Methods of reducing surface roughness of reflectance coatings for DUV mirrors
10345494 ยท 2019-07-09
Assignee
Inventors
Cpc classification
International classification
Abstract
A method of reducing surface roughness of DUV reflectance coatings for a DUV mirror to improve the reflectance of the DUV mirror includes: forming the reflectance coating on a substrate, the reflectance coating including a film stack comprising multiple dielectric layers, including an uppermost layer. The method also includes adding to the uppermost layer a cap layer comprising SiO.sub.2 and having an upper surface with an initial RMS amount of surface roughness. The method further includes adding a sacrificial layer to the upper surface of the cap layer, wherein the sacrificial layer comprises SiO.sub.2. The method also includes etching the sacrificial layer down to the cap layer so that the upper surface of the cap layer has a final RMS amount of surface roughness that is less than the initial amount of surface roughness.
Claims
1. A method of improving a reflectance of a deep ultraviolet (DUV) reflectance coating, comprising: a) forming the reflectance coating on a substrate, the reflectance coating including a film stack comprising multiple dielectric layers, including an uppermost dielectric layer; b) adding to the uppermost dielectric layer of the film stack a dielectric cap layer having a thickness and having an upper surface with an initial root-mean-square (RMS) amount of surface roughness SR.sub.0, and wherein the cap layer is deposited at a first deposition rate; c) adding a sacrificial layer to the upper surface of the cap layer, wherein the sacrificial layer is made of the same material as the dielectric cap layer, and wherein the sacrificial layer is deposited at a second deposition rate; and d) etching the sacrificial layer down to the cap layer without substantially reducing the thickness of the cap layer so that the upper surface of the cap layer has a final RMS amount of surface roughness SR.sub.F that is less than the initial amount of surface roughness SR.sub.0.
2. The method according to claim 1, wherein the material that makes up the dielectric cap layer and the sacrificial layer comprises either silicon dioxide or doped silicon dioxide.
3. The method according to claim 1, wherein the material that makes up the dielectric cap layer and the sacrificial layer consists of either silicon dioxide or doped silicon dioxide.
4. The method according to claim 1, further comprising: e) repeating acts c) and d) so that the final RMS amount of surface roughness SRF is at least 10% smaller than the initial RMS amount of surface roughness SR.sub.0.
5. The method according to claim 1, further comprising: e) repeating acts c) and d) so that the final RMS amount of surface roughness SRF is at least 20% smaller than the initial RMS amount of surface roughness SR.sub.0.
6. The method according to claim 1, further comprising: e) repeating acts c) and d) between 5 and 10 times.
7. A method of improving a reflectance of a deep ultraviolet (DUV) reflectance coating, comprising: a) forming the reflectance coating on a substrate, the reflectance coating including a film stack comprising multiple dielectric layers, including an uppermost dielectric layer; b) adding to the uppermost dielectric layer of the film stack a cap layer comprising silicon dioxide (SiO.sub.2), wherein the cap layer has a thickness and wherein the cap layer has an upper surface with an initial root-mean-square (RMS) amount of surface roughness SR.sub.0, and wherein the cap layer is deposited at a first deposition rate; c) adding a sacrificial layer to the upper surface of the cap layer, wherein the sacrificial layer comprises SiO.sub.2, and wherein the sacrificial layer is deposited at a second deposition rate; and d) etching the sacrificial layer down to the cap layer without substantially reducing the thickness of the cap layer so that the upper surface of the cap layer has a final RMS amount of surface roughness SR.sub.F that is less than the initial amount of surface roughness SR.sub.0.
8. The method according to claim 7, further comprising: e) repeating acts c) and d) so that the final RMS amount of surface roughness SRF is at least 10% smaller than the initial RMS amount of surface roughness SR.sub.0.
9. The method according to claim 7, further comprising: e) repeating acts c) and d) so that the final RMS amount of surface roughness SR.sub.F is at least 20% smaller than the initial RMS amount of surface roughness SR.sub.0.
10. The method according to claim 7, further comprising: e) repeating acts c) and d) between 5 and 10 times.
11. The method according to claim 7, wherein the etching comprises plasma etching with a plasma that contains oxygen radicals.
12. The method according to claim 7, wherein the cap layer and the sacrificial layer each comprise either SiO.sub.2 or doped SiO.sub.2.
13. The method according to claim 7, wherein the cap layer and the sacrificial layer each consists of either SiO.sub.2 or doped SiO.sub.2.
14. The method according to claim 7, wherein one or more of the dielectric layers of the multiple dielectric layers includes fluoride.
15. The method according to claim 7, wherein the multiple dielectric layers are made of materials layers selected from the group of materials consisting of: aluminum fluoride, gadolinium fluoride, magnesium fluoride, lanthanum fluoride, silicon dioxide and aluminum oxide.
16. The method according to claim 7, wherein the film stack resides upon a base film stack that resides immediately adjacent the substrate and the film stack comprises alternating layers of aluminum oxide and silicon dioxide.
17. The method according to claim 7, wherein the thickness of the silicon dioxide cap layer is in the range from 55 nm to 70 nm.
18. The method according to claim 7, wherein the substrate comprises silicon dioxide.
19. The method according to claim 7, wherein the cap layer is deposited at the first deposition rate and the sacrificial layer is deposited at the second deposition rate that is slower than the first deposition rate by at least 5%.
20. The method according to claim 19, wherein the first deposition rate is 0.25 nm/s and the second deposition rate is 0.15 nm/s.
21. The method according to claim 7, wherein the reflectance coating after performing the act b) has a reflectance R<99% and wherein the reflectance coating after performing the acts c) and d) one or more times is R>99%.
22. The method according to claim 7, wherein the reflectance of the reflectance coating is optimized over a wavelength band that includes at least one of the following wavelengths: 193 nm, 213 nm and 266 nm.
23. A method of improving a reflectance of a deep ultraviolet (DUV) reflectance coating, comprising: a) forming the reflectance coating on a substrate, the reflectance coating including a film stack comprising multiple dielectric layers, including an uppermost layer; b) adding to the uppermost layer of the film stack a cap layer consisting of either silicon dioxide or doped silicon dioxide, wherein the cap layer has a thickness and has an upper surface with an initial root-mean-square (RMS) amount of surface roughness SR.sub.0, and wherein the cap layer is deposited at a first deposition rate; c) adding a sacrificial layer to the upper surface of the cap layer, wherein the sacrificial layer consists of the same material as the cap layer, and wherein the sacrificial layer is deposited at a second deposition rate; d) plasma etching the sacrificial layer with a plasma containing oxygen radicals down to the cap layer; and e) performing acts c) and d) multiple times until the upper surface of the cap layer has a final RMS amount of surface roughness SRF that is less than the initial RMS amount of surface roughness SRF by at least 10%.
24. The method according to claim 23, wherein act e) includes repeating acts c) and d) between 2 and 10 times.
25. The method according to claim 23, wherein the cap layer is deposited at the first deposition rate and the sacrificial layer is deposited at the second deposition rate that is slower than the first deposition rate by at least 5%.
26. The method according to claim 23, wherein the multiple dielectric layers are made of materials selected from the group of materials consisting of: aluminum fluoride, gadolinium fluoride, magnesium fluoride, lanthanum fluoride, silicon dioxide and aluminum oxide.
27. The method according to claim 23, wherein the reflectance coating after performing the act b) has a reflectance R<99% and wherein the reflectance coating after performing act e) is R>99%.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the Detailed Description serve to explain principles and operation of the various embodiments. As such, the disclosure will become more fully understood from the following Detailed Description, taken in conjunction with the accompanying Figures, in which:
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DETAILED DESCRIPTION
(12) Reference is now made in detail to various embodiments of the disclosure, examples of which are illustrated in the accompanying drawings. Whenever possible, the same or like reference numbers and symbols are used throughout the drawings to refer to the same or like parts. The drawings are not necessarily to scale, and one skilled in the art will recognize where the drawings have been simplified to illustrate the key aspects of the disclosure.
(13) The claims as set forth below are incorporated into and constitute part of this Detailed Description.
(14) Cartesian coordinates are shown in some of the Figures for the sake of reference and are not intended to be limiting as to direction or orientation.
(15) The terms method and process are used interchangeably herein.
(16) In the discussion below, the terms final cap layer and final upper surface are used to describe the resulting cap layer and resulting upper surface, respectively, when the methods described herein are carried out to completion. Thus, the word final in this context does not relate to a physical position of the cap layer or the upper surface relative to the underlying film stack but rather to the result of the last or final step in the process of reducing surface roughness as described in detail below.
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(19) The cap layer 120 has an upper surface 122 with a surface roughness SR, which in an example is measured as a root-mean-square (RMS) value, as is commonly done in the art. The cap layer 120 is used to protect the dielectric layers 102 and 104 from the environment in which DUV mirror may be used. For example, cap layer 120 can be used to prevent moisture from adversely affecting the dielectric layers 102 and 104. In an example, cap layer 120 is not a functional layer, i.e., it is configured to not substantially change the designed reflectance of the reflectance coating 50 based on interference effects as defined by the underlying dielectric layers 102 and 104.
(20) The cap layer 120 has a physical thickness TH.sub.C that defines an optical thickness or optical path length OPL=(TH.sub.C).Math.n.sub.C, where n.sub.C is the refractive index of the material making up the cap layer at wavelength , usually the center wavelength .sub.0. In an example of obtaining an optimal reflectance, the OPL is designed to be a multiple of a half-wave, i.e., OPL=(TH.sub.C).Math.n.sub.C=m.Math..sub.0/2, where m is an integer. Thus, in an example, the physical thickness of cap layer is TH.sub.C=(m.Math..sub.0)/(2.Math.n.sub.C).
(21) In an example, cap layer 120 comprises SiO.sub.2, e.g., the cap layer 120 can consist of pure SiO.sub.2 or can consist of doped SiO.sub.2, e.g., fluorine-doped SiO.sub.2 (FSiO.sub.2). In an example, the thickness TH.sub.C of cap layer 120 is in the range from 55 nm to 75 nm, and further in an example, the thickness TH.sub.C is within this range subject to the above-described half-wave requirement for the OPL.
(22) The reflectance coating 50 has an initial reflectance R.sub.0 over a select wavelength band that includes at least one DUV wavelength .sub.0, which in example is a center wavelength of the wavelength band. Example DUV wavelengths .sub.0 can fall within the range from 193 nm to 266 nm and so can include 193 nm, 213 nm and 266 nm, as well as other wavelengths within the range.
(23) In an example, the initial reflectance R.sub.0<99%, e.g., 98.5% or 98%. This initial reflectance R.sub.0 is less than the theoretical reflectance R.sub.T based on the design of reflectance coating 50. This difference is due to the aforementioned manufacturing shortcomings when forming reflectance coating 50, including in particular the surface roughness SR of cap layer 120.
(24) The initial reflectance R.sub.0 is defined in part by upper surface 122 of cap layer 120 having an initial amount of surface roughness SR.sub.0 as defined when the cap layer 120 is first formed atop the underlying stack 100.
(25) The reflectance coating 50 can include one or more multilayer stacks 100.
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(28) Also in an example, cap layer 120 is deposited at a first deposition rate DR.sub.1 and the sacrificial layer 220 is deposited at a second deposition rate DR.sub.2 that is slower than the first deposition rate DR.sub.1. In an example, the second deposition rate DR.sub.2 is between 5% and 60% slower than the first deposition rate DR.sub.1, while in another example the second deposition rate DR.sub.2 is between 10% and 50% slower than the first deposition rate DR.sub.1, while in another example the second deposition rate DR.sub.2 is between 20% and 50% slower than the first deposition rate DR.sub.1. In an example, the first deposition rate DR.sub.1 is in the range from 0.2 nm/s to 0.3 nm/s and the second deposition rate is in the range from 0.1 nm/s to 0.2 nm/s DR.sub.2, subject to the condition that DR.sub.2<DR.sub.1, and preferably subject to the condition that DR.sub.2<(0.95).Math.DR.sub.1 or DR.sub.2<(0.9).Math.DR.sub.1 or DR.sub.2<(0.80).Math.DR.sub.1. For example, the first deposition rate can be 0.25 nm/s while the second deposition rate can be 0.15 nm/s.
(29) The next step in the method involves removing sacrificial layer 220 from cap layer 120.
(30) In an example, the removal of sacrificial layer 220 from cap layer 120 is preferably carried out in a manner that does not leave behind any substantial amount of the sacrificial layer and that does not remove any substantial amount of cap layer 120. In other words, there can be some amount of sacrificial layer 200 remaining and/or there can be some amount of material removed from cap layer 120 so long as the functionality of cap layer 120 and the overall performance of reflectance coating 50 is not substantially adversely affected. In an example, an adverse effect is not considered substantial when it results in a reduction in the reflectance of 0.1% or less. In an example, small amounts of material from sacrificial layer 220 may remain on upper surface 122 of cap layer 120 and fill in the valleys defined by surface roughness, thereby reducing the amount of surface roughness without substantially changing the overall thickness TH.sub.C of cap layer 120.
(31) The cap layer 120 and its upper surface 122 are respectively denoted 120P and 122P in
(32) In an example, the acts of depositing sacrificial layer 220 on cap layer 120 and then removing the sacrificial layer illustrated in
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(34) In an example where the surface roughness SR is expressed as an RMS value, the final RMS amount of surface roughness SR.sub.F for cap layer upper surface 122F is at least 5% less than the initial RMS amount of surface roughness SR.sub.0 of the cap layer 120. In another example, the final RMS amount of surface roughness SR.sub.F for cap layer upper surface 122F is at least 10% less than the initial RMS amount of surface roughness SR.sub.0 of the initial cap layer 120. In another example, the final RMS amount of surface roughness SR.sub.F for cap layer upper surface 122F is at least 20% less than the initial RMS amount of surface roughness SR.sub.0 of the initial cap layer 120. In another example, the final RMS amount of surface roughness SR.sub.F for cap layer upper surface 122F is at least 25% less than the initial RMS amount of surface roughness SR.sub.0 of the initial cap layer 120. In another example, the final RMS amount of surface roughness SR.sub.F for cap layer upper surface 122F is at least 30% less than the initial RMS amount of surface roughness SR.sub.0 of the initial cap layer 120. In another example, the final RMS amount of surface roughness SR.sub.F for cap layer upper surface 122F is at least 40% less than the initial RMS amount of surface roughness SR.sub.0 of the initial cap layer 120.
(35) In an example where the initial reflectance R.sub.0<99%, after processing cap layer 120 using the method described above to reduce the cap layer surface roughness, the reflectance coating has a final reflectance R.sub.F>99%.
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(37) Thus, the example reflectance coating 50 of
Experimental Results
(38) In one experiment, an example mirror 10 was formed with a reflectance coating 50 designed to operate at a DUV wavelength 0=193 nm. The reflectance coating 50 was formed using a vacuum-based deposition process in a vacuum coater. The reflectance coating 50 included a first oxide stack 100A immediately adjacent the substrate with multiple periods of SiO2 and Al2O3 layers 102A and 104A, respectively. The reflectance coating also had a fluoride stack 100B atop the oxide stack 100A. The fluoride stack had multiple periods of layers 102B and 104B of low-index and high-index fluoride materials, respectively. The fluoride stack 100B was capped with a half-wave FSiO2 capping layer. The upper surface 122 of cap layer 120 had an initial surface roughness SR0 of 1.691 nm RMS as measured using an atomic force microscope (AFM).
(39) The mirror 10 was then re-loaded into the vacuum coater and a sacrificial layer 220 of FSi02 having a thickness THS of 5 nm was deposited on upper surface 122 of cap layer 120 using a reversed mask and a plasma-ion assisted deposition process. The sacrificial layer 220 was then removed using a plasma etch process with a bias voltage of 110 V, a coil current of 1.6 A and a duration of 11 minutes. The plasma included oxygen radials O* and Ar gas. The 11 min plasma treatment removed sacrificial layer 220. Since the process only included one iteration of addition and removal of sacrificial layer 220, the processed upper surface 122P of cap layer 120 was also the final upper surface 122F and was measured using an AFM and found to have a final amount of surface roughness SRF of 1.533 nm RMS, which is a reduction in surface roughness of 0.158 nm RMS, or about 9%.
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(41) Additional experiments were conducted on an example mirror 10 with a reflectance coating 50 the same as described in the above example but that had a cap layer 120 with a thickness THC of 30 nm and an initial surface roughness SR0 of 2.790 nm RMS. A sacrificial layer 220 with a thickness THS of 5 nm was added and then removed from cap layer 120 six times, i.e., six processing cycles or iteration were performed, using the same plasma-based removal process as described above. The final surface roughness SRF of final upper surface 122F of the final cap layer 120F was measured via AFM to be 1.646 nm RMS, which is a reduction in surface roughness of 1.114 nm RMS or about 41%. In addition, the six plasma-etch treatment cycles were found to bring reflectance spectral curve substantially back to its ideal shape in the both of the side bands. The reduction in the surface roughness resulted in about a 2 reduction in scatter loss at the DUV wavelength 0 of 193 nm.
(42) It will be apparent to those skilled in the art that various modifications to the preferred embodiments of the disclosure as described herein can be made without departing from the spirit or scope of the disclosure as defined in the appended claims. Thus, the disclosure covers the modifications and variations provided they come within the scope of the appended claims and the equivalents thereto.