EP4594267A1 - Glaszusammensetzung zur herstellung strukturierter glaselemente aus alkalifreien gläsern und strukturierte, alkalifreie glaselemente - Google Patents
Glaszusammensetzung zur herstellung strukturierter glaselemente aus alkalifreien gläsern und strukturierte, alkalifreie glaselementeInfo
- Publication number
- EP4594267A1 EP4594267A1 EP23769148.0A EP23769148A EP4594267A1 EP 4594267 A1 EP4594267 A1 EP 4594267A1 EP 23769148 A EP23769148 A EP 23769148A EP 4594267 A1 EP4594267 A1 EP 4594267A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glass
- glass element
- recess
- mol
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
-
- 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
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
Definitions
- the invention relates to glass articles with structured glass surfaces.
- the invention relates to an alkali-free glass composition for producing structured, alkali-free glass articles by basic etching in aqueous solutions.
- alkaline glasses are not suitable for use in components in electronic packaging applications or semiconductors, for example, because the high mobility of the alkali ions, particularly potassium and lithium ions, can lead to diffusion into other components and thus contamination.
- alkali-free glasses have excellent dielectric properties, so alkali-free glasses are very important in the field of semiconductor and electronic packaging production. At the same time, these production areas require microstructuring, which can be achieved in particular by microstructuring. Pure quartz glass is unsuitable because of its unadapted thermal expansion and the complex production at very high temperatures.
- alkali-free glasses usually contain higher levels of alkaline earth oxides.
- Alkaline earth oxides are problematic in alkaline etching, however, because in the basic pH range, poorly soluble alkaline earth silicates form, which precipitate on the glass surface and form a passivation layer. The etching process thus comes to a local halt or is at least greatly slowed down, so that the etching process causes the initially created filaments to expand into channels and the channel walls to deform.
- a further object of the invention is to provide a structured glass element.
- a glass element is provided and glass material is removed locally or in selected areas using an etching process.
- the glass element is brought into contact with an etching solution, at least in the areas to be structured.
- the method provides at least the following steps a) to c): a) provision of a glass element b) production of at least one filament-shaped channel by means of a laser beam of an ultrashort pulse laser, wherein the longitudinal direction of the channel runs transversely to the surface of the glass element, c) treatment of the glass element obtained in step b) with a basic etching solution, wherein the glass of the glass element is removed by the etching solution so that the channel produced in step b) is widened so that a recess is formed.
- the glass composition according to the invention or a glass element with a corresponding glass composition has proven to be particularly advantageous for use in the etching process described above in terms of the etching rate and very little or even no formation of deposits or coatings on the glass surface.
- the glass element comprises an alkali-free glass with a CaO content of less than 7 mol%.
- An alkali-free glass is understood in particular to mean a glass which, apart from unavoidable traces, ie traces introduced by the raw materials used, does not contain any alkali oxides.
- the total content of alkali oxides in the glass is less than 500 ppm or 0.0005 mol%.
- the glass is alkali-free, it is particularly suitable for use in electronic components.
- alkali metal oxides are used in particular to adjust the glass viscosity or the softening temperature, whereby the softening temperature can be lowered by adding alkali metal oxides.
- the softening temperature is adjusted via the content of alkaline earth metals such as calcium oxide. This means that a minimum content of alkaline earth metal oxides cannot usually be avoided in alkali-free glasses.
- the glass element is laser filamented.
- a pulsed ultra-short laser is used to specifically generate filaments, for example in the form of fine channels, in the glass element. These can go completely through the substrate and thus extend from side surface to side surface, or they can only be connected to one of the surfaces of the side surface.
- the prerequisite for this process is that the glass element used is transparent to the wavelength of the laser radiation used.
- This process step is generally called laser filamenting.
- the basis of this process is that the laser radiation used causes damage to the glass substrate. This damage forms the point of attack for the following etching process. Accordingly, glasses that react efficiently to laser irradiation, ie that can show a sufficient degree of damage, are advantageous.
- step c) following step b), the glass element structured in this way is brought into contact with a basic etching solution at least with the areas to be structured. This results in an expansion or an enlargement of the introduced filaments or structures through the etching process that takes place in step c).
- etching glasses containing alkaline earth metal with acidic etching solutions for example when using etching solutions containing HF
- an inhibition usually occurs relatively soon during the etching process, so that the etching process only takes place at very low etching rates.
- the inhibition is in particular a result of poorly soluble precipitates such as calcium fluoride, which precipitate on the glass surface and act as a passivation layer.
- the acid is also inactivated.
- the glasses according to the invention are therefore particularly suitable for use in basic etching processes.
- the high pH value in the exposed areas of the glass element causes the SiCh matrix to dissolve, forming silicates, and thus also the other glass components in the corresponding area to be released.
- the etching process is not inhibited, or at least not as quickly.
- the high pH value of the etching solution means that the silicate released from the glass is present as a Lewis base and has a high nucleophilicity. Accordingly, the silicate as a released component can also act as an attacking nucleophile. Since the concentration of silicates increases during the etching process, the effects described above are further intensified.
- the glass element or the glass composition has a CaO content of less than 7 mol%, preferably less than 6 mol%.
- the CaO content is in the range from 0.2 mol% to ⁇ 7 mol%, in particular from 1 mol% to ⁇ 7 mol% or from 2 to ⁇ 7 mol%, particularly preferably in the range from 3 to 6 mol%.
- Calcium ions can form calcium silicate during the etching process. (CaSiCh) which is deposited as a precipitate on the glass surface. This is disadvantageous on the one hand because it can lead to passivation of the glass surface. On the other hand, the properties of the glass surface are changed by CaSiCh deposits.
- the CaO content according to the invention reduces this effect so that the etching process can take place at sufficiently high etching rates.
- NaOH or KOH solutions have proven to be particularly suitable as etching media.
- One embodiment of the invention provides that the etching rate in a 6 molar KOH solution at an etching temperature of 100 ° C is at least 1.0 pm/h, preferably more than 1.0 pm/h.
- the glass has a ratio of the content of CaO to the total content of alkaline earth oxides MO, comprising CaO, MgO, SrO and BaO, for which the following applies:
- CaO/ ⁇ MO ⁇ 1, preferably in the range 0.4 to ⁇ 1.
- This ratio is particularly advantageous because it ensures that the properties required for processing and using the glass, such as lowering the softening temperature and adjusting the thermal expansion coefficient, can be achieved even without the presence of alkali oxides by means of an appropriate content of alkaline earth oxides, and at the same time the content of the oxides of the higher alkaline earth metals, whose silicates have particularly low solubility products, can be kept relatively low in the glass, so that the disadvantages described above do not occur or only occur to a small extent during the etching process.
- the total content of alkaline earth oxides MO in the glass is less than 13 mol%, preferably less than 12 mol%.
- the content of alkaline earth oxides in the glass is in the range from 9 to 12 mol%.
- the content of barium oxide and/or strontium oxide in the glass is less than 1.6 mol%.
- a strontium oxide content of less than 1.4 mol%, preferably less than 1 mol%, has proven to be particularly advantageous. It is assumed that by limiting the content of higher alkaline earth metal oxides it can be avoided that the very low solubility products of the strontium or barium silicates are exceeded during the etching process and thus precipitate formation and inhibition of the etching process occurs.
- a barium oxide content of more than 0.7 mol% has proven to be advantageous.
- the BaO content is therefore in the range >0.7 to ⁇ 1.6 mol%.
- Alkaline-free borosilicate glasses have proven to be particularly advantageous.
- a further aspect of the invention relates to the provision of an alkali-free glass with the following composition in mol%:
- AI2O3 10.9 - 12, preferably 11 - 18,
- MgO 3 - 8 preferably 3.4 to 5
- a further aspect of the invention relates to a plate-shaped glass element made of the alkali-free glass described above with a first and a second surface arranged opposite the first.
- the plate-shaped glass element has at least one recess which breaks through at least one of the two surfaces of the glass element.
- the recess extends over a longitudinal direction (L) and a transverse direction (Q), wherein the longitudinal direction is arranged transversely to the surface of the glass element which is broken through by the recess.
- the recess is designed as a channel which extends at least from one surface of the glass element through the glass element in the direction of the other surface. According to one embodiment, the recess is arranged as a continuous channel or opening between the first and the second surface of the glass element.
- At least one wall of the recess of the glass element has a plurality of dome-shaped depressions.
- Such dome-shaped structures are obtained in particular by etching processes with basic etching solutions.
- the glass element is produced or can be produced by a process comprising the steps of laser filamentation and subsequent etching with basic, aqueous etching solution.
- the glass element has a plurality of openings which directly adjoin one another, so that an edge is formed.
- the edge here forms an outer edge which surrounds at least parts of the glass element.
- the glass element has an edge formed by a plurality of openings, which forms an inner edge of the glass element that at least partially surrounds the recess.
- the plate-shaped glass elements are particularly suitable for use in an electronic component, preferably as a spacer.
- Corresponding electronic components can be used in particular as components for the hermetic packaging of electro-optical functionalities, as components for camera imaging modules or as components in semiconductor production. Detailed description
- FIG. 1 Schematic representation of the generation of damage in the glass element by a laser
- FIG. 2 Schematic representation of a glass element with multiple defects
- FIG. 3 Schematic representation of an etching process of the glass element
- Fig. 1 shows schematically a glass element 1 with a first 2 and a second 3 surface, as well as a thickness D.
- the first surface 2 is arranged opposite, and in particular preferably plane-parallel to the second surface 3.
- the glass element 1 further extends in a longitudinal direction L and a transverse direction Q.
- the glass element 1 also has at least one side surface 4, which ideally surrounds the glass element 1 and whose height corresponds to the thickness D of the glass element 1.
- the thickness D of the glass element 1 and the height of the side surface 4 extend in the longitudinal direction L.
- the first 2 and second 3 surfaces can continue to extend in the transverse direction.
- Fig. 1 shows step b) of the method according to the invention according to an embodiment.
- damage in particular channels 15 or channel-shaped damage 15, is generated in the volume of the glass element 1 by a laser 101, preferably an ultrashort pulse laser 101.
- the laser beam 100 is focused by means of a focusing optics 102, for example a lens or a lens system, and directed onto a surface 2, 3, preferably the first surface 2 of the glass element 1.
- the energy of the laser beam 100 radiated thereby ensures that a filament-shaped damage is generated, which, for example, widens the damage to form a channel 15 by means of several laser pulses, for example in the form of a pulse packet.
- a structure 16 created in this way corresponds to a shape of a recess to be created.
- a distance and a number of channels 15 are selected so that outlines of recesses to be created are formed.
- a distance and a number of channels 15 are selected so that outlines of recesses to be created are formed.
- step c) of the method according to an exemplary embodiment is shown schematically.
- the glass element 1 is arranged on holders 50 in a detachable manner.
- the glass element 1 can only rest on the holders 50 or can be fixed to them.
- certain areas of the holders 50 serve to cover or shield defined areas of the glass element 1.
- the glass element 1 To etch the glass element 1, it is held in the basic etching solution 200 by means of the holders 50. In the embodiment shown in Fig. 3, the glass element 1 is immersed in the etching solution 200 in the etching tank 202. A basic etching solution that can be stirred using a stirrer 60 is used as the etching solution 200. Reference number 70 indicates etched surface areas of the glass element. Table 1 shows the glass compositions of the various embodiments 1 to 3 in mol% and the etching rate in pm/h. For this purpose, the glasses were etched with a 6 molar, aqueous KOH solution at a temperature of 100°C for 22 hours. The etching rates were determined by determining the glass weight before and after the etching process.
- Table 1 Glass compositions and etching rates of exemplary embodiments 1 - 3
- the “Deposit” line indicates whether a white deposit is visible to the naked eye on the etched areas after an etching period of 22 hours. Based on Table 1 it is clear that all exemplary embodiments 1 to 3 can be etched basic with relatively high etching rates of more than 1 pm/h without a visible deposit forming on the etched surfaces.
- the glass compositions according to exemplary embodiments 1 to 3 are adjusted with regard to their total content of alkaline earth metal oxides as well as with regard to the content of the various alkaline earth metal oxides MgO, CaO, SrO and BaO so that the formation of poorly soluble alkaline earth metal silicates can be avoided or at least significantly reduced , so that neither an inhibition of the etching process nor a deposit formation occurs.
- the solubility product of the respective alkaline earth silicate decreases as the atomic number of the corresponding alkaline earth silicate increases. It is therefore advantageous if a relatively large proportion of the alkaline earth metal oxides in the glass are present as calcium oxide.
- This is described by the CaO/JjMO ratio. In exemplary embodiments 1 to 3, this is in the range from >0.44 to ⁇ 1.
- In exemplary embodiments 1 and 2 there is also the Total alkaline earth metal oxide content below 12 mol%.
- the CaO content is below 7 mol%.
- Comparative examples 4 to 9 illustrate the relevance of a low CaO content to the etching performance. Although the comparative examples have a total alkaline earth metal oxide content of less than 12 mol% and a CaO/JjMO ratio of more than 0.44, the CaO content is above 7 mol%. Comparative examples 4 to 7 show a low etching rate of less than 1 pm/h and a visible coating on the glass surface.
- Comparative example 9 is comparable to the exemplary embodiments in terms of the total content of alkaline earth oxides, the CaO content and the CaO/ ⁇ MO ratio, but comparative example 9 has an SrO content of more than 1.6 mol%.
- the etching rate here is only 0.89 pm/h and a visible coating was formed.
- Comparative examples 14 and 15 illustrate the influence of the BaO content on deposit formation and etching rates during the etching process. A BaO content that is too high leads to deposit formation.
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- Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Glass Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102022125004.0A DE102022125004A1 (de) | 2022-09-28 | 2022-09-28 | Glaszusammensetzung zur Herstellung strukturierter Glaselemente aus alkalifreien Gläsern und strukturierte, alkalifreie Glaselemente |
| PCT/EP2023/074741 WO2024068239A1 (de) | 2022-09-28 | 2023-09-08 | Glaszusammensetzung zur herstellung strukturierter glaselemente aus alkalifreien gläsern und strukturierte, alkalifreie glaselemente |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4594267A1 true EP4594267A1 (de) | 2025-08-06 |
Family
ID=88060602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23769148.0A Pending EP4594267A1 (de) | 2022-09-28 | 2023-09-08 | Glaszusammensetzung zur herstellung strukturierter glaselemente aus alkalifreien gläsern und strukturierte, alkalifreie glaselemente |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4594267A1 (de) |
| DE (1) | DE102022125004A1 (de) |
| WO (1) | WO2024068239A1 (de) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011082000A1 (de) * | 2011-09-01 | 2013-03-07 | Schott Ag | Energieübertragungskabel und Verfahren zur Herstellung eines solchen |
| DE102013103370A1 (de) | 2013-04-04 | 2014-10-09 | Lpkf Laser & Electronics Ag | Verfahren zum Einbringen von Durchbrechungen in ein Glassubstrat sowie ein derart hergestelltes Glassubstrat |
| JPWO2016088778A1 (ja) * | 2014-12-02 | 2017-09-14 | 旭硝子株式会社 | ガラス板およびそれを用いた加熱器 |
| WO2016115685A1 (en) * | 2015-01-20 | 2016-07-28 | Schott Glass Technologies (Suzhou) Co. Ltd. | Low cte glass with high uv-transmittance and solarization resistance |
| DE102018100299A1 (de) * | 2017-01-27 | 2018-08-02 | Schott Ag | Strukturiertes plattenförmiges Glaselement und Verfahren zu dessen Herstellung |
| US11952310B2 (en) * | 2019-05-10 | 2024-04-09 | Corning Incorporated | Silicate glass compositions useful for the efficient production of through glass vias |
| DE102021100181A1 (de) * | 2021-01-08 | 2022-07-14 | Schott Ag | Verfahren zur Verminderung erhabener Strukturen an Glaselementen und verfahrensgemäß hergestelltes Glaselement |
-
2022
- 2022-09-28 DE DE102022125004.0A patent/DE102022125004A1/de active Pending
-
2023
- 2023-09-08 WO PCT/EP2023/074741 patent/WO2024068239A1/de not_active Ceased
- 2023-09-08 EP EP23769148.0A patent/EP4594267A1/de active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE102022125004A1 (de) | 2024-03-28 |
| WO2024068239A1 (de) | 2024-04-04 |
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