Lens-based, high-resolution x-ray microscopy largely resulted from research work at synchrotron radiation facilities in Germany and United States starting in the 1980's. While projection-type x-ray imaging systems with up to micrometer resolution have been widely used since the 1930s, ones using x-ray lens with sub-100 nanometer (nm) resolution began to enter the market only this century. These high-resolution microscopes are configured similarly to visible-light microscopes with an optical train typically including an x-ray source, condenser lens, objective lens, and detector.
Because x rays do not refract significantly in most materials, nearly all such x-ray microscopes use diffractive objective lenses, called Fresnel zone plates. A zone plate is a circular grating with linearly decreasing pitch as a function of radius. The grating comprises sets of radially symmetric circular rings separated by annular spaces. The rings are typically fabricated from a material of a high density to maximize the interaction with x-rays by either absorption, phase shift or a combination of both.
Traditionally, zone plates have been manufactured with a multi-level lithographic process to produce high aspect ratio structures that are necessary to produce zone plates with high efficiency. In one example, a silicon nitride membrane layer is deposited with a seed layer of metal, and a thick organic resist layer on top of the seed metal layer is deposited with a thin layer of metal such as titanium to form a hard mask for deep reactive etching. A very thin resist layer is coated on top of the hard mask layer, which is then patterned with the desired widths of the rings and the annular spaces via electron-beam lithography, and developed. The pattern is then transferred into the hard mask by a dry etching step, and the entire structure is transferred into the thick organic resist by highly directional dry etch to form a plating mold. Finally, the structure of the zone plate is created by electroplating into the mold and the mold is removed by dry etching, leaving the zones of the zone plate.
With higher energy x-ray radiation, thicker zone plates are required to achieve optimal efficiency. For example, a zone plate having a thickness of 1650 nanometers (nm) of gold reaches a maximum focusing efficiency of 30.66% at 10 keV. At this same energy, a 350 nm thick zone plate has an efficiency below 3%. Therefore, the challenge of making high resolution and high efficiency zone plate lenses becomes the challenge of making structures with high thickness-to-width aspect ratios, especially with increasing x-ray energy.
The criticality in fabricating thicker zone plates comes in the fabrication and the mechanical stabilization of the outer zones. It is here that the aspect ratios become extreme since the outer zones are the narrowest zones, yet have to be the same height as the other, inner, wider zones. Fabricating these zones challenges existing fabrication processes such as etching and plating technology due to the narrowness of the zones. And then, once fabricated, those high aspect ratio zones can be easily toppled by mechanical stress or other stresses such as charging effects.
A newer zone plate fabrication method uses Atomic Layer Deposition (ALD) to eliminate some of the critical fabrication steps, provide higher aspect ratios and provide higher yields than traditional zone plate manufacturing methods. Atomic Layer Deposition (ALD) Zone plates and fabrication methods are discussed in “Ultra-high resolution zone-doubled diffractive X-ray optics for the multi-keV regime,” Vila-Comamala, J. et al., 3 Jan. 2011, Vol. 19, No. 1, OPTICS EXPRESS 175-184, and “Zone Plate Microscopy to Sub-15 nm Spatial resolution with XM-1 at the ALS,” Chao, W. et al, Proc. 8th Int. Conf. X-ray Microscopy, IPAP Conf. Series 7, pp. 4-6.
In the ALD zone plate fabrication method, a resist layer, typically made of a material with a low refractive index, such as hydrogen silsesquioxane (HSQ), is directly exposed using electron beam lithography and developed to form ring-like HSQ structures as a template for the ALD deposition. Then, zones of the zone plate are formed by conformal coating of a high electron density material, such as a Platinum or Iridium, to the template via ALD. Since the ALD process is a conformal coating process, the deposited metal layer coats both the top, bottom and sidewalls of the template to form the zones of the zone plate. However only the coatings on the sidewalls form the diffractive structures of the zone plate.
ALD zone plate fabrication requires fewer steps, is less complex, improves the quality of outermost zones, and provides a frequency doubling aspect as compared to traditional zone plate plating methods. ALD can also provide an increase in the achievable aspect ratios. The ALD layer can be as thin as a 1 nm and possibly even thinner. Moreover, using a resist layer or template such as HSQ, a straighter sidewall can be obtained as compared to plating methods. The limit to the aspect ratio of ALD zone plates is determined by the straightness of the fabricated sidewalls, i.e. the lateral displacement of the top and bottom of a sidewall has to be less than the coating thickness or zone width.
In ideal zone plates, the zones have varying zone widths. The width of the zones increases with decreasing radial distance from the center of the zone plate. And, the width of each zone and its annular space are similar to achieve best focusing efficiency in the first diffraction order. This generally leads to a fixed duty cycle (DCY) of 0.5 across the ideal zone plates, where DCY is a ratio of the width of a given zone and grating period.
Unlike ideal zone plates, conventional ALD zone plates have been constrained to a fixed zone width, which is equal to the thickness of the ALD layer. However, the width of the annular spaces will often increase with decreasing radial distance from the center of the zone plate, as in ideal zone plates. This causes the duty cycle of zones in conventional ALD zone plates to decrease with decreasing radial distance from the center of the zone plate, and therefore, the efficiency of the zones to decrease with decreasing radial distance from the center of the zone plate as compared to ideal zone plates.
As a result, though the ALD process provides many fabrication advantages over traditional methods, by design, conventional ALD zone plates suffer from decreased efficiency by as much as 30% as compared to an ideal zone plate.
The present invention provides a system and method for improving efficiency of ALD zone plates or zone plates fabricated using a similar conformal coating process. Embodiments of the present invention can provide efficiency improvements for zones across all sections of the zone plate, with significant efficiency improvements of up to twice that of conventional ALD zone plates, especially for the zones of innermost sections.
The present invention accomplishes the efficiency increase of the zones of the zone plate by first designing the template to allow for thicker zone widths, from one times a thickness of the conformal (ALD) coating layer up to and including two times the thickness of the conformal coating layer, in one example. The design of the template includes increasing the spatial frequency of the annular rings of the template as compared to conventional ALD zone plates. The spatial frequency of the annular rings is determined by a mark-to-space ratio of the annular rings, which compares the width of the annular rings to the width of annular channels formed by the annular rings of the template.
Then, the ALD or other conformal layer is deposited until it substantially fills at least some of the annular channels between the annular rings, which creates wider zones. The wider zones increase the duty cycle of the zones, which improves their diffraction efficiency as compared to conventional ALD zone plates.
In embodiments, the invention can provide efficiency improvements for zones of inner sections only, or for zones across all sections of the zone plate, including outermost zones, as compared to conventional ALD zone plates.
In general, according to one aspect, the invention features a method for fabricating a zone plate. The method comprises patterning a resist layer to form a template with annular rings that define annular channels, and then depositing a conformal coating layer to form zones of the zone plate on sidewalls of the annular rings, the conformal coating layer substantially filling at least some if not all of the annular channels to form wider zones.
Preferably, depositing the conformal coating layer to form the zones is accomplished using atomic layer deposition (ALD). The resist layer is patterned to form the template, in which the template is designed to have an increasing mark-to-space ratio of the annular rings towards a center of the zone plate over more traditional designs.
Examples of the method use a mark-to-space ratio of Wr-A:A for the annular rings of the template zones located at a local radius r from the center of the zone plate, r being up to ½ times a radius R of the zone plate. A is a thickness of an ALD conformal coating layer, and Wr is an ideal zone width at the local radius r.
A mark-to-space ratio of 1:1 can be used for the annular rings of template zones located at a local radius r from the center of the zone plate, r ranging from where Wr=2A (ideal zone width at radius r equal to two times the ALD coating thickness) up to radius R of the zone plate. This follows the ideal zone plate construction rule.
Preferably, depositing the conformal coating layer to form the zones further includes varying a mark to space ratio of the annular rings of the template to allow zone widths from one times the thickness of the conformal coating layer up, or less, to and including two times the thickness of the conformal coating layer. The thickness of the conformal coating layer is typically chosen to be approximately the width of the outermost zone of an ideal zone plate.
According to one embodiment, the method substantially fills the annular channels with the conformal coating layer for all zones, preferably using a mark-to-space ratio of 1:1 for the annular rings of the outermost zones of the template.
According to another embodiment, the method substantially fills the annular channels with the conformal coating layer for all zones except outermost zones, preferably using a mark-to-space ratio of 1:3 for the annular rings of the outermost zones of the template.
In general, according to another aspect, the invention features a zone plate comprising a grating template including annular rings that define annular channels and a conformal coating layer on the template to form zones of the zone plate, the conformal coating layer substantially filling at least some if not all of the annular channels to form wider zones.
In general according to still another aspect, the invention features a grating device such as possibly an array of linear grating structures, rather than circular structures of a conventional zone plate. The device comprises a template including pillars that define channels and a conformal coating layer on the template to form a grating structures, the conformal coating layer substantially filling at least some if not all of the channels to form wider grating structures.
The above and other features of the invention including various novel details of construction and combinations of parts, and other advantages, will now be more particularly described with reference to the accompanying drawings and pointed out in the claims. It will be understood that the particular method and device embodying the invention are shown by way of illustration and not as a limitation of the invention. The principles and features of this invention may be employed in various and numerous embodiments without departing from the scope of the invention.
In the accompanying drawings, reference characters refer to the same or similar parts throughout the different views. The drawings are not necessarily to scale; emphasis has instead been placed upon illustrating the principles of the invention. Of the drawings:
The distance between the center 10 of the zone plate to any given zone 130 is referred to as the local radius r of the zone. In general, the efficiency of each zone can be expressed as a function of its local radius r, the radius of the zone plate R, and its duty cycle.
E(r)=sin2 (πDCY(r))
Because the duty cycle is the same optimum value of 0.5 across all zones 130 in the ideal zone plate, the local efficiency 600-1 of zones 130 in an ideal zone plate simplifies to E(r)=sin2(π0.5), or E(r)=1 for all r. The efficiency E(r) in this figure and the following is the efficiency relative to an ideal binary zone plate.
Because E(r)=1 for all r for the ideal zone plate, this simplifies
As a result, the DCY decreases for the inner zones, and therefore the diffraction efficiency decreases for the inner zones as compared an ideal zone plate. This is especially the case for the zones 130 of the first inner section 102-1, the zones 130 of which are noticeably thinner in width 116 than the corresponding zones 130 of the first inner section 102-1 of the ideal binary zone plate of
For example,
Compared to the ideal zone plate in
calculated for conventional ALD zone plates is:
Of the sections, there is an outermost section 102-4, a third inner section 102-3, a second inner section 102-2, and a first inner section 102-1. For each section 102, the ideal zone width 116 of the zones 130 is a multiple of Δr, the zone width of the outermost zones. The ideal zone width at local radius r is also known as Wr.
The first inner section 102-1 includes zones having a local radius r on the order of ⅓ times the radius R of the zone plate, measured from the center 10 of the zone plate 100. The zone widths 116 of the zones 130 in the first inner section 102-1 are on the order of 3 times Δr. The zones 130 of the first inner section 102-1 are also referred to as innermost zones.
A second inner section 102-2 includes zones having a local radius r on the order of ½ times R measured from the center 10 of the zone plate. The zone widths 116 of the zones 130 in the second inner section 120-2 are on the order of 2 times Δr.
A third inner section 102-3 includes zones having a local radius r on the order of ⅔ R measured from the center 10 of the zone plate 100. Finally, an outermost section 102-4, associated with outermost zones, includes zones having a local radius r on the order of R measured from the center 10 of the zone plate 100.
For all zone plates, the ideal zone widths Wr (r) as a function of local radius r for zones 130 in each of the sections 102 are as follows:
The template 160 has a mark-to-space ratio of the annular rings that compares the width of annular rings 110 to the width of their annular channels 150. The mark-to-space ratio of the annular rings 110 is selected with a priori knowledge of the thickness of the ALD layer. This is because the mark-to-space ratio of the annular rings 110 is both a function of the thickness of the ALD layer, A, and the ideal zone width Wr at local radius r for the zones 130 of each section 102.
Conventional ALD zone plates have an optimum mark width of (2Wr−A) and an optimum space width of (2Wr+A) for the annular rings 110 of the template 160, where A is the thickness of the ALD conformal coating layer and Wr is the ideal zone width at local radius r. As a result, the mark-to-space ratio of the annular rings 110 decreases with increasing radial distance from the center 10 of the zone plate. At the same time, the zone width 116 of all zones 130 is fixed by the thickness of the ALD layer. This causes the duty cycle of the zones 130 to decrease with decreasing radial distance from the center 10 of the zone plate for zones 130 of inner sections 102-3 through 102-1, and therefore, the efficiency to decrease as compared to the ideal zone plate.
To overcome the limitation of fixed zone widths in conventional ALD zone plates, the conformal coating layer is then deposited until the ALD coating substantially fills the annular channels 150. When viewed in a cross-section or slice, the annular rings 110 are slightly trapezoidal in shape, being slightly wider at the bottom and thinner at the top. This minimizes the possibility of the annular channels 150 becoming “pinched off” at the top before being substantially filled by the conformal coating layer. The annular channels 150 are substantially filled when the sidewalls 140 of adjacent annular ring 110 meet and are pinched off, as indicated by reference 142, thus forming wider zones.
This can provide an increase in the zone width 116 of the zones 130 from a value of 1 times A, up to and including 2 times A, as compared to conventional ALD zone plates.
This embodiment increases the mark-to-space ratio of the annular rings 110 of outermost zones. Because the annular rings 110 of outermost zones were already thin and also had the highest aspect ratios in conventional ALD zone plates, this embodiment increases fabrication challenges and eliminates the advantage of frequency doubling as compared to conventional ALD zone plates.
The ALD layer can additionally be deposited beyond the point of substantially filling the annular channels 150, allowing the ALD layer to accumulate on the tops of the annular rings 110 and the annular channels 150. This is indicated by reference 144. This additional accumulation of material can act as a thin filter, in examples.
Of the sections 102, outermost section 102-4 and third and second inner sections 102-3 and 102-2, respectively, can achieve full density 1:1 zone mark-to-space ratios of the annular rings 110 up to zone widths 116 of two times the conformal coating layer thickness, A. This corresponds to an optimum duty cycle of 0.5 for the zones 130 in sections 102-4, 102-3, and 102-2. For first inner section 102-1, the innermost section, the optimum mark-to-space ratios of the annular rings 110 is according to (Wr−A): A, with the width of the annular channels 150 at a constant value of 2 times A across the zones of section 102-1. This optimizes the mark-to-space ratio of the annular rings 110 for zone widths of 2 Δr for the zones 130 of first inner section 102-1.
The outermost section 102-4, however, uses the same mark-to-space ratio of the annular rings 110 as that of the outermost section 102-4 of the conventional ALD zone plate of
The second embodiment provides wider zones as compared to the conventional ALD zone plate in
In
In
and the total efficiency, normalized over the area of the zone plate (πR2), Etot is:
In a similar fashion,
In
and the total efficiency, normalized over the area of the zone plate (πR2), Etot is:
Up to this point, to optimize efficiency the ALD coating thickness is equal to the outermost zone width (A=Δr). In a variant approach, by allowing the ALD coating thickness to be greater than the outermost zone width, total efficiency can be further optimized at the expense of perfect outermost zones. This concept is discussed in “Zone-Doubling Technique to Produce Ultrahigh-Resolution X-Ray Optics,” Jefimovs, K. et al., 31 Dec. 2007, Vol. 99, PHYSICAL REVIEW LETTERS 264801-1-264801-4.
To apply this concept to conventional ALD zone plates, the term, x, is added to the duty cycle vs. radius curve of ALD zone plates to describe a fraction of radius R where DCY equals 0.5. So now the duty cycle of an ALD zone plate can be described as
Therefore if A=Δr, the value of x is 1. To determine the optimum value of x to maximize efficiency, we solve for the following argument:
When calculated for a conventional ALD zone plate that has been optimized for efficiency using x=0.77, the total efficiency is:
The concept of allowing the ALD coating thickness to be greater than the outermost zone width can be applied to both embodiments. With respect to the first embodiment, this theoretically provides the ability to better approach 100% efficiency with the current model. The ALD layer can be deposited beyond the point of substantially filling the annular channels 150, allowing the ALD layer to accumulate on the tops of the annular rings 110 and the annular channels 150. This is indicated by reference 144. However, the excess accumulation of material becomes substantial if the thickness A is selected to be substantially larger than the outermost zone width Δr, or A>>Δr.
The concept of optimizing the efficiency of the zone plate by allowing the ALD coating thickness to be greater than the outermost zone width can be applied similarly to the second embodiment to further improve total efficiency. To determine the optimum value of x to maximize efficiency, we solve for the following argument:
Efficiency curve 600-3 shows an efficiency plot for the embodiment of
In a similar fashion,
In
and the total efficiency, normalized over the area of the zone plate (πR2), Etot is:
Zone plate 100A focuses x-rays from an x-ray source 310 onto a sample 350. Zone plate 100B accepts transmitted x-rays 328 transmitted through the sample 350, and focuses the transmitted x-rays 328 onto a detector 326.
The system has an x-ray source 310 that generates an x-ray beam 312 along the optical axis 322. In the example, the source is a beamline of a synchrotron x-ray generation facility. In other embodiments, lower power sources are used, such as laboratory sources. Such sources often generate x-rays by bombarding a solid target anode with energetic electrons. Specific examples include microfocus x-ray sources, liquid metal jet, and rotating anode sources.
The x-ray beam 312 is preferably a hard x-ray beam. In one embodiment, its energy is about 10 keV or higher. Generally, the beam's energy is between about 2 keV and 25 keV. These higher energies ensure good penetration through any intervening coating, e.g. fluid layer, onto the sample 350.
Zone plates 100A and 110B are held by respective holders 324. Zone plate 100A acts as a condenser and focuses the x-ray beam 112 from the source 310 unto the sample 350. A sample holder 320 is used to hold the sample 350 in the x-ray beam 312. The stage 316 scans the sample holder 320 in both the x and y axis directions, i.e., in a plane that is perpendicular to the axis 322 of the x-ray beam 312. In other examples, the stage 316 further rotates the sample 350 to obtain projections at different angles, which are often used for tomographic reconstruction in an image processor 318.
Zone plate 100B acts as an x-ray objective. It collects transmitted x-rays 328, from the sample 350 and focuses them onto the detector system 326. The detector system 326 is preferably a high-resolution, high-efficiency scintillator-coupled CCD (charge coupled device) camera system for detecting x-rays from the sample 350.
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
This application claims the benefit under 35 USC 119(e) of U.S. Provisional Application No. 62/054,632, filed on Sep. 24, 2014, which is incorporated herein by reference in its entirety.
Number | Date | Country | |
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62054632 | Sep 2014 | US |