffusion Welding.These materials Material can also be provided with partially sealed temperature, and the temperature is suitable for the transparent laser welding of Diffusion Welding.This Diffusion Welding So that corresponding glass baseplate is carried out low-power and low temperature laser welding, and can be generated with effective and quick speed of welding excellent Different Vitreous solder.It may also rely on colour center shape according to Exemplary laser welding procedure described in some embodiments of the disclosure The photoinduction hydrophilicity characteristic of glass after, to include temperature-induced absorption.

The air-tightness encapsulating of the workpiece carried out using disclosed material and method can contribute to long-time operation originally The device for sensitivity of degrading caused by being invaded to oxygen and/or moisture.Exemplary workpiece, device or application include flexible, rigidity or Semi-rigid organic LED, OLED illumination, OLED TV, photovoltaic part, MEM display, electrochromic, fluorogen, alkali metal electricity Pole, transparent conductive oxide, quantum dot etc..

For practical purposes, inner liner used herein is substantially air impermeable, and to moisture and/or oxygen Substantially without infiltrative layer.For example, gastight seal can be configured to be restricted to be less than by oxygen transpiration (diffusion) About 10^-2cm³/m²/ day is (for example, be less than about 10^-3cm³/m²/ day), and water flow ease (diffusion) is restricted to about 10^-2g/m²/ day (for example, being less than about 10^-3g/m²/ day, 10^-4g/m²/ day, 10^-5g/m²/ day or 10^-6g/m²/ day).In embodiments, air-tightness Sealing element is suppressed to air and water contacts shielded workpiece.In some embodiments, it is a kind of to two substrates into The method that row combines includes: that the first glassy layer is formed on the sealing surfaces of first base material；On the sealing surfaces of the second substrate Form the second glassy layer；The first glassy layer of at least part is placed, it is physically contacted with the second glassy layer of at least part；With And each glassy layer is heated with each glassy layer of local melting and sealing surfaces, thus between first base material and the second substrate Form the welding of glass and glass.In every kind of sealing structure disclosed herein, can then it be cooled down by local heating, fusing Glassy layer and the glass baseplate material of neighbouring seal interface realize the sealing carried out using low melting temperature glassy layer.

Therefore, embodiment of the present disclosure will form gastight seal relevant to laser welding on one side Easiness combination, to be similarly formed the air-tight packaging part of active OLED or other devices, allows it to manufacture extensively.It is this Manufacture needs to be welded above conductive interface film.Different from method disclosed herein, conventional laser encapsulating method can be with This interfacial conductive lead is cut off, especially if interface temperature becomes the phase of excessively high or laser emission with conductive lead line material Interaction be it is harmful, then can cut off this interfacial conductive lead.However, embodiment of the present disclosure uses low melting temperature glass Glass material interface film, which can obtain, requires the apparatus structure of electrical bias to operate for air-tightness device.Therefore, the reality of this theme The mode of applying can provide the successful laser welding of other substrates of sheet glass or conductive interfacial film, without destroying or damaging Lose performance.

It in some embodiments, include: to form nothing in the top on first base material surface to the method that workpiece is combined Machine film；Workpiece to be protected is arranged between first base material and the second substrate, wherein connect the film with the second substrate Touching；And by using with predetermined wavelength laser emission to film carry out local heating by workpiece be incorporated in first base material with Between second substrate.Inoranic membrane, first base material or the second substrate can have transmittance at about 420nm to about 750nm.Another In a embodiment, transmittance is all had under inoranic membrane, first base material and each leisure about 420nm to about 750nm of the second substrate.? In other embodiment, absorption of the inoranic membrane under predetermined optical maser wavelength is higher than 10%.In other embodiment, inorganic The composition of film may be, but not limited to, SnO₂、ZnO、TiO2、ITO、Zn、Ti、Ce、Pb、Fe、Va、Cr、Mn、Mg、Ge、SnF₂、 ZnF₂And combinations thereof.In other embodiments, the composition of inoranic membrane can be selected to reduce induction first base material, the The activation energy of two substrates or the first and second substrate creep flowages.In another embodiment, the composition of inoranic membrane can be with It is that absorption of the liquidus temperature less than or equal to about 1000 DEG C, less than or equal to about 600 DEG C or less than or equal to about 400 DEG C swashs The low liquidus temperature materials of light.In other embodiment, combination can be formed in conjunction with step, synthesis bond strength is greater than The synthesis bond strength of first base material, the second substrate or the residual stress field in the first and second substrates.Some exemplary It is this in conjunction with can only be failed by cohesional failure in embodiment.In other embodiment, the composition of inoranic membrane can be with Include 20-100 moles of %SnO；0-50 moles of %SnF₂；With 0-30 moles of %P₂O₅Or B₂O₃.In some embodiments, inorganic The combination internal transmission rate of film and the first and second substrates at about 420nm to about 750nm is higher than 80%.In other embodiment party In formula, in conjunction with step further include by with the laser emission with predetermined wavelength come local heating inoranic membrane and first base material with Workpiece is combined between second substrate, it is described to change in conjunction with according to the impurity composition variation in first or second substrate, and root Change according to the composition variation of inoranic membrane.Exemplary impurity in first or second substrate can be, but be not limited to As, Fe, Ga, K, Mn, Na, P, Sb, Ti, Zn, Sn and combinations thereof.In other embodiment, the first and second substrates have different transverse directions Size, different CTE, different thickness or combinations thereof.In some embodiments, one of first and second substrates can be with It is glass or glass ceramics.Certainly, the another kind in the first and second substrates can be glass ceramics, ceramics or metal.One In a little embodiments, the method may also include the step of annealing to the workpiece of combination.In other embodiments, laser Radiation includes the UV radiation at about 193nm to the predetermined wavelength between about 420nm, in about 780nm between about 5000nm NIR radiation under predetermined wavelength, laser emission may include the pulse width of 1 to 40 nanosecond and the repetition rate of at least 1kHz, and And/or person can be continuous wave.In other embodiment, the thickness of inoranic membrane is in the range of about 10nm to 100 μm.? In some embodiments, first base material, the second substrate or the first and second substrates may include alkaline-earth metal boroaluminosilicate glass Glass, thermal reinforced glass, chemically reinforced glass, borosilicate glass, alkali aluminosilicate glass, soda-lime glass and combinations thereof. In other embodiments, the method can comprise the following steps that mobile by laser with the speed of about 1mm/s to about 1000mm/s The laser facula formed is radiated, to form the smallest heating zone.In some embodiments, which is no more than laser facula Diameter multiplied by the repetition rate of laser emission product.In other embodiment, in conjunction with step can formation width be about 50 μ M to about 1000 μm of bonding wire.In other embodiments, before and after combining step, inoranic membrane, first base material or the Two substrates the optical clarity under about 420nm to about 750nm can in following range: greater than 80%, 80% to 90% Between, be greater than 85% or be greater than 90%.A kind of illustrative workpiece can be, but be not limited to light emitting diode, organic light emission two Pole pipe, conductive lead wire, semiconductor chip, ITO lead, patterned electrodes, continuous electrode, quanta point material, phosphor and its group It closes.

In other embodiments, a kind of coupling apparatus is provided comprising in the nothing that first base material surface is formed Machine film, and the shielded device between first base material and the second substrate, wherein inoranic membrane is contacted with the second substrate.? In such embodiment, described device include and with the laser emission with predetermined wavelength come local heating inoranic membrane The combination formed between first base material and the second substrate, this becomes in conjunction with according to the impurity composition variation in first or second substrate Change, and is changed according to the composition of inoranic membrane and changed.In addition, inoranic membrane, first base material or the second substrate are in about 420nm to about There can be transmittance under 750nm.In another embodiment, inoranic membrane, first base material and each leisure about 420nm of the second substrate Transmittance is all had under to about 750nm.In other embodiment, absorption of the inoranic membrane under predetermined optical maser wavelength is higher than 10%.In other embodiment, the composition of inoranic membrane may be, but not limited to, SnO₂、ZnO、TiO₂、ITO、Zn、Ti、Ce、 Pb、Fe、Va、Cr、Mn、Mg、Ge、SnF₂、ZnF₂And combinations thereof.In other embodiments, the composition of inoranic membrane can be carried out Selection is to reduce induction first base material, the second substrate or the activation energy of the first and second substrate creep flowages.In another reality Apply in mode, the composition of inoranic membrane can be liquidus temperature less than or equal to about 1000 DEG C, less than or equal to about 600 DEG C or The low liquidus temperature materials of absorption laser less than or equal to about 400 DEG C.In other embodiment, in conjunction with comprehensive knot Close the synthesis bond strength that intensity is greater than first base material, the second substrate or the residual stress field in the first and second substrates.? It is this in conjunction with can only be failed by cohesional failure in some illustrative embodiments.In other embodiment, inoranic membrane Composition may include: 20-100 moles of %SnO；0-50 moles of %SnF₂；With 0-30 moles of %P₂O₅Or B₂O₃.In other reality It applies in mode, the composition of inoranic membrane includes: 10-80 moles of %B₂O₃, 5-60 moles of %Bi₂O₃With 0-70 moles of %ZnO.One In a little embodiments, the combination internal transmission rate of inoranic membrane and the first and second substrates at about 420nm to about 750nm is higher than 80%.Exemplary impurity in first or second substrate can be, but be not limited to As, Fe, Ga, K, Mn, Na, P, Sb, Ti, Zn, Sn and combinations thereof.In other embodiment, the first and second substrates have different lateral dimensions, different CTE, difference Thickness or combinations thereof.In some embodiments, one of first and second substrates can be glass or glass ceramics.When So, the another kind in the first and second substrates can be glass ceramics, ceramics or metal.In other embodiment, inorganic The thickness of film is in the range of about 10nm to 100 μm.In some embodiments, first base material, the second substrate or the first and Second substrate may include alkaline-earth metal Boroalumino silicate glasses, alkali metal aluminosilicate glass, thermal reinforced glass, chemical strengthening glass Glass, soda-lime glass, borosilicate glass and combinations thereof.In other embodiments, inorganic before and after combining step Film, first base material or the second substrate the optical clarity under about 420nm to about 750nm can in following range: greater than 80%, between 80% to 90%, greater than 85% or greater than 90%.A kind of illustrative device can be, but be not limited to shine Diode, Organic Light Emitting Diode, conductive lead wire, semiconductor chip, ITO lead, patterned electrodes, continuous electrode, quantum dot Material, phosphor and combinations thereof.In some embodiments, in conjunction with can be air-tightness, there is closed loop or to be greater than about 1 The seal line that the angle of degree is intersected, may include the binding site being spatially separated, and/or can be located at the temperature-sensitive from combination At position of the material less than about 1000 μm.In other embodiments, it can be patterned in conjunction with the birefringent of surrounding.

In other embodiment, the method that a kind of pair of device is protected is provided, the method includes first The first part surface of substrate forms inorganic film；By device to be protected be arranged in first base material and the second substrate it Between, wherein contacting sealant with the second substrate；And use laser emission local heating inorganic film and first and second base Material is so that sealant and substrate melt and form sealing between each substrate.First base material may include glass or glass ceramics, and Second substrate may include metal, glass ceramics or ceramics.In some embodiments, the first and second substrates have different cross To size, different CTE, different thickness or combinations thereof.In other embodiments, described device may be, but not limited to, ITO lead, patterned electrodes and continuous electrode.In some embodiments, the step of local heating further includes adjustment laser spoke The power penetrated is to reduce the damage of the sealing to formation.A kind of illustrative film can be, but be not limited to low Tg glass, it includes 20-100 moles of %SnO, 0-50 moles of %SnF2 and 0-30 moles of %P₂O₅Or B₂O₃, or alternately rub comprising 10-80 You are %B₂O₃, 5-60 moles of %Bi₂O₃With 0-70 moles of %ZnO.In other embodiments, can composition to inoranic membrane into Row selection is to reduce induction first base material, the second substrate or the activation energy of the first and second substrate creep flowages.At another In embodiment, the composition of inoranic membrane can be liquidus temperature less than or equal to about 1000 DEG C, less than or equal to about 600 DEG C or The low liquidus temperature materials of absorption laser of the person less than or equal to about 400 DEG C.It in other embodiment, can in conjunction with step It is formed and is combined, synthesis bond strength is greater than the residual stress field in first base material, the second substrate or the first and second substrates Synthesis bond strength.It is this in conjunction with can only be failed by cohesional failure in some illustrative embodiments.

According to other non-limiting embodiment, a kind of sealing device is provided comprising on first base material surface It is rectangular at inoranic membrane；The second substrate contacted with inoranic membrane；And welding region, the welding region be included in first base material and The combination formed between second substrate, and the combination extends to second in the second substrate from the first depth in first base material Depth.Inoranic membrane may include at least one inoranic membrane element, and one or both of first base material and the second substrate include At least one inorganic substrate element.In other embodiment, the first nothing of the first or second substrate in welding region Machine film concentration of element is higher than the second inoranic membrane concentration of element of the first or second substrate outside welding region.According to other implementation Mode, the first base material concentration of element of welding region can be higher than the second substrate concentration of element of the inoranic membrane outside welding region. In other embodiment, the second inoranic membrane can be formed above the second substrate surface.

In some embodiments, inoranic membrane and optionally at least one of first or second substrate about 420nm extremely There is transmittance under wavelength within the scope of about 750nm.In other embodiment, first base material, the second substrate and inoranic membrane In each all have transmittance under the wavelength within the scope of about 420nm to about 750nm.In other embodiments, it welds Region can be transparent.One of first base material or the second substrate or both can be selected from glass or glass ceramics, such as Soda lime glass, sillico aluminate glass, alkali metal aluminosilicate glass, borosilicate glass, alkali-metal borosilicates glass Glass, aluminium borosilicate glass, composite alkali aluminum borosilicate glass and alkaline-earth metal aluminium borosilicate glass.According to certain embodiment party Formula, first base material or the second substrate may include polymer, ceramics or metal.Inoranic membrane can have the group comprising following substance Close object: 20-100 moles of %SnO；0-50 moles of %SnF₂；With 0-30 moles of %P₂O₅Or B₂O₃.Inoranic membrane can also have The composition of following substance: 10-80 moles of %B₂O₃；5-60 moles of %Bi₂O₃；With 0-70 moles of %ZnO.According to each implementation The thickness of mode, inoranic membrane can be in the range of about 0.1 micron to about 10 microns.In other embodiment, welding region Thickness can be in the range of about 0.3 micron to about 14 microns.In some embodiments, sealing device may also include at least Surround the stress area of welding region, wherein the first stress in stress area is greater than the second stress outside stress area.Example Such as, the first stress can be in the range of greater than about 1MPa to about 25MPa.In other embodiment, the first stress relative to The ratio of second stress is in the range of about 1.1:1 to about 25:1.According to certain embodiments, the thickness of stress area can be about In the range of 20 microns to about 500 microns.

In other embodiment, a kind of sealing device is provided comprising formed in first base material surface Inoranic membrane；The second substrate contacted with inoranic membrane；And welding region, the welding region are included in first base material and the second base The combination formed between material.One or both of first base material and the second substrate may include at least one inorganic substrate element. In each embodiment, welding region compared to welding region outside a part of inoranic membrane be rich in the inorganic base of at least one Material element.In other embodiment, a kind of sealing device is provided comprising in the nothing that first base material surface is formed Machine film；The second substrate contacted with inoranic membrane；And welding region, the welding region are included in first base material and the second substrate Between the combination that is formed.Inoranic membrane may include at least one inoranic membrane element.In some embodiments, first or second substrate Including the first part in welding region and the second part outside welding region.According to other embodiment, compared to Second part, first part is rich at least one inoranic membrane element.It in other embodiment, can be in the second substrate The top on surface forms the second inoranic membrane.

Following examples further illustrate various aspects of the disclosure, these embodiments are only non-limiting and illustrate Property, the scope of the present invention is limited by claims.

Embodiment

Experimental method

With comprising low-melting glass 1 μ m-thick inoranic membrane coat the first glass baseplate (200 μ m-thicks it is healthy and free from worry), And make the inoranic membrane and the second glass baseplate (healthy and free from worry EAGLE of 500 μ m-thicks) contact to prepare stack.Use with 50mm/s translation, and pulse width is 10 seconds and average incident power is 6W 35kHz pulse UV laser (355nm) carries out Welding.Laser slightly defocuses (focus below interface~3mm) from interface, and spot diameter is 200 microns, and the residence time is 4ms.Continuously linear is carried out above substrate by the way that form 200 microns thick of each welding portion W, they pass through unwelded part I and be spaced 200 microns, as shown in figure 37.

4mm pit C with flat bottom is pierced in sealing device, depth of 5 μm from weld interface is drilled into.Pit C Periphery be represented by dashed line in Figure 37.Then in the welding region in welding portion W and near welding region, and non- In seal interface in welding portion I and seal interface nearby carries out depth distribution analysis, and wherein exemplary analysis region is by scheming Square A in 37 is indicated.Depth zero corresponds to the flat bottom of pit, while having following approximate depth correlation:(depth :~0-2 μm), LMG (depth :~2-3 μm), EAGLE(depth :~3-8 μm).Using it is secondary from Sub- mass spectrography (SIMS) carries out element research to membrane element plain (F, P, Sn) and substrate element (Al, B, Si).

Welding region: film migration of element

The data sampler from non-solder region I is collected, indicates the interface composition of welding " before ".It also collects and carrys out self-brazing The data sampler of region W is connect, indicates being welded to form for welding " later ".Figure 38 A-C shows the number of membrane element plain (F, P, Sn) According to sample.By being superimposed " before " and " later " spatial distribution of every kind of element, normalizing is carried out to the maximum intensity MAX of peak value Change, and compares all-wave half-peak FWHM value to be compared to determine migration length M.

With reference to Figure 38 A, the migration length M of fluorine can be calculated by FHWM: 3.973 μm -3.368 μm=0.608 μm.However, by The migration except known film thickness is shown (possibly due to from adjacent welding in fluorine data in non-solder region Heat effect), therefore, it is considered that the migration length of fluorine may be even higher, such as up to 1 μm.The migration that Figure 38 B instantiates phosphorus is long It spends (3.468 μm -3.204 μm=0.264 μm), and Figure 38 C instantiates the migration length (3.636 μm -3.253 μm=0.383 of tin μm).Figure 38 A-C illustrates respectively the asymmetric depth distribution of welding region W, for example, F, P and Sn towardsSubstrate (depth: 0-2 μm) ratio is migrated towards EAGLEThe migration (depth: 3-8 μm) of substrate is faster.Without being bound by theory, it is believed that Migration is driven by faster heat dissipation relevant to relatively thin glass baseplate, even if under fast laser trace time section (~4ms) So.

It can be by by " apparent diffusion " coefficient for square calculating every kind of membrane element element divided by the residence time of migration length. For example, in the case where fluorine, D_F=(0.608x10^-4cm)²/ 0.004s=9.2x10^-7cm²/s.The similar system of phosphorus can be calculated Number (D_P=1.7x10^-7cm²/ s) and tin similar coefficient (D_Sn=3.7x10^-7cm²/s).The apparent expansion of laser welding process Dissipating coefficient total amount value is about 10^-7cm²/s.Even if the problem of spreading in the environment may be influenced (for example, membrane element element is big by considering Small, chemical valence, chemical potential, temperature etc.), compared with the typical element diffusion rate in glass melt, this diffusivity is also fast Much, at high temperature so.For example, having measured the phosphorus diffusion of phosphorus glass melt at 1000 DEG C about 10^-14cm²/ S to about 10^-16cm²In the range of/s.Therefore, at similar temperature, " apparent diffusion " rate measured is more than typical diffusion " apparent diffusion " about 7 or 8 orders of magnitude of rate in system, this may indicate that the chemical composition change of welding region is by except expansion What the event except dissipating drove.

For example, in the welding process, the swelling (for example, " convex " is formed) and local deformation of film and/or substrate can be with Explain film migration of elements and these elements and the mixing of substrate element and welding region that form chemical composition different.? To the thickness of welding region can be the function of membrane element element migration length, for example, t_w=t_i+M₁+M₂, wherein t_wIt is welding region Thickness, t_iIt is the original depth of inoranic membrane, M₁It is that given element moves to migration length in first base material, and M₂It is element Move to the migration length in the second substrate.With reference to Figure 35 C, in some embodiments, migration length M₁It can correspond to depth D1, and migration length M₂It can correspond to depth d2.

Welding region: substrate migration of element

Figure 39 A-C is collected and is compared from the substrate of non-solder region I (" before ") and welding region W (" later ") member The data sampler of plain (Al, B and Si).By being superimposed the spatial distribution of " before " and " later " of every kind of element, and compare sealing Boundary strength range (Δ r) and welding region strength range (Δ e) is compared, to determine enrichment percentage according to the following formula:

With reference to Figure 39 A, the aluminium enrichment in welding region may be calculated 3.32/4.74x100%=70.0%.Figure 39 B is same Sample instantiates boron enrichment (1.15/2.59x100%=44.4%), and Figure 39 C instantiates silicon enrichment (0.69/1.46x100%= 47.3%).It assume that these enrichment values indicate to form point of matched welding region composition with substrate based on element one by one Number.Without being bound by theory, it is believed that as laser residence time extension and/or welding temperature increase, enrichment value will also increase, because It is swollen in another substrate for described two substrates, mixing and effectively " dilution " welding region.The journey that this thing happens It spends the intensity that may depend on welding temperature and substrate is exposed to the time of the temperature.

There is substrate element since welding region is highly enriched, even if under very of short duration laser residence time (~4ms), Also the viscoplasticity expansion for thinking substrate may be to make substrate migration of element, and mix these elements and formationization with membrane element element Learn the main process for forming different welding regions.In consideration of it, thinking that applying pressure can also rise in the formation of welding region To effect, for example, applying enough pressure to ensure substrate towards swelling each other and expand to form covalent bond, then again from weldering Area is met to remove the heat from laser beam and obtain final welding region composition.

Stress area

The first glass baseplate is coated by the 1 μ m-thick inoranic membrane that apparatus difference shown in following Table I forms, and is made described Inoranic membrane contacts to prepare various stacks with the second glass baseplate.It is translated using the friction speed that following table I is indicated, and arteries and veins The 35kHz pulse UV laser (355nm) that width is 10 seconds and average incident power is 6W is rushed to be welded.Laser is omited from interface It is micro- to defocus (focus below interface~3mm), and spot diameter is 200 microns.It measures in welding region and welding region is all The stress that encloses simultaneously is depicted as depth function in Figure 40.

Table I: film composition and laser scanning speed

Sample	Composition	Laser speed (mm/s)
			A	TiO2	20
B	TiO2	50
			C	ZnO	20
D	ZnO	50
			E	LMG200	20
F	LMG200	50
			G	LMG
H	Stainless steel

As that, for every kind of test sample, can observe the stress influence area of encirclement welding region simultaneously from seeing in Figure 40 And it can be large enough to several hundred microns or bigger.Stressed zone can indicate that the stress on glass increases at least about 1-5MPa, or very Up to 25MPa or higher is increased to being, such as in following range: about 2MPa to about 20MPa, about 3MPa to about 15MPa, about 4MPa to about 10MPa or about 6MPa to about 8MPa, including therebetween all ranges and subrange.

Although this specification may include many details, these should not constitute the limitation of its range, but describe for tool Specific features for the embodiment of body.It is crossed above in the described in the text up and down of individual embodiment certain Feature is also implemented in combination with single embodiment.On the contrary, single embodiment it is upper and lower described in each feature can also Individually or with any appropriate subitem combination to implement in multiple embodiments.Moreover, although hereinbefore each feature can It is described as working in the form of certain combinations, or even is initially also to require in this way, but one in required combination Or multiple features can be removed from the combination in some cases, required combination can be related to subitem combination or subitem Combined version.

Similarly, although describing to operate according to particular order in attached drawing or picture, these operations are not construed as It needs the particular order by diagram or successively carries out, or carry out the operation of all diagrams, to obtain desired result.Certain In the case of, multitasking can be preferred with parallel processing.

Shown in the various constructions and embodiment illustrated in 0 picture 1-4, it has been described that using low-melting glass or absorb thin Each embodiment of film progress package sealing with laser.

Herein, range can be expressed as since " about " occurrence and/or terminate to " about " another occurrence. When stating this range, example includes stopping from a certain occurrence beginning and/or to another occurrence.Similarly, when using leading When word " about " indicates that numerical value is approximation, it should be appreciated that specific value constitutes on the other hand.It will also be appreciated that each model The endpoint value enclosed is all meaningful in and independently of another endpoint value in the case where related to another endpoint value.

The term as used herein " basic ", " substantially " and its version are intended to indicate that the feature is equal or approximate to Equal to a numerical value or description.For example, " substantially flat " surface is intended to indicate that flat or general planar surface.In addition, " essentially similar " is intended to indicate that two values are equal or approximately equal.

Although each feature, element or the step of particular implementation can be disclosed using interlanguage "comprising", answer Understand, which imply include can be used interlanguage " by ... constitute " or " substantially by ... constitute " describe including replace Transsexual embodiment.Thus, for example, the implicit alternative embodiment of the device comprising A+B+C is including wherein device by A+B The embodiment of+C composition and the embodiment that wherein device is substantially made of A+B+C.

It will be apparent to those skilled in the art the disclosure can be carry out various modifications and change and Without departing from the scope of the present disclosure and spirit.Because those skilled in the art is contemplated that the spirit and essence for having merged the disclosure Disclosed embodiment it is various it is improved combination, subitem combination and variation, therefore, it is considered that the disclosure includes appended power Full content and its equivalent within the scope of sharp claim.

Claims (26)

1. a kind of sealing device comprising:

In the inoranic membrane that first base material surface is formed；

The second substrate contacted with the inoranic membrane；With

Welding region, it includes the combinations formed between first base material and the second substrate, and it is from first base material One depth extends to the second depth in the second substrate；

Wherein, inoranic membrane includes at least one inoranic membrane element, and wherein, one of first base material and the second substrate or two Kind includes at least one inorganic substrate element；And

Wherein, the first inoranic membrane concentration of element of the first base material in welding region or the second substrate is higher than outside welding region Second inoranic membrane concentration of element of first base material or the second substrate.

2. sealing device as described in claim 1, wherein in inoranic membrane and optional first base material or the second substrate at least There is transmittance under a kind of wavelength within the scope of about 420nm to about 750nm.

3. such as sealing device of any of claims 1-2, wherein the welding region is transparent.

4. sealing device as claimed in any one of claims 1-3, wherein at least one of first base material or the second substrate Including glass, glass ceramics, ceramics, polymer or metal.

5. such as sealing device of any of claims 1-4, wherein first base material and the second substrate include glass or Glass ceramics.

6. sealing device according to any one of claims 1 to 5 further includes being formed in the surface of the second substrate Second inoranic membrane.

7. such as sealing device of any of claims 1-6, wherein the inoranic membrane has consisting of:

20-100 moles of %SnO；

0-50 moles of %SnF₂；With

0-30 moles of %P₂O₅Or B₂O₃。

8. such as sealing device of any of claims 1-6, wherein the inoranic membrane has consisting of:

10-80 moles of %B₂O₃；

5-60 moles of %Bi₂O₃；With

0-70 moles of %ZnO.

9. such as sealing device of any of claims 1-8, wherein at least one inoranic membrane element is selected from: F, P, Sn, B, Bi, Zn, Ti, W, Ce, Nb, Pb, Fe, Va, Cr, Mn, Mg, Ge and combinations thereof.

10. sealing device as claimed in any one of claims 1-9 wherein, wherein the first inoranic membrane concentration of element is more inorganic than second Film concentration of element up at least about 5 moles of %.

11. sealing device as described in claim 1, wherein the first base material concentration of element in welding region is higher than welding section Second substrate concentration of element of overseas inoranic membrane.

12. sealing device as claimed in claim 11, wherein it is described at least one inorganic substrate element be selected from Al, B, Si, Na, Li, K, Mg, Ca, Ba, and combinations thereof.

13. sealing device as claimed in claim 11, wherein first base material concentration of element is up to than the second substrate concentration of element Few about 30 moles of %.

14. such as sealing device of any of claims 1-13, wherein the thickness of the inoranic membrane is at about 0.1 micron To in the range of about 10 microns.

15. such as sealing device of any of claims 1-13, wherein the thickness of the welding region is micro- about 0.3 In the range of 14 microns of meter Zhi Yue.

16. the sealing device as described in any one of claim 1-15 further includes the stressed zone at least surrounding welding region Domain, wherein the first stress in stress area is greater than the second stress outside stress area.

17. sealing device as claimed in claim 16, wherein the first stress is in the range of greater than about 1MPa to about 25MPa.

18. sealing device as claimed in claim 16, wherein the first stress relative to the second stress ratio in about 1.1:1 To about 25:1.

19. sealing device as claimed in claim 16, wherein the thickness of stress area is at about 20 microns to about 500 microns In range.

20. a kind of sealing device comprising:

In the inoranic membrane that first base material surface is formed；

The second substrate contacted with the inoranic membrane；With

Welding region, it includes the combinations formed between first base material and the second substrate, and it is from first base material One depth extends to the second depth in the second substrate；

Wherein, inoranic membrane includes at least one inoranic membrane element, and wherein, one of first base material and the second substrate or two Kind includes at least one inorganic substrate element；And

Wherein, the first base material concentration of element in welding region is dense higher than the second substrate element of the inoranic membrane outside welding region Degree.

21. a kind of sealing device comprising:

In the inoranic membrane that first base material surface is formed；

The second substrate contacted with the inoranic membrane；With

It include the welding region of the combination formed between first base material and the second substrate；

Wherein, one or both of first base material and the second substrate include at least one inorganic substrate element；And

Welding region compared to welding region outside a part of inoranic membrane be enriched at least one inorganic substrate element.

22. sealing device as claimed in claim 21, wherein the first inorganic substrate concentration of element that welding region includes is than weldering Meet the second inorganic substrate concentration of element height at least 30 moles of % in a part of inoranic membrane outside region.

23. a kind of sealing device comprising:

In the inoranic membrane that first base material surface is formed；

The second substrate contacted with the inoranic membrane；With

It include the welding region of the combination formed between first base material and the second substrate；

Wherein, inoranic membrane includes at least one inoranic membrane element；

Wherein, first base material includes the first part in welding region and the second part outside welding region；And

Compared to second part, first part is enriched at least one inoranic membrane element.

24. sealing device as claimed in claim 23, wherein the first inoranic membrane concentration of element that first part includes is than second The second inoranic membrane concentration of element height at least 5 moles of % in part.

25. the sealing device as described in any one of claim 23-24, wherein first part extends to from seal interface In one substrate, the depth of extension is in the range of about 0.1 μm to about 2 μm.

26. the sealing device as described in any one of claim 23-25, wherein the second substrate includes the in welding region Part IV outside three parts and welding region, and wherein, compared to Part IV, Part III is enriched with described at least one Kind inoranic membrane element.