CN105593182A - Methods of treating glass surfaces - Google Patents
Methods of treating glass surfaces Download PDFInfo
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- CN105593182A CN105593182A CN201480053148.XA CN201480053148A CN105593182A CN 105593182 A CN105593182 A CN 105593182A CN 201480053148 A CN201480053148 A CN 201480053148A CN 105593182 A CN105593182 A CN 105593182A
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- glass surface
- overetched
- glass
- cleaning
- sludge
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
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- Life Sciences & Earth Sciences (AREA)
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- Surface Treatment Of Glass (AREA)
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Abstract
Disclosed herein are methods for treating an etched glass surface comprising applying a cleaning solution comprising at least one mineral acid to a glass substrate that has been etched. Also disclosed herein is a cleaning solution comprising at least one mineral acid for cleaning a glass substrate that has been etched.
Description
The cross reference of related application
The application requires No. 61/858292, U.S. Provisional Application series number submitting on July 25th, 2013Priority, herein, taking the content of this application as basis, the full content of this application is included in herein by reference.
Technical field
The present invention relates to a kind of processing method through overetched glass surface, described method comprise by comprise toThe solution of few a kind of inorganic acid is applied to this through overetched glass surface. In some embodiment at least,Glass surface is through a kind of etching of the etchant that comprises fluorine ion. In some embodiments, this solution bagContain at least one not inorganic acid of fluoride ion. The invention still further relates to for the treatment of through overetched glass surfaceThe solution that comprises at least one inorganic acid. In some exemplary embodiment, described cleaning solution is notFluoride ion. The invention still further relates to utilize comprise fluorine ion etchant etching cross through overetched glass tableFace, this glass surface is prepared by a kind of method, and the method comprises and will comprise at least one inorganic acidSolution be applied to this through overetched glass surface.
Background
Manufacturing in the process of face glass, make the processing (for example etching) of face glass thinning unrare,For example after assembling LCD module, will carry out this kind of processing. For example, can use hydrofluoric acid (HF) to makeFace glass is thinned to the substrate thickness in the scope of the 0.4mm of about 0.1mm～approximately. But, thinningOr etching process can produce a kind of slightly solubility accessory substance that is called as sludge. Sludge generates also in etching processCan be attached to glass surface, thereby glass is polluted. Physics and/or chemical method pair can utilizedFace glass carries out, after etching, cleaning and/or remove the sludge on this face glass.
For example, can after etching, scrub face glass clean. But, scrub clean may leadingCause the damage of the glass surface that can make strength of glass reduction and surface quality reduction. Scrubbing clean grade for physics sideIn method, can be first in rinse water to cleaning through overetched glass in advance, then scrub clean.In the time of pollutant water soluble, can use simple water to clean. But, scrub the clean glass that is usually used toThe poorly water-soluble of the lip-deep pollutant of glass and/or its are firmly attached in the situation of glass surface. But, brushWash down the clean pollutant that not only can remove glass surface, also can cause cut or defect at glass surface. TheseCut and defect can reduce intensity and the performance of glass greatly, even if the shape of defect is less and/or more shallow.
Another kind is to utilize Chemical cleaning to the method for cleaning through overetched glass surface. Chemical cleaningCan overcome some limitations of physical cleaning method. In Chemical cleaning, cleaning fluid is not water, but canRemove the solution of the sludge of glass surface, and in the time using Chemical cleaning, may scrub without use clean.
In the process of Chemical cleaning, the dirty contaminated glass surface of etched solution etching is carried outProcess, and obtained in theory the surface of brand-new clean contamination-free. Under desirable theoretical condition,Pollutant is from departing from and can again not be attached to the clean surface of regeneration through overetched surface; But, peopleRecognize that in etching process the pollutant departing from from glass surface may be attached to again through etchingGlass surface on, thereby cause being secondary polluted through overetched glass. Nonetheless, Chemical cleaning quiltFor example, for cleaning (processing) glass surface. Alkaline matter (for example potassium hydroxide (KOH), hydroxideSodium and ammonium hydroxide) and etchant (for example HF) all can be used for this object.
Therefore, need to be used for processing through overetched glass surface and/or from through overetched glassThe method of sludge is removed on surface, and the method can be avoided secondary pollution and/or introduce extra defect.
The present invention relates to novelty, effectively, safety and environmental protection for glass surface is being carried out to etching post processingTo remove the method for sludge.
Summary of the invention
The present invention relates to a kind of processing method through overetched glass surface, described method comprise by comprise toThe solution of few a kind of inorganic acid is applied to through overetched glass surface. In some embodiment at least, warpThe etching of the overetched glass surface etchant that process comprises fluorine ion in advance. In some embodiments,Cleaning solution is fluoride ion not, for example, derive from the ion of hydrofluoric acid.
The invention still further relates to for the treatment of comprising the molten of at least one inorganic acid through overetched glass surfaceLiquid. In some embodiment at least, not fluoride ion of this solution. The invention still further relates to involved fluorine ionEtchant etching cross through overetched glass surface, this glass surface is to prepare by a kind of method, the method comprises and uses the solution that comprises at least one inorganic acid to through overetched glass surface placeReason.
A kind of for example can contain in etching treatment procedure and giving birth to through overetched glass surface by HF etchingBecome slightly solubility sludge or polluted by this sludge. Sludge can comprise derive from through the metal of overetched glass fromSon, for example K+、Ca2+、Al3+And Si4+, and derive from the ion of etchant, for example ammonium ion (NH4+)And fluorine ion (F-). For example, the sludge that derives from glass and etchant can comprise Ca2+、Al3+And F-。Because sludge cannot be dissolved in the alkali or acid for traditional chemical cleaning solution of for example HF, so become silted upSolid impurity particle can depart from use alkali with in such as the sour Chemical cleaning processing procedure of HF and then be attached toOn glass surface. In this case, use existing chemical method to be not properly cleaned clean glass surface, because ofFor the sludge pollutant again adhering to can remain on glass. And Chemical cleaning solution for example may containThe dangerous chemical substance of KOH and/or HF. Traditional Chemical cleaning may have danger and its waste liquidProcess expensive.
Therefore, need to be to process or clean to recover the clean and nothing of glass surface through overetched glassDirt. Having developed some etchants that comprise fluorine ion in use carries out after etching, glass surface being carried out effectively clearlyThe method of washing, these methods comprise the solution that comprises at least one inorganic acid are applied to through overetched glassSurface. In some embodiment at least, method of the present invention can do not produce defect or reduce glass strongDegree condition under to cleaning through overetched glass surface. In various embodiments, side of the present inventionMethod or cost-effective, easy operating and environmental protection.
Overview above and detailed description are below only all exemplary, the present invention are not formed to limitSystem. Except description is listed, can provide other features and version. For example, this paper describes in detailThin various combinations and the sub-combination of describing the disclosed feature of part. In addition it should be pointed out that open,In the situation of step, described step needn't be carried out by described order, unless clearly stated.
Brief description of drawings
Fig. 1 is by EagleThe X-ray diffraction (XRD) of the glass sludge that glass and HF produceSpectrum.
Fig. 2 shows EagleGlass is at the Eagle of the dissolving of the HCl that comprises 6M and 12g/LThe figure of the etch-rate in the cleaning solution of using of glass sludge.
Fig. 3 shows EagleThe figure of glass sludge dissolving at room temperature.
Fig. 4 A and Fig. 4 B have shown the X ray photoelectricity that uses the glass after different cleaning methods cleanSon spectrum (XPS) result, comprises without etched glass, (for example glass is being entered through overetched glassAfter row etching, it is carried out the cleaning of 10 minutes in deionized water), utilize deionized water to add mechanical agitationClean through overetched glass, utilize that ultrasonic method cleans through overetched glassGlass, carrying out clearly in overetched glass and the HCl at 6M of cleaning in the HCl of 3MWash through overetched glass. After Fig. 4 A has shown that every kind of method of use is cleaned, glass surface is residualThe amount of B, Al, Si and F. After Fig. 4 B has shown that every kind of method of use is cleaned, glass surface is residualN, the Mg staying and the amount of Ca.
Fig. 5 A and 5B have shown and use the TOF-SIMS of the glass after different cleaning methods clean (to flyLine time ion microprobe) result, comprise without etched glass, through overetched glass (for exampleAfter glass is carried out to etching, it is carried out the cleaning of 10 minutes in deionized water), utilize deionized waterAdd that mechanical agitation cleans through overetched glass, the process of utilizing ultrasonic method to cleanEtched glass, in the HCl of 3M, clean in overetched glass, HCl at 6MClean through overetched glass, utilize that level scrubs to clean through overetched glass, profitWith vertically scrub to clean through overetched glass and utilize standard 1 (" SC1 ") million frequently superSound wave cleaning method clean through overetched glass. Fig. 5 A shown residual Al, Si, K,The amount of Ca, O and F. Fig. 5 B has shown the amount of residual B, Sr and Mg.
Fig. 6 is the surface strength comparison diagram that uses the glass surface of different cleaning methods, comprises EagleThe sample, the Eagle that draw without etched process of glassGlass through overetched baseline sample,Utilization scrub clean to clean through overetched glass, the warp that utilizes Ultrasonic Cleaning to cleanOveretched glass and utilize that HCl cleans through overetched glass.
To the description of illustrative embodiments
For example utilize after the etch processes such as the etching of HF having carried out, can think that glass surface remains dirty, because glass surface may contain the sludge generating in etching treatment procedure. Therefore, need to be in advanceProcess or clean through overetched glass surface. Disclose a kind of brand-new for comprising in utilization hereinThe etchant of fluorine ion carries out the method for after etching, this glass surface being cleaned to glass surface, wherein,In some embodiment at least, this method can not produce defect or cut and/or not right at glass surfaceGlass substrate causes secondary pollution.
In some embodiments of the present invention, by sludge pollutant is dissolved in cleaning solution so that become silted upSlag pollutant chemically cannot again be attached to through overetched glass surface glass surface is being carried out clearlyWash. In some embodiments of the present invention, can from glass surface, wash away sludge completely and not occur twoInferior pollution, because sludge is dissolved in cleaning solution completely or substantially completely.
" cleaning " used herein refer in some way to process through overetched glass surface withReduce the amount of the sludge on overetched glass surface. " processing " used herein is to instigate glass tableFace and/or sludge are exposed in cleaning solution. In some embodiment at least, cleaning can comprise becomes silted up surfaceSome or all in slag are dissolved, and described surperficial sludge is the etchant that comprises fluorine ion that utilizes for example HFTo glass surface carry out etching and make generate. Can be through being the common of this area through overetched glass surfaceThe etching of any etchant that what technical staff knew comprise fluorine ion. For example, in some embodiments,Of the present invention can be through the etching of following at least one through overetched glass surface: HF, HF and inorganicAcid, buffering HF (for example ammonium fluoride and hydrofluoric acid), ammonium acid fluoride and ammonium fluoride and at least oneAcid.
In some exemplary embodiment, of the present invention for the treatment of the solution bag through overetched glassContaining at least one inorganic acid, the inorganic acid that for example acidity is stronger than etchant. In some exemplary enforcement sideIn formula, the pKa of this at least one inorganic acid is less than the pKa of HF (3.16). In other exemplary realityExecute in mode, the concentration of this at least one inorganic acid is at least about 3M, is for example at least about 6M.
According to some embodiment of the present invention, operable exemplary and non-limiting inorganic acid comprises saltAcid (HCl) and nitric acid (HNO3). Sulfuric acid (H2SO4) can be used in some embodiment, for example, existingIn sludge, do not contain Ca2+Exemplary embodiment in. This is because H2SO4Can with Ca2+React andGenerate the calcium sulfate (CaSO of indissoluble4). But, when being to utilize HF to carry out through overetched glass surfaceWhen etching, can consider that any pKa is less than the inorganic acid of the pKa of HF.
Cleaning solution of the present invention also can comprise at least one surfactant. In some embodiments, tableSurface-active agent can help sludge depart from and/or sludge particles is suspended in cleaning solution from glass surface,Although this not necessarily. In some embodiments, the sludge particles of suspension can be dissolved in bag quicklyContaining in the cleaning solution of at least one surfactant. According to some embodiment of the present invention, can useExemplary surfactant comprise fluorine-containing surfactant, the FS-10 of for example Du Pont (DuPont).Other exemplary surfactant can comprise the anionic surfactant of for example lauryl sodium sulfateFor example TritonTMThe nonionic surface active agent of X-100.
In some embodiment at least, improve the temperature of cleaning solution of the present invention and can further accelerate to cleanProcess. In some embodiments, the temperature of cleaning solution can be room temperature or higher, for example, be at least largeApproximately 22 DEG C, be for example at least about 25 DEG C or be at least about 30 DEG C.
A kind of component of the sludge being generated by cleaning treatment as mentioned above, can comprise and derives from HF etchingThe fluoride of journey. In the time dissolving sludge with the cleaning solution that comprises at least one inorganic acid of the present invention,The sludge that contains fluoride can be first dissociation slightly, and discharge the free fluorine ion of certain concentration. Comprise toProton (the H that derives from inorganic acid ion that the cleaning solution of few a kind of inorganic acid contains high concentration+). ProtonCan by with F-Ions binding also forms water miscible HF and plays fluorine ion (F-) effect of scavenger.F-The consumption of ion can further promote dissociating of sludge until sludge is almost dissolved in cleaning solution completely,Or be dissolved in completely in some embodiments in cleaning solution.
Following reaction equation 1 (EQ1) is illustrated in utilizes the etchant that comprises fluorine ion to glass surfaceCarry out forming in etched processing procedure the general mechanism of glass sludge, wherein, M represents metal ion. ComeThe metal ion that comes from glass sludge combines with the fluorine ion that comes from fluorine containing etchant agent, compound (MFn)Because its strong bond precipitates with joint efforts.
Reaction equation 1:Mn++nF-→MFn
Reaction equation 2 (EQ2) is the back reaction of EQ1, and it is also referred to as dissociation reaction. Glass is heavy(MF forms sedimentn) can dissolve by the reaction shown in EQ2.
Reaction equation 2:MFn→Mn++nF-
But, glass precipitation (MFn) dissociate may be a little less than. Therefore, in order to promote the solution of glass precipitationFrom, can add proton (deriving from strong acid) to catch free fluorine ion, as reaction equation 3 (EQ3) shown in:
Reaction equation 3:H++F-→HF
Because the fluorine ion deriving from EQ2 is constantly consumed and (is had at least one by EQ3Inorganic acid), so the reaction in EQ2 can be moved from left to right, therefore glass precipitation dissolves.
In some embodiments, glass cleaning method of the present invention can be used for removing the silicic acid that contains of any kindThe sludge being generated by HF etching that salt is on glass. For example, in some embodiments, can be to displayGlass, for example clean for the glass of liquid crystal display. In some embodiments, glass can selectFrom alumina silicate glass and borosilicate glass. In some exemplary embodiment, can be right Glass cleans, and for example comprisesGlass 2 HesGlass 3.
Some embodiment of the present invention can have advantage aspect some, although these advantages are not wantedAsk. For example, method of the present invention can be relatively efficient, because cleaning solution can make sludge from glassDissolve fast on surface, thereby clean at short notice glass. Only for instance, at some embodiment at leastIn, cleaning solution of the present invention makes sludge dissolve the required time from glass surface to be less than or equal to about 25Minute, be for example less than or equal to about 10 minutes, or be less than or equal to about 5 minutes. In some exampleProperty embodiment in, can in about 5 minutes, dissolve a large amount of glass sludges (for example approximately 4g/L).
In other exemplary embodiments, method of the present invention can be to glass table in cleaning processFace causes physical damnification, or can alleviate the physics of glass is damaged compared with traditional chemical cleaning methodWound. Therefore, method of the present invention can substantially maintain the intact of glass surface and not produce defect and/or reductionStrength of glass.
In addition, in some exemplary and nonrestrictive embodiment at least, cleaning solution of the present invention canOnly comprise a kind of inorganic acid, for example HCl. In some embodiments, cleaning solution of the present invention comprise 3M,The HCl of 4.5M or 6M.
In various other exemplary embodiments, the processing side through overetched glass surface of the present inventionMethod is compared relative safer with traditional chemical cleaning method, because may be in traditional chemical cleaning methodUnder excessive temperature, use HF and/or KOH, this may produce danger. In some embodiments, originallyThe cleaning solution of invention can not contain HF and/or KOH, and/or this processing can at room temperature be carried out. SeparatelyOutward, because cleaning solution of the present invention can only comprise inorganic acid, raw-material cost also can be relatively low.
In some exemplary embodiment, the processing method through overetched glass surface of the present invention existsIn cleaning solution, generate HF. Be used further alternatively and/or circulate with to additionally with the cleaning solution of crossingGlass surface carry out etching. As described herein, utilize the HCl can to the processing through overetched glass surfaceEffectively from getting on except fluoride residue through overetched glass surface, but also can be to through not overetchedThe surface strength of glass surface causes as for example traditional and scrubs the clean that negative influence that can cause.
In some embodiments of the present invention, sludge can comprise F-For example Al3+、Ca2+、Si4+、Mg2+、And Sr2+In at least one. In some embodiments, sludge can comprise AlF3And SiF4In at least oneKind. In some other embodiment, the key component of sludge can be CaAlFX, wherein, x can be for exampleIn about scope of 3～about 5, but not limit by this scope. For example, in some embodiments,The key component of sludge can be CaAlF5. In some embodiments, the less important of sludge can be mutuallyMgAlF5(H2O)2. About this point, Fig. 1 has shown by being dissolved in the HF of 3M and the HCl of 6MIn EagleThe XRD spectrum of the exemplary glass sludge that glass generates. In theory, low angleMain peak under degree may be CaAlFX(wherein x is unknown), and the less important of sludge is mutuallyMgAlF5(H2O)2。
" cleaning efficiency " used herein refers to the rate of dissolution of glass sludge in cleaning solution. At thisIn some embodiment of invention, can be some because usually further improving cleaning efficiency by adjusting. OneThe factor that can improve the rate of dissolution of glass sludge is the kind of used inorganic acid, because derive from inorganicThereby the cation of acid can react and suppress course of dissolution with glass sludge. For example,, at EagleGlassIn glass sludge, when by H2SO4While use as at least one inorganic acid, derive from CaAlFXCa2+Meeting and SO4 2-React and form CaSO4. But it should be pointed out that in some embodiments,H2SO4Can have the ability of dissolving sludge, this sludge is not containing for example Ca2+Can react with sulfateMetal ion. On the other hand, for example HCl can dissolve Eagle very rapidlySludge, because chlorineIon does not react with the metal ion that comes from sludge.
Another factor that can improve the rate of dissolution of glass sludge is the concentration of used inorganic acid. ImproveThe concentration of inorganic acid can reduce dissolves the glass required time of sludge. For example in some embodiments, inorganicThe concentration of acid can be at least about 3M, for example, be at least about 4.5M or be at least about 6M. ExtremelyIn few a kind of exemplary embodiment, can be by the concentration of HCl be increased to about 6 from about 3MM will dissolve the Eagle of about 4g/LThe time of sludge was down to about 10 points from about 80 minutesClock.
It should be pointed out that to the fluorine ion source that adds for example HF in cleaning solution and may reduce dissolvingSpeed. Therefore,, in some embodiment at least, this cleaning solution does not basically contain fluorine ion. For example,In some embodiments, cleaning solution is not containing HF.
The factor of the rate of dissolution of extra improved a glass sludge is reaction temperature. In some enforcement sideIn formula, by reaction temperature is for example increased to about 30 DEG C from about 22 DEG C, can improve reaction rateAnd shortening dissolution time. In some embodiments, for example stir and/or the stirring such as sonication also can be acceleratedCourse of dissolution, for example, for example, because reaction betides the interface of solid (sludge) and liquid (cleaning solution)Place.
In some embodiments of the present invention, with cross cleaning solution can be further used in by circulation rightGlass surface carries out etching. By cleaning solution again for glass surface is carried out etching can reduce raw material andThe cost of liquid waste processing. In cleaning treatment process described in some embodiment in this article, can make to containFluorine sludge is dissolved in inorganic acid, thereby in cleaning solution, generates HF in cleaning treatment process. At certainIn a little embodiments, can carry out glass surface with the HF in the cleaning solution of mistake and the mixture of inorganic acidEtching.
For example, in a kind of exemplary embodiment, the about 16g's of HCl solubilized of the 6M of 1LEagleSludge. In the exemplary embodiment of another kind, of the present invention by by the Eagle of 12g/LSludge be dissolved in the HCl of 6M and the cleaning agent of using generating to EagleThe erosion of glassEtching speed is about 0.1 μ m/ minute. For example, referring to Fig. 2, Fig. 2 has shown for to EagleGlass carries out the etched cleaning solution of the using (Eagle of the dissolving of the HCl+12g/L of 6MSludge)Etch-rate. In some embodiments of the present invention, can be by adding in the cleaning solution to crossingExtra fluorine ion, for example, add HF and improve etch-rate.
Method of the present invention has many advantages such as the simplicity of comprising and low cost. Can utilize any is this areaMethod known to a person of ordinary skill in the art is applied to solution of the present invention through overetched glass surface. For example,Can be by immersing in solution or pass through spray solution extremely through overetched through overetched glass surfaceGlass surface is used this solution. In some embodiments, at room temperature glass is immersed in cleaning solution,Then in deionized water, clean, this cleaning is enough to remove glass sludge from glass surface.
In some embodiments of the present invention, cleaning method of the present invention can maintain the intact of glass surface and makesIt there is no defect. Clean cleaning of the present invention owing to not using brush to carry out physics to glass surfaceMethod can avoid producing cut or other defect in cover glass surface in cleaning course.
Except as otherwise noted, otherwise all numerical value that use in description and claims are all interpreted asModified by term " approximately ", and no matter whether with " approximately ". Should also be understood thatDescription and claims all accurate numerical value used forms other embodiment of the present invention. WeThrough making great efforts to ensure the degree of accuracy of disclosed numerical value in embodiment. But the numerical value of any mensuration will inevitably containThere is some error being caused by the standard deviation existing in various determination techniques.
" being somebody's turn to do " used herein, " one " or " one " expression " at least one (one) ",Should not be limited as " only one (one) ", unless made clearly contrary instruction.
Should be understood that, above-mentioned general description and following detailed description are only exemplary and illustrative, and nonrestrictive.
Comprising in this manual and forming its a part of accompanying drawing is not for limiting object, but explanation thisWorking of an invention mode.
Those skilled in the art, by considering description and implementing present disclosure, can expect apparentlyOther embodiment.
Embodiment
Following examples are not intended to limit the present invention.
Embodiment 1
By EagleSludge is dissolved in three kinds of different solution: the potassium hydroxide of 15 % by weight(KOH), the HF of the HCl of 6M and 10 % by weight. To the Eagle that adds respectively 4g/L in every kind of solutionSludge is (for example, to the Eagle that adds respectively 0.2g in every kind of solution of each 50mLSludge).EagleSludge was dissolved in completely in the HCl of 6M in 10 minutes, obtained settled solution. This sludge existsAfter some days, be still insoluble in other two kinds of solution, obtain obviously muddy solution.
Fig. 3 has shown EagleSludge is the dissolubility in the HCl of 6M at room temperature. As Fig. 3Shown in, in course of dissolution, metal ion (for example Ca2+、Al3+And Mg2+) from sludge, be discharged intoIn the HCl cleaning solution of 6M. EagleThe rate of dissolution of sludge can pass through in the different time pairThe concentration of metal ion monitors to obtain. By based on to Ca in course of dissolution2+Change in concentration and enterThe calculating of row, demonstrates in initial 2 minutes, and sludge has dissolved and approached 65%.
Embodiment 2
The HF (the HF mother liquors of the 50 volume % of for example 24 volume %) of use 12% is to EagleGlassGlass carries out etching, uses different cleaning methods to cleaning through overetched sheet material. Proof is utilized HClCleaning of carrying out effectively removed fluoride residue and do not reduced through overetched sample from surfaceThe surface strength of product.
Etching is to complete in the automatic etching system of the HF of use 12%. Make 10 " × 14 ", thickness isThe Eagle of 1.1mmSheet material is thinned to 0.7mm, make substrate the each attenuation in two sides 200 microns,Altogether attenuation 400 μ m. In thinning and cleaning process, use N2Bubbling. After thinning, use deionizationWater carries out twice cleaning to sheet material, for example, sheet material is carried out after the cleaning of 5 minutes, removes rinse water with freshDeionized water is carried out the cleaning of 5 minutes again to sheet material. After then using following different cleaning method to thinningSample cleans:
(1) under mechanical agitation, carry out the cleaning of 5 minutes by deionized water;
(2) semi-cleanKG (KOH) cleaning agent of use 4% carries out ultrasonic wave (40Khz) clearlyWash;
(3) clean 5 minutes with the HCl of 3M;
(4) clean 5 minutes with the HCl of 6M;
(5) use NH4OH、H2O2And H2O carries out the cleaning of SC1 megasonic;
(6) use Ben Tele (Bentler) hairbrush to carry out level clean, when clean, use 4%Semi-cleanKG (KOH) cleaning agent; And
(7) use Ben Tele hairbrush vertically to clean, when clean, use 4% Semi-cleanKG(KOH) cleaning agent.
Also use following three kinds of reference glass samples:
(1) 10 " × 14 " sheet material, passes through thinning and in deionized water, carried out the cleaning of 10 minutes;
(2) 1.1mm thickness without thinning (through drawing) 2 " × 2 " sheet material; And
(3) clean through scrubbing.
Obtain reference sample and clean after 10 × 14 " the side light image of sheet material. By through clean 10× 14 " plate cutting becomes 2 × 2 " small pieces and analyze. The x-ray photoelectron spectroscopy that it is carried out(XPS) research (seeing Fig. 4 A and 4B) is confirmed to have calcium and fluorine on sordid (through thinning) surface.As shown in Figure 4 A, HCl has consumed more lip-deep Al and has got on except fluorine from surface. Although superSound wave cleans has removed lip-deep fluoride residue effectively, but uses deionized water under mechanical agitation5 minutes additional cleanings of carrying out are not enough to wash away this residue.
TOF-SIMS analysis confirmation is through overetched sample surfaces and the sample crossed by washed with de-ionized waterSurface there is calcium, magnesium and fluorine. Referring to Fig. 5 A and 5B. As shown in Figure 5A, the HCl of 3M has consumedLip-deep Al has also removed fluorine effectively. Scrub clean sample all through level and horizontal+verticalBe presented at surface and have potassium. Although scrub clean effectively removed fluoride residue, this surface toolThere are some potassium. These potassium may derive from scrubs the semi-cleanKG cleaning agent using in cleaning course.
Side light studies show that in the sample of scrubbing after cleaning and has some cuts. The figure of light microscopePicture has also confirmed this observed result. Optical microscope image is presented at after the storage life of 10 weeks, through erosionFormation crystal in surface that carve and uncleanly glass. In the clean sample of process, do not find crystal shapeBecome. This has further confirmed the effective cleaning side for removing the residual fluoride residue of etch processThe importance of method.
All chemical treatment method, be included in the washed with de-ionized water under mechanical agitation, the HCl of 3MCleaning, Ultrasonic Cleaning and the megasonic of HCl of cleaning, 6M clean all at least partly effectivelyRemove the chemical residue through overetched glass surface. Although scrub clean can removal through overetchedSome chemical residues on glass, hurtful but hairbrush has caused the surface quality of glass substrateCut. Carry out 5 minutes additional cleanings by deionized water and be not enough to effectively remove the fluoride on glass surfaceResidue. Even if the HCl solution of 6M has been removed fluoride residue effectively, but it causes glassInfringement. The HCl of 3M is proved to be able to effectively clean through overetched glass surface.
Embodiment 3
Use 10% HF (the HF mother liquors of the 50 volume % of for example 20 volume %) will be of a size of 4 " × 4 "EagleSheet material is thinned to 300 microns from 500 microns. Clean, HCl cleaning and super that use is scrubbedSound wave is clean to be cleaned these samples. Test these samples, through overetched reference product and drawingAfter EagleThe surface strength of glass sample. As shown in Figure 6, than using Ultrasonic Cleaning sideMethod carries out clean sample and through overetched reference product, the intensity of scrubbing the sample after cleaning is minimum. ?In the method for testing, the highest by the intensity of the clean sample of HCl. Referring to Fig. 6.
Under the table 1 that shows shown the cleaning method that uses and surface quality and surface strength knot separately thereofThe summary of fruit.
Table 1
Embodiment 4
Under the table 2 that shows shown dissolving EagleThe time that sludge is used and cleaning solution. Make 4g/LEagleSludge is suspended in each solution for test.
Table 2
Claims (20)
1. through a processing method for overetched glass surface, described glass surface is through comprising fluorine ionThe etching of etchant, described method comprises:
To the described solution that comprises at least one inorganic acid of using through overetched glass surface.
2. the method for claim 1, is characterized in that, described at least one inorganic acid is selected from saltAcid, nitric acid and sulfuric acid.
3. the method for claim 1, is characterized in that, described at least one inorganic acid is hydrochloric acid.
4. the method for claim 1, is characterized in that, described solution is being applied to through erosionBefore the glass surface of carving, do not basically contain hydrofluoric acid.
5. the method for claim 1, is characterized in that, the concentration of described at least one inorganic acidBe at least about 3M.
6. the method for claim 1, is characterized in that, the concentration of described at least one inorganic acidBe at least about 4.5M.
7. the method for claim 1, is characterized in that, described solution is applied to through etchingThe operation of glass surface carry out time of about 5 minutes～about 80 minutes.
8. the method for claim 1, is characterized in that, described solution also comprises at least one tableSurface-active agent.
9. the method for claim 1, is characterized in that, at the temperature of at least about 22 DEG C, executesUse described solution.
10. treated through an overetched glass surface, described glass surface is through comprising fluorine ionThe etching of etchant, described treated be by comprising, one to be comprised through overetched glass surfaceThe solution of at least one inorganic acid is applied to be prepared through the technique of overetched glass surface.
11. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,Described at least one inorganic acid is selected from hydrochloric acid, nitric acid and sulfuric acid.
12. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,Described at least one inorganic acid is selected from hydrochloric acid.
13. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,Described solution does not basically contain hydrofluoric acid being applied to before overetched glass surface.
14. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,The concentration of described at least one inorganic acid is at least about 3M.
15. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,The concentration of described at least one inorganic acid is at least about 4.5M.
16. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,Described solution is applied to through the operation of overetched glass surface and is carried out about 5 minutes～about 80 minutesTime.
17. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,Described solution also comprises at least one surfactant.
18. as claimed in claim 10 treatedly it is characterized in that through overetched glass surface,At the temperature of at least about 22 DEG C, use described solution.
19. 1 kinds of processing methods through overetched glass surface, described glass surface is through comprising fluorine ionThe etching of etchant, described method comprises:
The solution that comprises concentration and be at least the hydrochloric acid of about 3M is applied to described glass surface, wherein,Described solution does not basically contain hydrofluoric acid being applied to before overetched glass surface.
20. methods as claimed in claim 19, is characterized in that, described solution is applied to through erosionThe time of about 5 minutes～about 80 minutes is carried out in the operation of the glass surface of carving.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361858292P | 2013-07-25 | 2013-07-25 | |
| US61/858,292 | 2013-07-25 | ||
| PCT/US2014/047734 WO2015013360A1 (en) | 2013-07-25 | 2014-07-23 | Methods of treating glass surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105593182A true CN105593182A (en) | 2016-05-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480053148.XA Pending CN105593182A (en) | 2013-07-25 | 2014-07-23 | Methods of treating glass surfaces |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2016528146A (en) |
| KR (1) | KR20160037952A (en) |
| CN (1) | CN105593182A (en) |
| TW (1) | TW201504177A (en) |
| WO (1) | WO2015013360A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365459A (en) * | 2016-08-24 | 2017-02-01 | 赣州帝晶光电科技有限公司 | Chemically thinning method for liquid crystal glass substrate |
| CN107640907A (en) * | 2017-10-27 | 2018-01-30 | 惠州市清洋实业有限公司 | A kind of preprocess method of glass thinning |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9488857B2 (en) | 2014-01-10 | 2016-11-08 | Corning Incorporated | Method of strengthening an edge of a glass substrate |
| CN105016629B (en) * | 2015-08-05 | 2018-01-23 | 福耀玻璃工业集团股份有限公司 | A kind of pickle and method for washing glassy silicate glass plate |
| CN106348613A (en) * | 2016-08-24 | 2017-01-25 | 赣州帝晶光电科技有限公司 | Liquid crystal glass base plate thinning pretreatment method |
| US11208344B2 (en) * | 2017-03-28 | 2021-12-28 | Corning Incorporated | Textured glass articles and methods of making the same |
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|---|---|---|---|---|
| CN1809513A (en) * | 2003-05-30 | 2006-07-26 | 兰姆研究公司 | Methods of finishing quartz glass surfaces and components made by the methods |
| JP2008056544A (en) * | 2006-09-01 | 2008-03-13 | Nishiyama Stainless Chem Kk | Method for producing glass sheet having fine linear groove and glass sheet produced thereby |
| CN103107086A (en) * | 2013-01-29 | 2013-05-15 | 淄博晨启电子有限公司 | Manufacturing technique of low-voltage chip and low-voltage chip thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010168270A (en) * | 2008-12-26 | 2010-08-05 | Hoya Corp | Glass substrate and method for manufacturing the same |
-
2014
- 2014-07-23 CN CN201480053148.XA patent/CN105593182A/en active Pending
- 2014-07-23 KR KR1020167004472A patent/KR20160037952A/en not_active Application Discontinuation
- 2014-07-23 WO PCT/US2014/047734 patent/WO2015013360A1/en active Application Filing
- 2014-07-23 JP JP2016529851A patent/JP2016528146A/en not_active Ceased
- 2014-07-25 TW TW103125570A patent/TW201504177A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809513A (en) * | 2003-05-30 | 2006-07-26 | 兰姆研究公司 | Methods of finishing quartz glass surfaces and components made by the methods |
| JP2008056544A (en) * | 2006-09-01 | 2008-03-13 | Nishiyama Stainless Chem Kk | Method for producing glass sheet having fine linear groove and glass sheet produced thereby |
| CN103107086A (en) * | 2013-01-29 | 2013-05-15 | 淄博晨启电子有限公司 | Manufacturing technique of low-voltage chip and low-voltage chip thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365459A (en) * | 2016-08-24 | 2017-02-01 | 赣州帝晶光电科技有限公司 | Chemically thinning method for liquid crystal glass substrate |
| CN107640907A (en) * | 2017-10-27 | 2018-01-30 | 惠州市清洋实业有限公司 | A kind of preprocess method of glass thinning |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160037952A (en) | 2016-04-06 |
| WO2015013360A1 (en) | 2015-01-29 |
| TW201504177A (en) | 2015-02-01 |
| JP2016528146A (en) | 2016-09-15 |
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