Sensitized, photo-sensitive glass and its production

Abstract

A sensitized, photo-structurable glasses and methods for producing are provided. The glasses includes Si.sup.4+, one or more crystal-agonist, one or more crystal-antagonist, and one or more pair of nucleating agents. The glasses are sensitized in that the glass reacts more sensitive to irradiation with UV-light and can be crystallized easier and with higher aspect ratios than a non-sensitized glass with equal composition. Furthermore, the sensitized glasses of this invention have smaller crystal sizes after irradiation and tempering than a non-sensitized glass with equal composition. The invention also relates to a structured glass product. Such product can be obtained by submitting the crystallized glass product to a subsequent etching step. The structured product can be used in components or as component for the application fields micro-technology, micro-reaction-technology, electronic packaging, micro-fluidics, FED spacer, bio-technology, interposer, and/or three-dimensional structured antennae.

Claims

1. A photo-structurable glass, which comprises Si.sup.4+, one or more crystal-agonist, one or more crystal-antagonist and one or more pair of nucleating agents, wherein the crystal-agonists are selected from Na.sup.+, K.sup.+, and Li.sup.+, wherein the crystal-antagonists are selected from Al.sup.3+, B.sup.3+, Zn.sup.2+, Sn.sup.2+ and Sb.sup.3+, wherein the pair of nucleating agents comprises cerium and at least one agent from the group of silver, gold and copper, wherein the molar proportion of the crystal-agonists in cat.-% in relation to the molar proportion of Si.sup.4+ is at least 0.3 and at most 0.85, and wherein the glass has a position accuracy value of less than or equal to 0.3%.

2. The glass according to claim 1, wherein the position accuracy value is less than or equal to 0.2%.

3. The glass according to claim 1, comprising the following components in cat.-%: TABLE-US-00008 Si.sup.4+ 45 to 65 Crystal-agonists 30 to 45 Crystal-antagonists 3.5 to 9

4. The glass according to claim 1, comprising the following components in cat.-%: TABLE-US-00009 Si.sup.4+ 45 to 65 Crystal-agonists Li.sup.+ 25 to 40 K.sup.+ 0 to 8 Na.sup.+ 0 to 8 Crystal-antagonists B.sup.3+ 0 to 5 Al.sup.3+ 0 to 10 Zn.sup.2+ 0 to 4 Sb.sup.3+ 0 to 0.4 Nucleating agents Ce.sup.3+/Ce.sup.4+ >0 to 0.3 Ag.sup.+ >0 to 0.5

5. The glass according to claim 1, wherein the glass contains between 0.02 and 0.2 cat.-% Sb.sup.3+.

6. The glass according to claim 1, wherein the transmittance value is at least 8% at a glass thickness of 1 mm and a wavelength of 280 nm.

7. The glass according to claim 1, having an internal transmittance of at most 50% at 314 nm and at a thickness of 1 mm.

8. The glass according to claim 1, wherein the surface of the glass has a roughness Ra of less than 5 nm.

9. The glass according to claim 1, wherein the glass has a transmittance value of at least 0.2% at a wavelength of 160 nm and a sample thickness of 1 mm.

10. The glass according to claim 1, wherein the glass has cooling state, which corresponds to a steady cooling from a temperature T1 to a temperature T2 with a cooling rate K of at most 200 C./h, wherein temperature T1 is at least above the glass transition temperature T.sub.g of the glass and the temperature T2 is at least 150 C. below T1.

11. A method for producing a glass according to claim 1, comprising the steps of: mixing the respective raw materials for obtaining a mixture; melting the mixture for obtaining a melt; and solidifying the melt for obtaining a glass.

12. The method according to claim 11, further comprising a sensitizing the glass step subsequent to solidifying the melt, wherein the sensitizing step comprises cooling the glass from a temperature T1 to a temperature T2 with an average cooling rate of at most 200 C./h, subsequent to re-heating the glass.

13. The method according to claim 11, wherein the solidifying the melt step comprises cooling the glass from a temperature T1 to a temperature T2 with an average cooling rate of at most 200 C./h.

14. The method according to claim 12, wherein temperature T1 is at least above the glass transition temperature T.sub.g of the glass and temperature T2 is at least 150 C. below T1.

15. A crystallized product obtainable by light exposure and tempering of a glass according to claim 1.

16. The crystallized product according to claim 15, wherein the depth of light exposure is at least 1 mm.

17. A structured product obtainable by light exposure, tempering and structuring of a glass according to claim 1.

18. A photo-structurable glass, which comprises Si.sup.4+, one or more crystal-agonist, one or more crystal-antagonist and one or more pair of nucleating agents, wherein the crystal-agonists are selected from Na.sup.+, K.sup.+, and Li.sup.+, wherein the crystal-antagonists are selected from Al.sup.3+, B.sup.3+, Zn.sup.2+, Sn.sup.2+ and Sb.sup.3+, wherein the pair of nucleating agents comprises cerium and at least one agent from the group of silver, gold and copper, wherein the molar proportion of the crystal-agonists in cat.-% in relation to the molar proportion of Si.sup.4+ is at least 0.3 and at most 0.85, and wherein the glass has a cooling state, which corresponds to a steady cooling from a temperature T1 to a temperature T2 with a cooling rate K of at most 200 C./h, wherein temperature T1 is at least above the glass transition temperature T.sub.g of the glass and the temperature T2 is at least 150 C. below T1.

19. The glass according to claim 1, wherein lithium is present, and a molar proportion of lithium exceeds the molar proportions of sodium and potassium.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the cooling curve of glass B1.

(2) FIG. 2 shows a cooling curve with logarithmically plotted x-axis.

(3) FIG. 3 shows the influence of sensitization of an example glass on the transmittance in the UV-region. Transmittance at 280 nm was measured at a sample thickness of 1 mm. The relative increase in transmittance is shown for the sensitized samples A to C in comparison to a non-sensitized comparative sample. Samples A to C differ with regard to the temperature during sensitization. Temperature T1 was lower in sample A than in sample B and in sample B lower than in sample C. It is evident that the increase in transmittance at 280 nm is more pronounced with increasing temperature T1.

(4) FIG. 4 shows transmittance of an example glass with a thickness of 1 mm in dependence from the wavelength.

(5) FIG. 5 shows the dependence of the achieved etching ratio from the tempering temperature. On the x-axis the tempering temperature and on the y-axis the achieved etching ratio is shown. The highest etching ratio is obtained at a tempering temperature of 580 C.

(6) FIG. 6 shows the standard deviation of the obtained hole-diameter in dependence from the designed hole-diameter. The standard deviations are shown both for the top side (diamonds) and the down side (squares) of the through holes. The standard deviation (in m) is shown on the y-axis. The designed hole-diameter is shown on the x-axis. The results show that the standard deviation is independent of the designed hole-diameter.

(7) FIG. 7 illustrates the distance measurements and the measurement layout with the fixed point in the center and the holes on the circumference.