METHOD OF STRUCTURING A GLASS ELEMENT AND STRUCTURED GLASS ELEMENT PRODUCED THEREBY
This application claims benefit under 35 USC § 119 of European Application EP 20 212 702.3 filed Dec. 9, 2020, the entire contents of which are incorporated herein by reference. The invention relates in general to a method of structuring a glass element. Further aspects of the invention relate to a structured glass element, in particular a glass element produced or producible by the method according to embodiments of the invention, and the use of such a glass element. In particular, the invention relates to a method for structuring a glass element using a pulsed laser beam of an ultrashort pulse layer, and to glass elements produced or producible by such a method, as well as their use. Methods for processing workpieces using an ultrashort pulse layer are frequently employed, for example, in order to prepare a workpiece for separation. For example, WO 2012/006736 A2 discloses a method for preparing a substrate for separation by using an ultrashort pulse laser, i.e., a laser with pulse lengths shorter than 100 ps. In the method disclosed by WO 2012/006736 A2, several spaced apart filaments are produced along an intended separation line, exploiting a nonlinear effect of self-focusing. WO 2017/009379 A1 describes a further development of the method of WO 2012/009736 A2. In the method according to WO 2017009379 A1, modifications are produced in the workpiece extending obliquely to the surfaces of the processed substrate. This is achieved by directing the laser pulses obliquely onto the surface of the respective workpiece. From EP 2 931 467 B1 it is known to include the ambient atmosphere as a further process parameter in order to prevent premature self-cleaving due to subcritical crack growth. Furthermore, DE 10 2015 116 848 A1 describes the introducing of a zone of defined strength by producing a filament using spherical aberration of a lens in which the Gaussian beam of the ultra-short pulsed laser is converted into a line focus with uneven intensity distribution along the optical axis. Further, DE 10 2018 126 381 A1 relates to a method for introducing a separation line into a transparent brittle material and an element thus obtained. However, all these methods are directed towards separating a workpiece. That is, several material modifications are generated in a workpiece using an ultrashort pulse layer, wherein the modifications are arranged along a predefined path along an intended separation line. Preferably, the material modifications lead to holes formed within the workpiece. Separation may then advantageously be achieved by exposing the workpiece to an etching medium or etching bath so that the holes are widened until adjacent holes or channels combine. In that way, the workpiece may be separated along the predefined path of material modifications (or filaments) formed in the workpiece. However, for several applications, it may be preferred to structure a glass element rather than separate it, for example if the glass element is used as an interposer. Further, known methods for producing filaments that are at an oblique angle to the surfaces of the workpiece require extensive process control in order to adjust and monitor, for example, laser parameters and/or workpiece positioning very precisely, for example, by providing special focusing optics that may compensate for astigmatic deformation of the beam profile. Therefore, there is a need for a process as well as glass elements thus producible that overcome the drawbacks of the state of the art at least partially. It is an object of the present invention to provide for a method of structuring a glass element that overcomes known drawbacks of the state of the art, that is, methods requiring extensive process control, at least partially. A further aspect of the present invention is directed towards a structured glass element as well as to the use of such a glass element. The invention therefore relates to a method of structuring a glass element. According to this structuring method, a pulsed laser beam of an ultrashort pulse laser is directed onto the glass element. The glass element is transparent for the laser beam and at least one filament-shaped flaw is produced in the glass element, the filament-shaped flaw extending transversely to the side faces of the glass element. The filament-shaped flaw is produced with a laser beam that is concentrated by means of a focusing optics to form a focus line in the glass element, wherein the intensity of the laser beam within the focus line is sufficient to produce the filament-shaped flaw. The focus line is adjusted so that the filament shaped flaw ends within the glass element. The glass element is exposed to an etching medium or an etching bath which removes glass by etching, so that the filament-shaped flaw widens to form a wall extending between the opposite side faces of the glass element, the wall having a boundary line that is tapered at the vertex between the wall and an adjacent side face, with a taper angle with respect to the perpendicular of the side face, the taper angle being adjusted by at least one of the position, the length and the intensity distribution of the focus line. These parameters can be combined to adjust the geometry of the filament shaped flaws, such as the depth of a flaw in form of a blind hole. Such a method offers several advantages. According to the method of the present disclosure, a structured glass element is obtained, wherein a filament-shaped flaw is formed that ends within the glass element. In a further process step, this filament-shaped flaw is widened by use of an etching medium or etching bath to form a wall extending between the opposite side faces of the glass element. In other words, by etching, a hole is obtained within the glass element, this hole follows the form of the previously formed filament-shaped flaw at least essentially. As the filament-shaped flaw ends within the glass element, therefore, a blind hole is obtained within the glass element. Here, the expression “the hole following the form of the flaw at least essentially” is understood to mean that the hole extends along the length of the previous filament-shaped flaw and is therefore formed as an elongate hole but may, however, be wider and longer than the flaw itself. The filament-shaped flaw extends transversely to the side faces, that is, the filament-shaped flaw and the side faces of the glass element draw an angle. In other words, the filament-shaped flaw is not parallel to either side face of the glass element. Preferably, the flaw may draw a right angle with at least one of the side faces of the glass element or may be oriented essentially perpendicular to at least one of the side faces of the glass element. Here, “being oriented at least essentially perpendicular” is understood to mean that the flaw and the normal of the respective side face draw an angle of not more than ±5°. However, and quite surprisingly, upon etching of the glass element in order to widen the filament-shaped flaw so that a wall (or a hole with a wall) is formed within the glass element, a wall (or hole having a wall) is obtained with a tapering boundary line. That is, the hole is at an oblique angle to at least one of the side faces. In particular, the angle drawn between the flaw and a side face may differ from the angle drawn between the hole (or the boundary line of the wall of the hole). This may achieved quite surprisingly by adjusting at least one the position and/or the intensity distribution of the focus line of the laser beam. However, controlling the position of the substrate orientation relative to the laser beam very precisely, for example, by providing supplemental optical devices such as a cylindrical lens or the like is not necessary. The disclosure therefore provides a simple process for forming structured glass elements having at least one blind hole formed within the glass element, wherein the boundary line of the wall of the hole the side face of the glass elements to which the hole opens draw an oblique angle. In the scope of the present invention, the following definitions apply: A filament is understood to refer to an elongate structure, that is, a structure with a dimension along a first direction of a Cartesian coordinate system that is greater by at least one order of magnitude than the dimensions of the structure along the two further directions of the Cartesian coordinate system that are perpendicular to the first direction. A flaw may, according to the present disclosure, be understood as an altered region within a workpiece (or glass element). That is, in the region the properties differ from that of the workpiece (or glass element) prior to forming the flaw. A filament-shaped flaw therefore may be understood as an altered, elongate region within the glass element. A plate-shaped element (or body) is understood to refer to a body whose dimension along a first direction of a Cartesian coordinate system is smaller by one order of magnitude than the dimensions along the two further directions of the Cartesian coordinate system perpendicular to the first direction. For example, a plate shaped glass element may also be denoted a glass plate or a glass ribbon. The plate-shaped element according to the disclosure may be formed as a flat or bend element. Further, in case of a flat element, the side faces may preferably be essentially parallel to each other, that is, the normals or perpendiculars of the side faces drawing an angle of preferably not more than 10°, in particular not more than 5°. An ultrashort pulse laser is understood as a laser with a pulse length not more than 100 ps. Preferably, pulse lengths are not longer than 10 ps, more preferably not longer than 1 ps or even smaller than 1 ps. According to an embodiment, a channel is produced by etching and widening of the filament-shaped flaw, wherein the channel opens to both opposite side faces. That is, with other words, a through hole is formed according to an embodiment. Such an embodiment may be advantageous in case the glass element is used as an interposer, for example, in printed circuit applications. According to a further development, a filament-shaped flat is produced that ends in the glass element by using a focusing optics which superimposes at least two partial beams of the laser beam so that the interference of the partial beams generates an intensity variation along the focus line. This is a very simple, yet effective way to generate a flaw (or material modification) in a workpiece. In this respect, the flaw may also be referred to as a “blind flaw”. Further, upon superimposing the two partial beams, thereby generating an intensity variation along the focus line, the resulting angle between the side face of the glass element and the boundary line of the wall may be adjusted in a very simple way. According to an embodiment, a multitude of filament-shaped flaws that are distributed over the glass element in a predefined pattern are produced. Further, these filament-shaped flaws may, upon etching, be formed by widening of the flaws. In this way, a multitude of channels that correspond to the previously produced flaws within the glass element and that are distributed over the glass element in a predefined pattern are produced. The disclosure further relates to a glass element, in particular a glass element that is produced or at least producible with a method according to an embodiment of the disclosure, preferably a plate-shaped glass element. The glass element comprises two opposite side faces and a multitude of etched channels that extend through the glass element so that the walls of the channels connect the side faces. The boundary lines of the channel walls are tapered at the vertices between the wall and the adjacent side faces. Preferably, at least two taper angles between the boundary lines and the perpendicular of the side faces at the vertices between the walls and the side face differ from each other. The invention will now be further explained with reference to the figures. In the figures, like reference numerals refer to the same or corresponding elements. Further, apart from glass elements, workpieces comprising or consisting of materials other than glass may also be structured by the method of the disclosure. At least one filament shaped, that is elongated, flaw 9, for example a material modification, is produced in glass element 1. Flaw 9 extends transversely to side faces 14, 15 of glass element 1, that is, an angle is drawn between flaw 9 and either of side faces 14, 15. In other words, flaw 9 is not parallel to either of side faces 14, 15. Laser beam 5 used to produce flaw 9 is concentrated by means of focusing optics 70 to form focus line 8 (not shown here) in glass element 1. The intensity of laser beam 5 within focus line 8 (not shown here) is sufficient to produce filament-shaped flaw 9. Furthermore, focus line 8 (not shown here) is adjusted so that filament-shaped flaw 9 ends within glass element 9. After laser treatment as described above, glass element 1 comprising at least one filament-shaped flaw 9 is then transferred to an etching tank 80 as schematically and not drawn to scale depicted in By etching, filament-shaped flaw 9 widens to form wall 6, as is depicted schematically and not drawn to scale in As an advantage of the method according to the disclosure, by adjusting position and intensity of focus line 8, preferably by aid of a suitable focusing optics 70, taper angle 94 may be controlled and adjusted according to a predefined value in a very simple and efficient way. A suitable focusing optics 70 may comprise a lens, such as a spheric or aspheric lens, or an axicon, or a spatial light modulator or suitable combinations thereof. According to an embodiment as shown schematically and not drawn to scale in Very advantageously, according to an embodiment, filament-shaped flaw 9 that ends in glass element 1 is produced using focusing optics 70, wherein focusing optics 70 superimposes at least two partial beams 50, 51 of laser beam 5 so that the interference of partial beams 50, 51 generates an intensity variation along focus line 8. In this way, taper angle 94 may be adjusted in a quick and easy manner. According to an embodiment and as schematically and not drawn to scale depicted in As depicted in According to a further embodiment, coaxially oriented flaws 9 According to an embodiment, at least two filament shaped flaws 9 are introduced into glass element 1, here, in Further, it may be contemplated to adjust the diameters of flaws 9 generated within glass element 1 according to a predefined value. For example, as can be seen in the schematic and not drawn to scale depiction of Furthermore, a channel 10 may be formed in that way, wherein the angles drawn between channel 10 (or rather, boundary lines 12 of wall 6 of channel 10) and side faces 14, 15 differ from each other. Such a glass element 1 comprising channels 10 with different taper angles at different vertices 16, 17, 18, 19 is depicted schematically and not drawn to scale in Channel 10 The diameter of channel 10 Further, channel 10 According to a further embodiment depicted schematically and not drawn to scale in According to a further embodiment, laser beam 5 is advanced relative to glass element 1 along predefined path 11. In that way, a multitude of flaws 9 results that are arranged side-by-side along path 11. In that case, etching is continued at least until adjacent channels 10 combine so that glass element 1 is divided into segments 100, 101 (shown schematically and not drawn to scale in According to a further embodiment, taper angle 94 between boundary line 12 of wall 6 and side face 14 and/or 15 is adjusted by selecting the molarity of the etching bath (or etching medium) 81. That is, it is possible to vary the taper angle by careful selection of the etching conditions, in particular, by adjusting the etching bath molarity. Preferably, a basic etching bath (or an etching medium) is used, for example an etching bath (or etching medium) comprising, as main component, KOH. Such an etching bath or etching medium is well suited for etching glasses that are commonly used in technical applications, such as glasses for interposers. Especially, borosilicate glasses may be etched using basic etching bathes (or basic etching media) comprising KOH. In this way, commonly employed acid etching media for glasses, that usually are based on HF or related compounds, need not be employed. This is favourable, as HF comprising and like etching media are harmful, especially with regard to safety and environmental issues. Preferably, taper angle 94 is adjusted by setting, in particular increasing the basic etching bath molarity (or basic etching medium molarity). This is favourable as in this way, the overall reaction rate is increased. Generally, the dependence of the taper angle to the molarity of the etching bath allows to produce predefined taper angles. As well, the taper angle may also generally depend on the viscosity of the etching bath and further parameters such as the etching depth or the etch removal. The etch removal depends on the etching time. Thus, in a further embodiment, to achieve a desired taper angle, a refined method is provided comprising the steps: defining a taper angle 94 of the edges of the segments 100, 101 to be achieved after etching; determining at least one of a molarity of the etching bath 81, a viscosity of the etching bath 81, an etch removal and an etching time depending on the defined taper angle 94; preparing an etching batch 81 having a molarity or viscosity as determined; and etching the glass element in the etching bath 81. This way, typically, the taper angle achieved after etching differs from the predefined, or, respectively, desired taper angle by less than 0.5°, preferred by less than 0.3, more preferred by less than 0.2°. Generally, determining at least one of a molarity and viscosity of the etching bath 81 depending on the defined taper angle 94 may include the extrapolation from one or more reference points or interpolation between one or more reference points relating the taper angle to at least one of the parameters molarity or viscosity of the etching bath. In this regard, it has been found that taper angle 94, for example a taper angle of the edges of segments 100, 101, may be increased by at least 0.1° by increasing the molarity of the basic etching bath or etching medium 81 by 2 mol/l. Thus, the step of determining the molarity may include an extrapolation from one or more reference points using a factor of at least 0,1°/2 mol/l. According to a further embodiment, taper angle 94, for example taper angle 94 of edges of segments 100, 101, may be increased in a range from 0.3° to 0.7° by increasing the molarity of the etching bath 81 (or etching medium 81) by a value of from 4 mol/l to 8 mol/l, preferably by increasing the molarity of KOH by 6 mol/l. Thus, according to this embodiment, determining the molarity of the etching bath may include the step of increasing the molarity of the etching bath 81 (or etching medium 81) by a value of from 4 mol/l to 8 mol/l, preferably by increasing the molarity of KOH by 6 mol/l to increase the taper angle in a range from 0.3° to 0.7° with respect to a reference point of the molarity and taper angle. Preferably, reference points which may be used according to the above explained embodiments for adjusting the parameters of the etching bath are derived from measurements, i.e., from measured taper angles at glass segments etched in etching baths with known molarity or viscosity. Of course, the values of the one or more reference points may be corrected, e.g., by averaging or linear regression. Generally, the determination of the molarity or viscosity may be accomplished using a reference function of the taper angle in dependence of the molarity or viscosity. The function returns the molarity or viscosity for the respective taper angle to be achieved. This function may also be represented by a table. For example, the above explained embodiment using a factor of at least 0,1°/2 mol/l in fact uses a linear reference function with a gradient given by this factor. Generally, a reference function may be obtained by a regression, particular a linear regression of multiple measurements, i.e., multiple measured reference points. The factor may even amount to at least 0.2°/(mol/l), e.g., to approximately 0.25°/(mol/l). It is to be understood that there are other parameters which also have an influence on the taper angle. Thus, other adaptations of the etching parameters may be chosen alternatively or additionally to the molarity or viscosity of the etching bath to obtain a desired taper angle. Specifically, as mentioned above, other etching parameters include the etching depth and the etch removal or the etching time which corresponds to the etch removal for a given molarity and temperature may influence the taper angle and therefore can be used to adjust the taper angle to its desired value. Further, the etching depth may be taken into account when adjusting the parameters to achieve a desired taper angle. The etching depth corresponds to the depth of the channels in the glass element and hence to the glass thickness if the filament shaped flaws 9 extend through the whole glass element from one side to the opposite side. Similarly, The etching rate and the dependence of the taper angle to the molarity of the etching bath also typically depends on the glass type. The examples disclosed herein with respect to the change of the taper angle with respect to the molarity refer to the glass type D263. However, the ranges given herein may also apply to other glasses. Generally, the changes of the taper angle with the molarity of the etching bath as disclosed herein typically apply to glasses having a content of SiO2in a range from 30 to 85 weight percent. The present invention is further directed to a plate shaped glass element 1. In particular, plate shaped glass element 1 may be produced or is produced or producible with a method according to embodiments of the present disclosure. Preferably, according to an embodiment, at least taper two taper angles 94 between boundary lines 12 and the perpendicular 13 of side faces 14, 15 differ from each other. According to a further embodiment, at least one of channels 10 has a wall 6 with boundary line 12 that has different taper angles to the perpendicular 13 of side faces 14, 15 at openings 60, 61 of channel 10 to the respective side faces 14, and 15. According to a further embodiment, boundary lines 12 of walls 6 at openings 60, 61 of channels 10 of side faces 14, 15 differ from each other. According to a further embodiment, within at least one section, wall 6 is concavely curved with respect to a direction perpendicular 13 to side faces 14, 15. According to a further embodiment, a multitude of channels 10 is distributed over glass element 1 in a predefined pattern. For example, the predefined pattern may constitute a grid, or a circle, or a spiral. According to a further embodiment, glass element 1 has a thickness of at most 200 μm and preferably at least 3 μm, more preferably at least 5 μm and most preferably at least 10 μm. Such glass elements 1 and/or segments 100, 101 may for example be used in printed circuit applications, microfluidic devices or for liquid lenses. A method of structuring a glass element having a first side face and a second side face is provided. The method includes the steps of: producing a filament-shaped flaw in the glass element with a pulsed laser beam along a focus line; etching to remove glass in the filament-shaped flaw to form a wall extending from the first side face towards the second side face, the wall having a boundary line that is tapered at a vertex between the wall and the first side face with a taper angle with respect to a perpendicular of the first side face; and adjusting the taper angle by controlling a feature of the focus line. The feature is selected from a group consisting of a position of the focus line, a length of the focus line, an intensity distribution of the focus line, and any combinations thereof. 1. A method of structuring a glass element having a first side face and a second side face, comprising:
producing a filament-shaped flaw in the glass element, the filament-shaped flaw extending transversely to first and second side faces of the glass element, wherein the step of producing the filament-shaped flaw comprises:
directing a pulsed laser beam onto the first side face of the glass element, the glass element being transparent for the pulsed laser beam, focusing, using focusing optics, the pulsed laser beam to form a focus line in the glass element such that the pulsed laser beam has an intensity within the focus line that is sufficient to produce the filament-shaped flaw, and adjusting the focus line so that the filament-shaped flaw ends within the glass element; etching to remove glass in the filament-shaped flaw to form a wall extending from the first side face towards the second side face, the wall having a boundary line that is tapered at a vertex between the wall and the first side face with a taper angle with respect to a perpendicular of the first side face; and adjusting the taper angle by controlling a feature of the focus line, the feature being selected from a group consisting of a position of the focus line, a length of the focus line between the first and second side faces, an intensity distribution of the focus line, and any combinations thereof. 2. The method of 3. The method of advancing the pulsed laser beam with respect to the glass element; and repeating the producing, etching, and adjusting steps to form a multitude channels that are distributed over the glass element in a predefined pattern. 4. The method of 5. The method of 6. The method of 7. The method of 8. The method of 9. The method of 10. The method of 11. The method of etching to remove glass in the second filament-shaped flaw to form a second wall extending from the second side face towards the first side face, the second wall having a second boundary line that is tapered at a second vertex between the second wall and the second side face with a second taper angle with respect to a perpendicular of the second side face 12. The method of 13. The method of 14. The method of 15. The method of 16. The method of 17. The method of 18. The method of 19. The method of 20. The method of 21. A plate shaped glass element, comprising:
a first side face; a second side face opposite the first side face; and a multitude of etched channels extending through the glass element, each channel having walls that connect the first and second side faces to one another, wherein the walls have a taper angle with respect to the first or second side faces, respectively.CROSS REFERENCE TO RELATED APPLICATIONS
BACKGROUND
1. Field of Invention
2. Description of Related Art
SUMMARY
BRIEF DESCRIPTION OF FIGURES
DETAILED DESCRIPTION
1 Glass element 5 Laser beam 6 Wall 7 Ultrashort pulse laser, laser 8 Focus line of laser beam 5 9, 9a, 9b, 9c, 9d, 9e, 9f, 9g, 9h Filament-shaped flaw, flaw 90 Series of flaws 10, 10a, 10b, 10c, 10d Channel 11 Path 12 Boundary line 13 perpendicular 14, 15 Side faces of glass element 1 16, 17, 18, 19 Vertices 20 Positioning means 50, 51 Partial beams of laser 5 52 Interference region 53 Length of interference region 54 Intensity maximum 55 Interference angle 60, 61 Openings of channel 10 62 Straight portion of channel 10d 70 Focussing optics 71 Computing means 80 Etching tank 81 Etching medium, etching bath 91 Blind hole 94 Taper angle 100, 101 Segments of glass element 1 102 Opening within segment 100 105 Edge of segments 100, 101







