SUBSTRATE FOR A REFLECTIVE OPTICAL ELEMENT
20210116616 · 2021-04-22
Inventors
Cpc classification
G02B7/181
PHYSICS
C03C3/06
CHEMISTRY; METALLURGY
C03C2217/734
CHEMISTRY; METALLURGY
International classification
Abstract
In order to reduce the degree of relaxation after an optical substrate has been compacted, in particular after a longer period, substrates (51) or reflective optical elements (50), in particular for EUV lithography, with substrates (51) of this type, are proposed. These substrates (51), which have a surface region (511) with a reflective coating (54), are characterised in that, at least near to the surface region (511), the titanium-doped quartz glass has a proportion of Si—O—O—Si bonds of at least 1*10.sup.16/cm.sup.3 and/or a proportion of Si—Si bonds of at least 1*10.sup.16/cm.sup.3 or, along a notional line (513) perpendicular to the surface region (511), over a length (517) of 500 nm or more, a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3.
Claims
1. A substrate for an optical element configured to reflect extreme ultraviolet wavelength light, wherein the substrate is made of titanium-doped quartz glass that has a surface region configured to be coated, and wherein the titanium-doped quartz glass has, at least in a vicinity of the surface region, a proportion of Si—O—O—Si bonds of at least 1*10.sup.16/cm.sup.3 and/or a proportion of Si—Si bonds of at least 1*10.sup.16/cm.sup.3.
2. The substrate as claimed in claim 1, wherein the titanium-doped quartz glass has, at least in the vicinity of the surface region, a proportion of the Si—O—O—Si bonds of at least 1*10.sup.19/cm.sup.3 and/or a proportion of Si—Si bonds of at least 1*10.sup.19/cm.sup.3.
3. The substrate as claimed in claim 1, wherein the titanium-doped quartz glass has an average hydroxyl content of at most 100 ppm by weight at least in the vicinity of the surface region.
4. The substrate as claimed in claim 3, wherein the titanium-doped quartz glass has a matrix terminator content of at most 20% of the hydroxyl content in the vicinity of the surface region.
5. The substrate as claimed in claim 3, wherein the titanium-doped quartz glass has a hydrogen content of less than 1×10.sup.16 molecules/cm.sup.3 at least in the vicinity of the surface region.
6. The substrate as claimed in claim 1, wherein the titanium-doped quartz glass has silicon fluoride or silicon chloride at least in the vicinity of the surface region.
7. A substrate for an optical element configured to reflect extreme ultraviolet wavelength light, wherein the substrate is made of titanium-doped quartz glass that has a surface region configured to be coated, and wherein the titanium-doped quartz glass has a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3 along an imaginary line perpendicular to the surface region over a length of at least 500 nm.
8. The substrate as claimed in claim 7, wherein the titanium-doped quartz glass has a hydrogen content of more than 1×10.sup.19 molecules/cm.sup.3 along the imaginary line perpendicular to the surface region over the length of at least 500 nm.
9. The substrate as claimed in claim 8, wherein the titanium-doped quartz glass has a hydrogen content of more than 1×10.sup.20 molecules/cm.sup.3 along the imaginary line perpendicular to the surface region over the length of at least 500 nm.
10. The substrate as claimed in claim 7, wherein the titanium-doped quartz glass has, at least in the vicinity of the surface region, a proportion of Si—O—O—Si bonds of at least 1*10.sup.16/cm.sup.3 and/or a proportion of Si—Si bonds of at least 1*10.sup.16/cm.sup.3.
11. An optical element configured to reflect extreme ultraviolet wavelength light, comprising a substrate according to claim 1 and a surface region with a reflective coating.
12. The reflective optical element as claimed in claim 11, wherein the substrate has a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3 along an imaginary line perpendicular to the surface region with the reflective coating over a length of at least 500 nm.
13. The reflective optical element as claimed in claim 12, wherein the substrate has a hydrogen content of more than 1×10.sup.20 molecules/cm.sup.3, along the imaginary line perpendicular to the surface region with the reflective coating over a length of at least 500 nm.
14. The reflective optical element as claimed in claim 12, wherein the length of at least 500 nm has a distance from the reflective coating of at most 1 mm.
15. The reflective optical element as claimed in claim 14, wherein the length of at least 500 nm has a distance from the reflective coating of at most 5 μm.
16. The reflective optical element as claimed in claim 12, wherein the substrate has a hydrogen content of less than 5×10.sup.17 molecules/cm.sup.3 along the imaginary line perpendicular to the surface region with the reflective coating at a distance therefrom of at least 1 mm.
17. The reflective optical element as claimed in claim 16, wherein the substrate has a hydrogen content of less than 1×10.sup.16 molecules/cm.sup.3, along the imaginary line perpendicular to the surface region with the reflective coating at a distance therefrom of at least 1 cm.
18. The reflective optical element as claimed in claim 11, wherein the substrate has a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3 within a time period of up to one month after application of the reflective coating along an imaginary line perpendicular to the surface region with the reflective coating over a length of at least 500 nm.
19. The reflective optical element as claimed in claim 18, wherein the substrate has a hydrogen content of more than 1×10.sup.18 molecules/cm.sup.3 within a time period from one month after the application of the reflective coating to seven years after the application of the reflective coating.
20. The reflective optical element as claimed in claim 18, wherein the substrate has a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3 along an imaginary line perpendicular to the surface region with the reflective coating over a length of at least 500 nm, wherein the substrate has a further surface region, which is located on a side of the substrate facing away from the surface region with the reflective coating and has no reflective coating, and wherein the substrate has, along the imaginary line over a further length of at least 500 nm with a distance of no more than 2 mm from the surface of the further surface region, a hydrogen content of no more than half and no less than one twentieth of the hydrogen content over the length at a distance of no more than 1 mm from the reflective coating.
21. An optical system having a reflective optical element as claimed in claim 11.
22. An EUV lithography apparatus having an optical system as claimed in claim 21.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The present invention will be explained in greater detail with reference to preferred exemplary embodiments. In this respect:
[0030]
[0031]
[0032]
[0033]
[0034]
DETAILED DESCRIPTION
[0035]
[0036] A plasma source or a synchrotron can serve for example as the radiation source 12. In the example illustrated here, the radiation source is a plasma source. The emitted radiation in the wavelength range of approximately 5 nm to 20 nm is initially focused by the collector mirror 13. The operating beam is then introduced into the illumination system 14. In the example illustrated in
[0037] In principle, all reflective optical elements 13, 15, 16, 17, 18, 19 of the EUV lithography apparatus 10 can have a substrate made of titanium-doped quartz glass that has a surface region that is to be coated, wherein the titanium-doped quartz glass has a proportion of Si—O—O—Si bonds of at least 1*10.sup.16/cm.sup.3 and/or a proportion of Si—Si bonds of at least 1*10.sup.16/cm.sup.3 at least in the vicinity of the surface region or a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3 along an imaginary line perpendicular to the surface region over a length of 500 nm or more. The possibility of being able to carry out a fine correction of the surface profile that is stable over the long term is important in particular in the case of mirrors of the projection system 20, since the projection system should ideally have the most exact imaging properties possible. Said reflective optical elements can have in their respective substrate a hydrogen content of more than 5×10.sup.18 molecules/cm.sup.3, preferably more than 1×10.sup.19 molecules/cm.sup.3, with particular preference more than 1×10.sup.20 molecules/cm.sup.3, at least along an imaginary line perpendicular to the surface region with the reflective coating over a length of 500 nm or more.
[0038] In the example shown here, the illumination system mirrors 15, 16, the photomask 17, and the projection system mirrors 18, 19 are mirrors 50 for quasi-normal incidence, the reflective coating of which is based on a multilayer system 54, as is shown schematically in
[0039] In the example illustrated here, the coating 52 additionally has an optional protective layer 53, which can also consist of more than one layer. In the case of a molybdenum-silicon multilayer system, for example, the protective layer 53 can be made up of, among other things, a layer of silicon nitride and a layer of ruthenium as a closing-off to the vacuum in order to be used at wavelengths of approximately 13.5 nm. Further suitable material combinations, also for other wavelengths in the EUV wavelength range, are known to a person skilled in the art.
[0040] In principle, the reflective optical elements proposed here can also be designed for grazing incidence. To this end, one or a few metallic layers that reflect the EUV radiation based on the phenomenon of total internal reflection can be provided on the substrate.
[0041] The coating 54 is arranged on a substrate 51 made of titanium-doped quartz glass. In a first variant, the substrate 51 of the reflective optical element for the extreme ultraviolet wavelength range, for example a mirror from the projection system of an EUV lithography apparatus, has a surface region 511 that is to be coated and has already been coated here as described. The substrate 51 has at least in the vicinity of the surface region 511 a proportion of Si—O—O—Si bonds of at least 1*10.sup.16/cm.sup.3 and/or a proportion of Si—Si bonds of at least 1*10.sup.16/cm.sup.3. It is particularly advantageous if the titanium-doped quartz glass has at least in the vicinity of the surface region 511 a proportion of Si—O—O—Si bonds of at least 1*10.sup.17/cm.sup.3 or even at least 5*10.sup.17/cm.sup.3, preferably at least 1*10.sup.18/cm.sup.3 or even at least 5*10.sup.18/cm.sup.3, with particular preference at least 1*10.sup.19/cm.sup.3 or even at least 5*10.sup.19/cm.sup.3, with very particular preference at least 1*10.sup.20/cm.sup.3, and/or a proportion of Si—Si bonds of at least 1*10.sup.17/cm.sup.3 or even at least 5*10.sup.17/cm.sup.3, preferably at least 1*10.sup.18/cm.sup.3 or even at least 5*10.sup.18/cm.sup.3, with particular preference at least 1*10.sup.19/cm.sup.3 or even at least 5*10.sup.19/cm.sup.3, with very particular preference at least 1*10.sup.20/cm.sup.3.
[0042] The higher the proportion of these bonds in the quartz glass matrix is, the more predetermined breaking points there are that break particularly easily under high-energy irradiation. As a result, the corresponding titanium-doped quartz glass can be compacted particularly well under high-energy irradiation. Since these bonds cannot be recombined as easily as normal matrix bonds, i.e. they do not return to their original state as easily after the radiation-induced combination, such substrates show less relaxation than conventional substrates based on titanium-doped quartz glass. Titanium-doped quartz glass with such a composition can be obtained in flame hydrolysis or via a soot process under oxidizing conditions for an increased proportion of Si—O—O—Si bonds or under reducing conditions for an increased proportion of Si—Si bonds. In the case of flame hydrolysis, the flame can be operated for example with an excess of oxygen (oxidizing conditions) or with an excess of hydrogen (reducing conditions). In the case of a soot process, the SiO.sub.2 powder can for oxidizing conditions instead or additionally be treated in an oxygen, nitrous oxide, or water vapor atmosphere at elevated temperatures. In order to achieve reducing conditions, physical drying with elevated temperatures and/or application of a vacuum or chemical drying with the addition of halogens can take place, so that silicon chloride or silicon fluoride are formed, for example.
[0043] In variants, the substrate 51 additionally has at least in the vicinity of the surface region 511 an average hydroxyl content of at most 100 ppm by weight in order to thereby provide a reduced number of matrix terminators and to reduce the probability of relaxation after compaction. The substrate 51 with particular preference has at least in the vicinity of the surface region 514 a matrix terminator content of at most 20% of the hydroxyl content in order to further reduce the probability of relaxation. Further matrix terminators in addition to OH groups can be, for example, SiOH, SiF, SiH, TiOH, TiF, TiH, TiO.sub.2, TiO.sub.3. The blanks for such substrates are preferably produced using soot processes. The hydroxyl content can be reduced, in particular, by way of drying or, respectively, producing and storing it in a particularly dry atmosphere.
[0044] In this variant, the substrate advantageously has a hydrogen content of less than 1×10.sup.16 molecules/cm.sup.3 in the vicinity of the surface region 511 or further inside the substrate 51 in order not to run the risk of reducing the effect achieved by the high purity of the titanium-doped quartz glass again by a slight increase in hydrogen-related matrix terminators such as SiOH and SiH. The hydrogen content can be reduced, for example, by carrying out direct deposition of quartz glass in a low-hydrogen, reducing atmosphere in the case of flame hydrolysis, for example by using natural gas or methane instead of oxyhydrogen gas as fuel. Quartz glass deposited using a soot process does not include any hydrogen a priori unless it is specifically added.
[0045] In a second variant, which is shown schematically in
[0046] The titanium-doped quartz glass blank can be loaded with a high hydrogen content even before it is machined into a substrate at temperatures above room temperature, for example in the range up to 600° C., preferably at approximately 100° C. to 200° C., in particular in the vicinity of the surface region 511. Higher temperatures, for example in the range from 400° C. to 600° C., make it possible for the desired hydrogen content or particularly high hydrogen contents to be reached more quickly. However, at higher temperatures, Ti3+ can form to a greater extent, which can lead to blackening of the quartz glass and can also have an undesirable influence on the coefficient of thermal expansion of the quartz glass.
[0047] The blank can also initially be largely or completely machined into its final shape, so that a substantially coatable substrate is available, which is loaded with hydrogen before coating. Both the blank and the substantially coatable substrate can preferably be loaded with hydrogen in an autoclave at hydrogen partial pressures in the range of preferably approximately 10 atm to 100 atm. Particularly narrow hydrogen gradients with high contents in the surface region can be obtained in particular at higher pressures.
[0048] In the event that material is removed from the surface by polishing after loading with hydrogen and before coating, the maximum of the distribution of the hydrogen content can be located particularly close below the reflective coating then applied. Simulations suggest that even if the hydrogen content in the surface region, especially in the immediate vicinity below the reflective coating, is somewhat lower than desired shortly after the coating, for example due to relatively long storage times between loading and coating or targeted tempering, the hydrogen content will increase over months and years below the reflective coating.
[0049] After coating, surface defects that are still present or that have occurred during the coating process can be corrected by compacting irradiation. It is also possible, optionally even before the coating, to carry out an extensive compaction process over at least the entire coated area, during which in the irradiated substrate regions having a high hydrogen content bonds are broken up and saturated as SiH or SiOH in order to additionally increase the long-term stability of the reflective optical element overall. During subsequent storage, the hydrogen can diffuse further into the substrate and can also emerge from the substrate at uncoated surfaces, in particular. For example, Mo/Si multilayer coatings are good diffusion barriers for hydrogen. Simulations suggest that substrates that are loaded with hydrogen in the region of their surfaces before coating, still have very high hydrogen contents in the region of the surface coated, for example, with a Mo/Si multilayer system even after several years of storage. On the uncoated surface regions, by contrast, the hydrogen content can drop significantly within merely months. In particular, reflective optical elements according to variant 2 and as described in connection with
[0050] As an example, reference is made to
[0051]
[0052] It should be noted that this effect is discussed here in relation to the surface with a reflective coating and the opposite surface without a coating for the sake of clarity. However, this effect is of course also expected for differently positioned surfaces, such as side surfaces. Here, too, a greater decrease in the hydrogen content over time is to be expected over time if the respective surface is not coated after loading with hydrogen compared to if it is coated.
[0053] In a modification of the variant described in connection with
[0054] The hydroxyl and hydrogen contents as well as the proportion of defects in the quartz glass matrix such as Si—O—O—Si bonds or Si—Si bonds can be determined, for example, via Raman spectroscopy on the finished substrate or reflective optical element with resolutions down to the sub-millimeter range. With confocal Raman spectroscopy, resolutions in the sub-micrometer range can also be achieved. Raman spectroscopy can also be used to determine the fictitious glass transition temperature of different substrate regions, for example via the ratio of three- to fourfold SiO.sub.2 rings. Depending on whether it is an uncorrected region or a region compacted for correction purposes by high-energy irradiation, different fictitious glass transition temperatures and different defect densities can be expected.
[0055] In the embodiments of a reflective optical element 50 shown in
[0056] The reflective optical elements proposed here show improved long-term stability of the surface shape. In particular, the relaxation of the corrections written by compacting is reduced. Even after seven years, for example, it can be expected that the corrections will still have an amplitude of over two thirds of their original amplitude.
[0057] Further preferred applications of the reflective optical elements based on the substrates proposed here include, in addition to EUV lithography, optical systems for inspection systems for, for example, wafers or masks or for spectroscopic applications, for example in astrophysics, in particular extra-terrestrial physics.
REFERENCE SIGNS
[0058] 10 EUV lithography apparatus [0059] 12 EUV radiation source [0060] 13 Collector mirror [0061] 14 Illumination system [0062] 15 First mirror [0063] 16 Second mirror [0064] 17 Mask [0065] 18 Third mirror [0066] 19 Fourth mirror [0067] 20 Projection system [0068] 21 Wafer [0069] 50 Collector mirror [0070] 51 Substrate [0071] 511 Surface region [0072] 512 Surface [0073] 514 Line [0074] 513 Line [0075] 515 Region [0076] 516 Region [0077] 517 Length [0078] 53 Protective layer [0079] 54 Multilayer system [0080] 55 Pair of layers [0081] 56 Absorber [0082] 57 Spacer