The embodiments of the invention disclosed herein relate to high-brightness sources of x-rays. Such high brightness sources may be useful for a variety of applications in which x-rays are employed, including manufacturing inspection, metrology, crystallography, spectroscopy, structure and composition analysis and medical imaging and diagnostic systems.
X-ray sources have been used for over a century. One common x-ray source design is the electron bombardment reflection x-ray source, in which an electron emitter generates a beam of electrons that are accelerated onto an x-ray target by a voltage differential. The collision of the electrons into the target induces several effects, including the generation of x-rays, including bremsstrahlung continuum and characteristic x-rays of the target material.
For many techniques such as micro x-ray fluorescence, micro x-ray diffraction, crystallography, etc., there is a general a need for a microfocus x-ray source and optic combination that delivers a high brightness beam of x-rays within a small spot size onto a sample, and preferably of x-ray energies that optimal for the specific application. Common approaches to improving brightness of the source include: use of electron optics to guide and shape the path of the electrons, forming a more concentrated, focused beam at the target, use of target materials with higher atomic number to increase bremsstrahlung production (its efficiency scales with atomic number), and use of thermal strategies that allow higher electron power loading onto the target before melting. Thermal approaches include depositing the x-ray generating material on top of a substrate of high thermal conductivity such as diamond or beryllium, mounting the target onto a heat sink or heat pipe, and/or adding water coolant channels within the target.
In addition, low take-off angles are utilized to maximize apparent brightness. Although x-rays may be radiated isotropically, only the x-ray radiation within a small solid angle produced in the direction of a window in the source will be useful. X-ray brightness (also called “brilliance” by some), defined as the number of x-ray photons per second per solid angle in mrad2 per area of the x-ray source in mm2, can be increased by adjusting the geometric factors to maximize the collected x-rays. Generally, the surface of an x-ray target in a source is mounted at lower take-off angles (the angle between the target surface and the center of the emitted x-ray cone), so that the apparent spot size is reduced and apparent brightness is increased.
In principle, it may appear that a take-off angle of 0° would have the largest possible brightness. In practice, radiation at 0° occurs parallel to the surface of a solid metal target for conventional sources, and since the x-rays must propagate along a long length of the target material before emerging, most of the produced x-rays will be attenuated (reabsorbed) by the target material, reducing brightness. Thus, a source with take-off angle of around 6° to 15° (depending on the source configuration, target material, and electron energy) is conventionally used.
Despite these developments, there are still limits on the ultimate x-ray brightness that may be achieved with micro-focus x-ray sources.
The present technology, roughly described, includes an x-ray illumination beam system that includes an electron emitter and a target having one or more target microstructures, collectively referred to as an x-ray source. The one or more microstructures may be the same or different material, and may be embedded or placed atop a substrate formed of a heat-conducting material. The x-ray source may emit x-rays towards an optic system.
The optic system may include one or more optics that are matched to one or more target microstructures. The matching may can be achieved by selecting optics with the geometric shape, size, and surface coating that collects as many x-rays as possible from the source and at an angle that satisfies the critical reflection angle of the x-ray energies of interest from the target. In some instances, the matching is based on maximizing the numerical aperture (NA) of the optics for x-ray energies of interest. The optic system may be configured to focus or collimate the beam, and may include a monochromator.
The x-ray illumination system allows for an x-ray source, comprised of an electron emitter and a target having one or more microstructures, to generate x-rays having different energies. The x-ray illumination system can be used in a variety of applications, including but not limited to spectroscopy, fluorescence analysis, microscopy, tomography, diffraction and other applications.
In some instances, an x-ray illumination beam system can provide multiple characteristic x-ray energies from a plurality of x-ray generating materials selected for its x-ray generating properties. The x-ray illumination system can include a vacuum chamber, first window, and an electron optical system. The vacuum chamber includes an electron emitter. The first window is transparent to x-rays and attached to a wall of the vacuum chamber. The electron optical system focusses an electron beam from the electron emitter. In the x-ray illumination beam system, a target can include a plurality of microstructures coupled to a substrate, wherein each microstructure includes a material selected for its x-ray generating properties, and in which a lateral dimension of said material is less than 250 microns;
The x-ray illumination beam system can include a means to position the x-ray target relative to the electron beam and a plurality of total external reflection mirror optics. The optics are matched to the x-ray spectra produced by at least one of the plurality of microstructures and positioned to collect x-rays generated by the at least one of the plurality of microstructures when bombarded by the focused electron beam.
Inside the chamber 20, an emitter 11 connected through the lead 21 to the negative terminal of a high voltage source 10 serves as a cathode and generates a beam of electrons 111. Any number of prior art techniques for electron beam generation may be used for the embodiments of the invention disclosed herein. Additional known techniques used for electron beam generation include heating for thermionic emission, Schottky emission (a combination of heating and field emission), or emitters comprising nanostructures such as carbon nanotubes). [For more on electron emission options for electron beam generation, see Shigehiko Yamamoto, “Fundamental physics of vacuum electron sources”, Reports on Progress in Physics vol. 69, pp. 181-232 (2006)].
As before, a target 1100 comprising a target substrate 1000 and regions 700 of x-ray generating material is electrically connected to the opposite high voltage lead 22 and target support 32, thus serving as an anode. The electrons 111 accelerate towards the target 1100 and collide with it at high energy. The collision of the electrons 111 into the target 1100 induces several effects, including the generation of x-rays, some of which exit the vacuum tube 20 and are transmitted through at least one window 40 and/or an aperture 840 in a screen 84.
In some embodiments of the invention, there may also be an electron beam control mechanism 70 such as an electrostatic lens system or other system of electron optics that is controlled and coordinated with the electron dose and voltage provided by the emitter 11 by a controller 10-1 through a lead 27. The electron beam 111 may therefore be scanned, focused, de-focused, or otherwise directed onto the target 1100.
As illustrated in
Targets such as those to be used in x-ray sources according to the invention disclosed herein have been described in detail in the co-pending US patent application entitled STRUCTURED TARGETS FOR X-RAY GENERATION (U.S. patent application Ser. No. 14/465,816, filed Aug. 21, 2014), which is hereby incorporated by reference in its entirety, along with the provisional Applications to which this co-pending application claims benefit. Any of the target designs and configurations disclosed in the above referenced co-pending application may be considered for use as a component in any or all of the x-ray sources disclosed herein.
A target 1100 according to the invention may be inserted as the target in a reflecting x-ray source geometry (e.g.
It should be noted that the word “microstructure” in this application will only be used for structures comprising materials selected for their x-ray generating properties. It should also be noted that, although the word “microstructure” is used, x-ray generating structures with dimensions smaller than the micrometer scale, or even as small as nano-scale dimensions (i.e. greater than 10 nm) may also be described by the word “microstructures” as used herein.
The microstructures may be placed in any number of relative positions throughout the substrate 1000. In some embodiments, as illustrated in
As discussed in Eqn. 1 above, the depth of penetration can be estimated by Potts' Law. Using this formula, Table II illustrates some of the estimated penetration depths for some common x-ray target materials.
For the illustration in
The majority of characteristic Cu K x-rays are generated within depth DM. The electron interactions below that depth are less efficient at generating characteristic Cu K-line x-rays but will contribute to heat generation. It is therefore preferable in some embodiments to set a maximum thickness for the microstructures in the target in order to optimize local thermal gradients. Some embodiments of the invention limit the depth of the microstructured x-ray generating material in the target to between one third and two thirds of the electron penetration depth of the x-ray generating material at the incident electron energy, while others may similarly limit based on the electron penetration depth with respect to the substrate material. For similar reasons, selecting the depth DM to be less than the electron penetration depth is also generally preferred for efficient generation of bremsstrahlung radiation.
Note: Other choices for the dimensions of the x-ray generating material may also be used. In targets as used in some embodiments of the invention, the depth of the x-ray generating material may be selected to be 50% of the electron penetration depth of either the x-ray generating material or the substrate material. In other embodiments, the depth DM for the microstructures may be selected related to the “continuous slowing down approximation” (CSDA) range for electrons in the material. Other depths may be specified depending on the x-ray spectrum desired and the properties of the selected x-ray generating material.
Note: In other targets as may be used in some embodiments of the invention, a particular ratio between the depth and the lateral dimensions (such as width WM and length LM) of the x-ray generating material may also be specified. For example, if the depth is selected to be a particular dimension DM, then the lateral dimensions WM and/or LM may be selected to be no more than 5×DM, giving a maximum ratio of 5. In other targets as may be used in some embodiments of the invention, the lateral dimensions WM and/or LM may be selected to be no more than 2×DM. It should also be noted that the depth DM and lateral dimensions WM and LM (for width and length of the x-ray generating microstructure) may be defined relative to the axis of incident electrons, with respect to the x-ray emission path, and/or with respect to the orientation of the surface normal of the x-ray generating material. For electrons incident at an angle, care must be taken to make sure the appropriate projections for electron penetration depth at an angle are used.
It should be noted that, although the illustration of
It should also be noted that materials are relatively transparent to their own characteristic x-rays, so that
Up to this point, targets that are arranged in planar configurations have been presented. These are generally easier to implement, since equipment and process recipes for deposition, etching and other planar processing steps are well known from processing devices for microelectromechanical systems (MEMS) applications using planar diamond, and from processing silicon wafers for the semiconductor industry.
However, in some embodiments, a target with a surface with additional properties in three dimensions (3-D) may be desired. As discussed previously, when the electron beam is larger than the electron penetration depth, the apparent x-ray source size and area is at minimum (and brightness maximized) when viewed at a zero degree (0°) take-off angle.
The distance through which an x-ray beam will be reduced in intensity by 1/e is called the x-ray attenuation length, designated by μL, and therefore, a configuration in which the generated x-rays pass through as little additional material as possible, with the distance selected to be related to the x-ray attenuation length, may be desired.
An illustration of a portion of a target as may be used in some embodiments of the invention is presented in
The surface normal in the region of the microstructures 711-717 is designated by n, and the orthogonal length and width dimensions are defined to be in the plane perpendicular to the normal of said predetermined surface, while the depth dimension into the target is defined as parallel to the surface normal. The thickness DM of the microstructures 711-717 in the depth direction is selected to be between one third and two thirds of the electron penetration depth of the x-ray generating material at the incident electron energy for optimal thermal performance. The width WM of the microstructures 711-717 is selected to obtain a desired source size in the corresponding direction. As illustrated, WM≈DM. As discussed previously, WM could also be substantially smaller or larger, depending on the shape and size of the source spot desired.
As illustrated, the length of each of the microstructures 711-717 is LM≈WM/10, and the length of the separation between each pair of microstructures is a distance LGap≈2LM, making the total length of the region 710 comprising x-ray generating material LTot=7×LM+6×LGap≈19×LM≈1.9×DM. In other embodiments, larger or smaller dimensions may also be used, depending on the amount of x-rays absorbed by the substrate and the relative thermal gradients that may be achieved between the specific materials of the x-ray generating microstructures 711-717 and the substrate 1000.
Likewise, the distance between the edge of the shelf and the edge of the x-ray generating material p as illustrated is p≈LM, but may be selected to be any value, from flush with the edge 1003 (p=0) to as much as 1 mm, depending on the x-ray reabsorption properties of the substrate material, the relative thermal properties, and the amount of heat expected to be generated when bombarded with electrons.
For a configuration such as shown in
The microstructures may be embedded in the substrate (as shown), but in some embodiments may they may also be partially embedded, or in other embodiments placed on top of the substrate.
The thermal benefits of a structured target such as that illustrated in
In the cited Provisional patent application, calculations therein for two targets are presented using the finite element modeling product Solidworks Simulation Professional.
The first target modeled has a uniform coating of copper 300 microns thick as the x-ray material, as is common in commercial x-ray targets. Simulation of bombardment of the copper layer with electrons over an ellipse 10 microns wide and 66 microns long predicts an increase in the temperature of the copper to over 700° C.
The second target, according to an embodiment of the invention, has 22 discrete structures of copper as the x-ray generating material, arranged in a one-dimensional array similar to that illustrated in
The length of each x-ray generating structure along the axis of the array LM is 1 micron, and elements are placed with a separation LGap of 2 microns. The width of the elements in the direction perpendicular to the array axis WM is 10 microns, and depth perpendicular from the surface into the target DM is also 10 microns.
In the simulation, both targets are modeled as being bombarded with an electron beam that raises the temperature to the operating temperature of ˜700° C. The uniform copper target reaches this temperature with an electron exposure of 16 Watts. However, in the case of the second, structured target, the copper reaches the operating temperature of ˜700° C. with an exposure of 65 Watts—a level 4 times higher. Normalizing for the reduced copper volume still gives more than twice the power deposited into the copper regions. Moreover, electron energy deposition rates between the materials is much more substantial in the higher density Cu than in diamond, and is therefore predicted to generate at least twice the number of x-rays. This demonstrates the utility of embedding microstructures of x-ray generating material into a thermally conducting substrate, in spite of a reduction in the total amount of x-ray generating material.
For a structure comprising the microstructures embedded in the substrate with a side/cross-section view as shown in
With a small value for DM relative to WM and LM, the ratio is essentially 1. For larger thicknesses, the ratio becomes larger, and for a cube (DM=WM=LM) in which 5 equal sides are in thermal contact, the ratio is 5. If an overcoat or cap layer of a material with similar properties as the substrate in terms of mass density and thermal conductivity is used, the ratio may be increased to 6.
The heat transfer is illustrated with representative arrows in
In other embodiments, this overcoat 725 may comprise a material selected for its thermal conductivity. In some embodiments, this overcoat 725 may be a layer of diamond, deposited by chemical vapor deposition (CVD). This allows heat to be conducted away from all sides of the microstructure. It may also provide a protective layer, preventing x-ray generating material from subliming away from the target during extended or prolonged use. Such protective overcoats typically have thicknesses on the order of 0.2 to 5 microns. Such a protective overcoat may also be deposited using an additional dopant to provide electrical conductivity as well. In some embodiments, two distinct layers, one to provide electrical conductivity, the other to provide thermal conductivity and/or encapsulation, may be used. In some embodiments, overcoats may comprise beryllium, diamond, polycrystalline diamond, CVD diamond, diamond-like carbon, graphite, silicon, boron nitride, silicon carbide and sapphire.
In other embodiments the substrate may additionally comprise a cooling channel 1200, as also illustrated in
Other configurations that may be used in embodiments of the invention, such as a checkerboard array of microstructures, a non-planar “staircase” substrate and various non-uniform shapes of x-ray generating elements, have been described in the above cited parent applications of the present application, U.S. patent application Ser. Nos. 14/490,672 and 14/999,147. Additional target configurations presented in U.S. patent application Ser. No. 14/465,816 are microstructures comprising multiple x-ray generating materials, microstructures comprising alloys of x-ray generating materials, microstructures deposited with an anti-diffusion layer or an adhesion layer, microstructures with a thermally conducting overcoat, microstructures with a thermally conducting and electrically conducting overcoat, microstructured buried within a substrate and the like.
Other target configurations that may be used in embodiments of the invention, as has been described in the above cited U.S. patent application Ser. No. 14/465,816, are arrays of microstructures that may comprise any number of conventional x-ray target materials patterned as features of micron scale dimensions on or embedded in a thermally conducting substrate, such as diamond or sapphire. In some embodiments, the microstructures may alternatively comprise unconventional x-ray target materials, such as tin (Sn), sulfur (S), titanium (Ti), antimony (Sb), etc. that have thus far been limited in their use due to poor thermal properties.
Other target configurations that may be used in embodiments of the invention, as has been described in the above cited U.S. patent application Ser. No. 14/465,816, are arrays of microstructures that take any number of geometric shapes, such as cubes, rectangular blocks, regular prisms, right rectangular prisms, trapezoidal prisms, spheres, ovoids, barrel shaped objects, cylinders, triangular prisms, pyramids, tetrahedra, or other particularly designed shapes, including those with surface textures or structures that enhance surface area, to best generate x-rays of high brightness and that also efficiently disperse heat.
Other target configurations that may be used in embodiments of the invention, as has been described in the above cited U.S. patent application Ser. No. 14/465,816, are arrays of microstructures comprising various materials as the x-ray generating materials, including aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, gallium, zinc, yttrium, zirconium, molybdenum, niobium, ruthenium, rhenium, rhodium, palladium, silver, tin, iridium, tantalum, tungsten, indium, cesium, barium, germanium, gold, platinum, lead and combinations and alloys thereof.
The embodiments described so far include a variety of x-ray target configurations that comprise a plurality of microstructures comprising x-ray generating material that can be used as targets in x-ray sources to generate x-rays with increased brightness.
It should be noted that, as drawn in
Assuming the ith sub-source 80i produces x-rays 8i8 along the axis to the right in
Using the definitions:
the total intensity of x-rays on-axis to the right of the array of N sub-sources can be expressed as:
For a source design in which all sub-sources produce approximately the same intensity of x-rays
I
i
≈I
0 [Eqn. 5]
the total intensity becomes
Furthermore, if the sub-sources are arranged in a regular array with essentially the same value for transmission between elements:
T
a,a-1
=T
2,1
,a>1, [Eqn. 7]
and if the sizes and shapes of the x-ray generating elements are similar enough such that the transmission through any given element will also be the same:
T
a
=T
1
,a>0, [Eqn. 8]
then the total intensity becomes
Note that Ti and Ti,i-1 represent a reduction in transmission due to losses, and therefore always have values between 0 and 1. If N is large, the sum on the right can be approximated by the geometric series
making the approximate intensity
Note that this can also be used to estimate how many generating elements can be arranged in a row before losses and attenuation would make the addition of another x-ray generating element unproductive. For example, if the width of a generating element is mL, the 1/e attenuation length for x-rays, transmission through the element gives Ti=1/e=0.3679. Assuming a transmission between elements of Ti,i-1=T2,1=0.98, this makes
This means that a large number of elements with a width equal to the 1/e length could only improve the intensity by a factor of 1.564. For 2 elements (a total x-ray generation length of 2×mL), Eqn. 9 indicates that Itot≈I0 T1,0 (1.361), 87% of the estimated maximum from Eqn. 12, while for 3 elements (a total x-ray generation length of 3×mL), Itot≈I0 T1,0 (1.490), 95% of the estimated maximum, and for 4 elements (a total x-ray generation length of 4×mL), Itot≈I0 T1,0 (1.537), which is 98% of the estimated maximum degree of linear accumulation from Eqn. 12. This suggests a general rule that linear accumulation near the maximum may be achieved from a total length of x-ray generating material of only 4×mL.
The 1/e attenuation length μL for a material is related to the transmission factors above for a length L by
T
i
=e
−α
L
=e
−L/μ
[Eqn. 13]
Therefore, a larger μL means a larger Ti.
As an example of using the values in
T
i
=e
−L/μ
=e
−20/200=0.905 [Eqn. 14]
For 60 keV x-rays in a beryllium substrate, μL=50,000 m, which makes the transmission of a 100 m wide beryllium gap between embedded tungsten x-ray generating elements to be:
T
i,i-1
==e
−L/μ
=e
−100/50,000=0.998 [Eqn. 15]
Therefore, for a periodic array of tungsten elements 20 μm wide embedded in a Beryllium substrate and spaced 100 m apart, the best-case estimate for the on-axis intensity is:
which would represent an increase in x-ray intensity by an order of magnitude when compared to a single tungsten x-ray generating element.
There are several variables through which a generic linear accumulation source may be “tuned” or adjusted to improve the x-ray output. Embodiments of the invention may allow the control and adjustment of some, all, or none of these variables.
In some embodiments, the beam or beams of electrons 111 or 1111, 1112, 1113, etc. bombarding the x-ray generating elements 801, 802, 803 . . . etc. may be shaped and directed using one or more electron control mechanisms 70 such as electron optics, electrostatic lenses or magnetic focusing elements. Typically, electrostatic lenses are placed within the vacuum environment of the x-ray source, while the magnetic focusing elements can be placed outside the vacuum.
In many embodiments, the area of electron exposure can be adjusted so that the electron beam or beams primarily bombard the x-ray generating elements and do not bombard the regions in between the elements. A source having multiple electron beams that are used to bombard distinct x-ray generating elements independently may also be configured to allow a different accelerating voltage to be used with the different electron beam sources. Such a source 80-B is illustrated in
This may offer advantages for x-ray radiation management, in that electrons of different energies may generate different x-ray radiation spectra, depending on the materials used in the individual x-ray generating elements. The heat load generated may also be managed through the use of different electron energies.
Although it is simpler to treat the x-ray generating elements as identical units, and to have the intervening regions also be considered identical, there may be advantages in some embodiments to having variations in these parameters.
In some embodiments, the different x-ray generating elements may comprise different x-ray generating materials, so that the on-axis view presents a diverse spectrum of characteristic x-rays from the different materials. Materials that are relatively transparent to x-rays may be used in the position closest to the output window 840 (e.g. the element 801 furthest to the right in
In some embodiments, the distance between the x-ray generating elements may be varied. For example, a larger space between elements may be used for elements that are expected to generate more heat under electron bombardment, while smaller gaps may be used if less heat is expected.
3.3. Rotating Anode Embodiments.
The target described above might also be used in an embodiment comprising a rotating anode, distributing the heat as the anode rotates. A system 580-C comprising these features is illustrated in
The target in the embodiment as illustrated is a rotating cylinder 5100 mounted on a shaft 530. In one end of the cylinder 5100, a set 5710 of rings of x-ray generating material 5711-5717 have been embedded into a layer of substrate material 5000, with a gap between each ring. The “length” (parallel to the shaft axis in this illustration, and perpendicular to the local normal n in the region under bombardment) of each ring may be comparable to the length discussed for the set of microstructures illustrated in
This substrate material 5000 may in turn be attached or mounted on a core support 5050 attached to the rotating shaft 530. The core support may comprise any number of materials, but a core of an inexpensive material with high thermal conductivity, such as copper, may be preferred. A solid core/substrate combination that comprises a single material may also be used in some embodiments. The substrate 5000 may be deposited using a CVD process, or pre-fabricated and attached to the core support 5050.
When bombarded with an electron beam 511-R, the portions of the set of rings 5710 of x-ray generating materials that are exposed will generate heat and x-rays 5588. X-rays radiated at a zero-angle (perpendicular to a local surface normal for the target in the region under electron bombardment) or near zero-angle may experience linear accumulation, and appear exceptionally bright. Embedding the set of rings 5710 of x-ray generating material into the substrate 5000 facilitates the transfer of heat away from the x-ray generating structures, allowing higher electron flux to be used to generate more x-rays without causing damage to the structures, as has been demonstrated for the non-rotating case.
It should be noted that the illustrations of
In practical embodiments, the substrate thickness may range from a few microns to 200 microns, while the core may typically have a diameter of 2 cm to 20 cm. A cylinder in which the core and substrate are the same material may also be used in some embodiments. Various overcoats for electrical conduction and/or protection, as discussed for planar targets and illustrated in
Although only parallel rings with zero take-off angle have been illustrated in
For the substrate of a target with microstructures of x-ray generating material, as shown above it is preferred that the transmission of x-rays T for the substrate be near 1. For a substrate material of length L and linear absorption coefficient s,
T=e
−α
L
=e
−L/μ
[Eqn. 17]
where μL is the length at which the x-ray intensity has dropped by a factor of 1/e.
Generally,
μL∝X3/Z4 [Eqn. 18]
where X is the x-ray energy in keV and Z is the atomic number. Therefore, to make μL large (i.e. make the material more transparent), higher x-ray energy is called for, and a lower atomic number is highly preferred. For this reason, both beryllium (Z=4) and carbon (Z=6) in its various forms (e.g. diamond, graphite, etc.) may be desirable as substrates, both because they are highly transparent to x-rays, but also because they have high thermal conductivity (see Table I).
The embodiments of the invention disclosed in this application can be especially suitable for making a high brightness x-ray source for use at one or more predetermined low take-off angles. In some embodiments, the arrangement of discrete structures of x-ray generating material can be arranged to increase the x-ray radiation into a predetermined cone of angles around a predetermined take-off angle. Such a predetermined cone can be matched to the acceptance angles of a defined x-ray optical system to increase or maximize the useful x-ray intensity that may be delivered to a sample in applications such as XRD, XRF, SAXS, TXRF, especially, with microbeams, such as microXRD, microXRF, microSAXS, microXRD, etc. Examples of such an x-ray optical system is one having a monocapillary x-ray optical element with a defined inner reflective surface, such as a paraboloidal collimator or a dual paraboloidal or ellipsoidal focusing surface.
In other embodiments, the arrangement of discrete structures of x-ray generating material can be arranged to increase the x-ray radiation into a predetermined fan of angles around a predetermined take-off angle. Such a distribution of x-rays may be matched to other x-ray optical elements designed to produce x-ray beams with a line profile or collimated to form a parallel beam instead of a focused spot.
The design of the layout of the x-ray generating elements in the target can be optimized to increase the x-rays radiated in specific directions using two factors. One is the management of the thermal load, so that heat is efficiently transported away from the x-ray generating elements. With effective thermal transfer, the x-ray generating elements can be bombarded with an electron beam of even greater power density to produce more x-rays. The second is the distribution of the x-ray generating materials such that the self-absorption of x-rays propagating through the remaining volume of x-ray generating material is reduced and linear accumulation of x-rays is optimized.
For the target 1100-T as illustrated, there is a local surface in the area of the x-ray generating elements that has a surface normal n. This defines an axis for the dimension of depth D into the target for determining the depth of the x-ray generating materials. This axis is also used to measure the electron penetration depth or the electron continuous slowing down approximation depth (CSDA depth).
For the target as illustrated, there is furthermore a predetermined take-off direction (designated by ray 88-T) for the downstream formation of an x-ray beam. This take-off direction is oriented at an angle θT relative to the local surface, and the projection of this ray onto the local surface (designated by ray 88-S) in the plane that contains both the take-off angle and the surface normal is a determinant of the dimension of length L for the target. The final dimension of width W is defined as the third spatial dimension orthogonal to both the depth and the length directions.
As illustrated, the set of discrete structures of x-ray generating material is in the form of a linear array of x-ray generating microstructures, each of length LM, width WM, and depth DM, the same as was that illustrated in
It should be noted that these dimensions of depth, length and width in a given target may or may not correspond to those that might be intuited merely from the layout of the discrete structures of x-ray generating material. As has already been illustrated, discrete structures of x-ray generating material may be laid out in 1-dimensional and 2-dimensional arrays, grids, checkerboards, staggered and buried structures, etc. and the alignment and relative orientation of these physical arrays and patterns with the predetermined take off angle and the surface normal may or may not be parallel. As defined in these embodiments, the coordinates of depth, length and width are defined only by the surface normal and the predetermined take-off angle.
As illustrated in
The actual design of the x-ray target may be more easily described using the concept of an “x-ray generating volume”, as discussed further below. This is the volume of the target from which the substantial majority of the x-rays of a desired energy will be radiated. In the embodiments of the invention, there are four primary factors that may affect the design rules for the structure of x-ray generating material within the x-ray generating volume that may be applied in embodiments of the invention to improve the x-ray brightness radiated into this predetermined cone. These four factors are:
the volume fraction of x-ray generating material;
the relative thermal properties of the x-ray generating material and substrate;
the distance of propagation of the X-rays through x-ray generating material; and
the depth of x-ray generation.
The “x-ray generating volume” of a target comprising discrete structures of x-ray generating material is the volume of the target that, when bombarded with electrons, generates x-rays of a desired energy. The energy is typically specified as the characteristic x-ray radiation generated by specific transitions in the selected x-ray generating material, although for certain applications, spectral bandwidths of continuum x-rays from the x-ray generating material may also be designated.
Two “volumes” must be considered to define the “x-ray generating volume”: a “geometric volume” encompassing the x-ray generating material, and the “electron excitation volume” encompassing the region in which electrons deliver enough energy to generate x-rays.
The “geometric volume” for the x-ray generating material is defined as the minimum contiguous volume that completely encompasses a given set of discrete structures of x-ray generating material and the gaps between them.
For the x-ray generating structures of
For other configurations, such as those shown in
The “electron excitation volume” is the volume of the target in which electrons deliver enough energy to generate x-rays of a predetermined desired energy.
The electron beam bombarding the target may have various sizes and shapes, depending on the electron optics selected to direct and shape the electron beam. For example, the electron beam may be approximately circular, elliptical, or rectangular. Various accelerating voltages may be used as well, although generally the accelerating voltage will be selected to be at least twice that needed to produce x-rays of a given energy (e.g. to produce x-rays with an energy of ˜8 keV, the accelerating voltage is preferred to be at least 16 keV).
If the entire region of x-ray generating structures is bombarded with an equivalent footprint of electrons of high energy, the x-ray generating volume may be identical to the “geometric volume” as described above. However, in some cases, the depth of the microstructured x-ray generating material DM may be significantly deeper than the electron penetration depth into the substrate, which may be estimated using Potts' Law (as discussed above), or deeper than the continuous slowing down approximation (CSDA) range (CSDA values normalized for element density may be computed using the NIST website physics.nist.gov/PhysRefData/Star/Text/ESTAR.html). In such cases, the deeper regions of x-ray generating material may be relatively unproductive in generating x-rays, and the x-ray generating volume is preferably defined by the area overlap of the electron footprint upon the sample with the minimal geometric area containing the microstructures and the electron penetration depth of the electrons into the substrate. For 60 keV electrons bombarding copper (density ˜8.96 g/cm3) the electron penetration depth by Potts' Law is estimated to be ˜5.2 microns, while the CSDA depth is ˜10.6 microns. For a diamond substrate (density ˜3.5 g/cm3), the Potts' Law penetration depth is ˜15.3 microns, while the CSDA depth for the diamond substrate is ˜18.9 microns.
In some embodiments, the depth of the x-ray generating structures DM measured from the target surface may be limited to be less than the penetration depth of the electrons into the x-ray target substrate material. In most cases (due to the typically lower mass density of the x-ray substrate relative to the x-ray generating material), the entire depth of x-ray generating material will be generating x-rays. In some embodiments, the depth of the x-ray generating structures DM measured from the target surface may be some multiple (e.g. 1×-5×) of the penetration depth of the electrons into the x-ray target substrate material. In this case, the depth DP of the electron excitation volume 7770-E in which x-rays are generated will be less than DM, as illustrated in
In other embodiments, the depth of the x-ray generating structures DM measured from the target surface may be limited to be less than the penetration depth of the electrons into the x-ray generating material. This may include 1× the penetration depth, or in some cases, preferably a fraction of the penetration depth such as ½ or ⅓ of the penetration depth.
For some embodiments, the depth DP of the electron excitation volume will be defined as being equal to half the penetration depth of the target X-ray generating material, since this is the depth over which the electrons will generate more characteristic x-rays. (See the discussion of
For any general embodiment, the x-ray generating volume will be defined as the volume overlap of the “geometric volume” for the x-ray generating material within the target and the “electron excitation volume” for electrons of a predetermined energy and known penetration depth and CSDA depth for materials of the target.
The volume fraction of the x-ray generating volume is defined as the ratio of the volume of the x-ray generating material within the x-ray generating volume to the overall x-ray generating volume. A typical prior art x-ray target with a uniform target of x-ray generating material will have a volume fraction of 100%. Targets such those illustrated in
A general rule for the x-ray sources according to the invention disclosed here is that the volume fraction of the x-ray generating volume be between 10 and 70%, with the non-x-ray generating portion being filled with material of a high thermal conductivity. The regions of non-x-ray generating material serve to conduct the heat away from the x-ray generating structures, enabling bombardment with an electron beam of higher power, thereby producing more x-rays.
The ideal volume fraction for a target typically depends on the relative thermal properties of the x-ray generating material and the substrate material in the x-ray generating volume. If the target is fabricated by embedding discrete structures of x-ray generating material with moderate thermal properties into a substrate of high thermal conductivity, good thermal transfer is generally achieved. If the thermal transfer between the x-ray generating material and the substrate is poor (for example, in circumstances of when the x-ray generating material has poor thermal properties), a smaller volume fraction may be desired. In general, for the embedded target structures described herein, a volume fraction of 30%-50% is preferred.
It should be noted that in some embodiments, the discrete x-ray structures are not manufactured through etching or ordered patterning processes but instead formed using less ordered discrete structures, such as powders of target materials.
Once the particles of x-ray generating material have been placed in the groove, the gaps between particles 7006 can be filled with a coating of material deposited by chemical vapor deposition (CVD) processes. This provides the thermal dissipation for the heat produced in the x-ray generating target structures. When bombarded by electrons 111, the x-ray generating material will produce x-rays 8088. As long as the space between particles is small, and the depth of the groove is less than half the penetration depth of the electrons into the substrate, the x-ray generating volume 7070 will be the overlap of the groove (defining the geometric volume) and the projection of the footprint of the electron beam at the surface.
In some embodiments, the powders may be pressed into an intact ductile substrate material. In some embodiments, additional overcoats as described for more regular structures and illustrated in
For a target formed using a powder of x-ray generating material, the substrate is preferably a material with high thermal conductivity, such as diamond or beryllium, and the filling material is a matching material (e.g. diamond) deposited by CVD.
The x-ray source target substrate material is preferred to have superior thermal properties, particularly its thermal conductivity, in respect to the x-ray generating material. Moreover, it is preferred that substrate materials of the target limit the self-absorption of x-rays produced in the target along the low take-off angle. In many embodiments, this leads to the selection of a substrate material having low atomic number, such as diamond, beryllium, sapphire, or some other carbon-based material.
For some materials, such as diamond, the thermal conductivity is severely reduced in very thin samples of the material. There may therefore be a minimum thickness required for the space between structures of x-ray generating material.
In general, for diamond having embedded structures of x-ray generating material, suitable results have been achieved when the thickness of the diamond between structures of x-ray generating material is 0.5 micrometer or more.
Likewise, if the discrete structures of x-ray generating material are too thick, heat cannot transfer efficiently from the center to the outside, and there is therefore a practical limit on how thick a given structure of x-ray generating material should be.
In general, when being embedded into diamond, suitable results have been achieved when the thickness of the x-ray generating structures is 10 micrometers or less.
As described previously, there will be a total length for x-ray generation after which additional x-rays generated cease to contribute additional x-rays to the output, due to reabsorption. There is therefore an upper bound on the length LM of the x-ray generating material within the x-ray generating volume.
For a given x-ray energy, which in general may correspond to a characteristic line of the selected x-ray generating material, μL is be defined to be the 1/e attenuation length for x-rays of that energy in the same material. Values for this number have been illustrated in
As a general rule, the propagation path through x-ray generating material for any given x-ray path should be less than 4×μL. For target structures such as the powder structure in
For more defined discrete target structures, such as that illustrated in
In
Although
Such a target design is illustrated in
If the take-off angle is in the plane of the microstructures, the path for x-rays at or near the take-off angle may be longer than the reabsorption upper bound. However, for x-rays emerging from the sides of the microstructures, low attenuation through the surrounding substrate and other x-ray microstructures may be achieved. The spacing between the microstructures may be adjusted so that x-rays emerging at the maximum cone angle θ2 in the plane orthogonal to the plane of the take-off angle (i.e. in the plane of
Note that these cone angles need not be in any particular plane, and therefore a design rule limiting the length of overlap must apply to certain rays within the cone, preferably those out of the plane of orientation for the microstructures. In some embodiments, a design rule limiting the length of the sum of segments will apply to any cone angle within a predetermined subset of cone angles. In some embodiments, a design rule limiting the length of the sum of segments will apply to a majority of cone angles.
A general design rule can be stated that, for any ray within a predetermined subset of cone of angles greater than or equal to θ1 and less than or equal to θ2 relative to the take-off angle ray, the sum of the segments of overlap with the x-ray generating material within the x-ray generating volume must be smaller than 4×μL. Note that for prior embodiments, this design rule may also be used rather than using the ray along the take-off angle to define the amount of x-ray generating material within a giving x-ray generating volume.
Design rules may also be placed on having a minimum length for sums of segments of overlap, to ensure that at least some accumulation of x-rays may occur. For some embodiments, the sum of the segments of overlap with the x-ray generating material within the x-ray generating volume must be greater than 0.3×μL. For other embodiments, the sum of the segments of overlap with the x-ray generating material within the x-ray generating volume must be greater than 1.0×μL. For other embodiments, the sum of the segments of overlap with the x-ray generating material within the x-ray generating volume must be less than 1×μL and in other embodiments this may be 2.0×μL.
As discussed above, the depth DM of the structures of x-ray generating material may be determined by any number of factors, such as the ease of reliably manufacturing embedded structures of certain dimensions, the thermal load and thermal expansion of the embedded structures, a minimum thickness to minimize source degradation due to delamination or evaporation, etc.
However, creating structures with a depth DM significantly deeper than the electron penetration depth into the substrate will generally result in deep regions that are unproductive in generating x-rays. For 60 keV electrons bombarding copper (density ˜8.96 g/cm3) the electron penetration depth by Potts' Law is estimated to be ˜5.2 microns, while the CSDA depth is ˜10.6 microns. For a diamond substrate (density ˜3.5 g/cm3), the Potts' Law penetration depth is ˜15.3 microns, while the CSDA depth for the diamond substrate is ˜18.9 microns.
As a general design rule, the depth of the x-ray structures DM measured from the target surface should be limited to be less than 5 times the penetration depth of the electrons into the x-ray target substrate material. This ensures that the depth of the structures of x-ray generating material, which typically have poorer thermal properties than the substrate, is minimized, as typically only the portion closer to the surface is efficient at generating characteristic x-rays. Although some x-rays are generated at lower depths, there is also associated heat generation. In some embodiments, the depth of the x-ray generating material is preferred to be a fraction (e.g. ½) of the electron penetration depth in the x-ray generating material, providing the overlap of electron excitation and x-ray generating material primarily in the zone in which most of the characteristic x-rays are generated (see previous discussion of
Conventional reflection-type x-ray target geometries are often arranged, such that the x-ray beam emitted is centered along a take-off angle of ˜6° measured from the x-ray target surface tangent. This angle is typically selected in an effort to both minimize apparent x-ray source size (smaller at lower take-off angles) and minimize self-attenuation by the x-ray target (larger at lower take-off angles).
The disclosed embodiments of the invention are preferably operated at take-off angles less than or equal to 3°, and for some embodiments at 0° take-off angle, substantially lower than for conventional x-ray sources. This is enabled by the structured nature of the x-ray source and the incorporation of an x-ray substrate, as discussed above, comprised of a material or structure that reduces or minimizes self-absorption of the x-ray energies of interest generated by the x-ray target.
Such a structured target is especially useful as a distributed, high-brightness source for use in systems that make use of an x-ray beam having the form of an annular cone.
This annular output can be selected to match the acceptance angle of an x-ray optical element, such as a capillary optic with a reflecting inner surface used for directing (e.g. focusing or collimating) the generated x-ray beam for downstream applications. The predetermined cone of x-rays generated by the x-ray source can be defined to correspond to the angles and dimensions of such downstream optical elements. Likewise, a central beamstop to block the x-rays propagating at the take-off angle T (which typically will not be collected by the downstream optical elements such as monocapillaries) can also be used, with the propagation angles blocked by the beam stop being those that correspond to the inner diameter of the predetermined annular x-ray cone. In some embodiments, annular cones may be defined by the acceptance angles of downstream optics, i.e. by the numerical aperture of such optics, or other parameters that may occur in such systems. Matching the volume to, for example, the depth-of-focus range for a collecting optic or to the critical angle of the reflecting surface of a collecting optic may maximize the number of useful x-rays, while limiting the total power that must be expended to generate them.
The angular range for the annular cone of x-rays is generally specified by having the inner cone angle 1 being greater than 2 mrad relative to the take-off angle, and having the outer cone angle 2 be less than or equal to 50 mrad relative to the take-off angle.
The previous discussion on take-off angles and cones of annular x-rays may also be applied to rotating anodes.
On the outer surface of the cylinder, a layer of substrate material 5000 such as diamond or CVD diamond has been formed, and embedded in this substrate are a number of rings 5711, 5712, . . . , 5717 comprising x-ray generating material. As before, the “length” (parallel to the shaft axis in this illustration, and perpendicular to the local normal n in the region under bombardment) of each ring may be comparable to the length discussed for the set of microstructures illustrated in
When a portion of the x-ray generating structures are bombarded by electrons 511-R, an x-ray generating volume 5070 is formed, generating x-rays 5088. Although x-rays may be radiated in many directions, for this system, as with the systems illustrated in
However, in the embodiment as illustrated, the cylinder is beveled at an angle in the region of the x-ray generating volume, and the take-off angle is at a non-zero angle 19T, similar to the configuration for the planar geometry of
Also illustrated in this embodiment, the cylinder 5105 may also be fabricated with an interface layer 5003, which may be provide a coupling between the beveled substrate 5005 and the core 5055.
Other rotating anode designs, such as patterns of lines, checkerboards, grids, etc. as have been illustrated U.S. Provisional Patent Application Ser. No. 62/141,847 (to which the Parent application of the Present application claims the benefit of priority) as well various designs and structures illustrated in other planar embodiments of the present application and the previously mentioned co-pending applications may be used in these configurations as well. These rotating anode embodiments may additionally be fabricated using conducting and/or protective overcoats, as was previously discussed for use with planar targets.
The present technology, roughly described, provides an x-ray beam delivery system comprised of at least one x-ray source comprising a plurality of x-ray target materials matched with a plurality of x-ray optics. Each matched target material and optic pair provides different spectra, allowing for analysis at different levels of sensitivity. The x-ray system can provide collimated or focused beams and a system with a very high throughput due to the matching of each target material and optic.
The matching is achieved by selecting optics designed with the geometric shape, size, and surface coating for collecting as many x-rays having energies of interest as possible from the source and at an angle that satisfies the critical reflection angle of the x-ray energies of interest. In some embodiments, the matching is based on maximizing the numerical aperture (NA) of the optics for x-ray energies of interest. The NA is related to the flux an optic can collect from a source. The square of the NA is proportional to the square of the critical angle of reflection of the reflecting surface material for a specific x-ray energy, which is proportional to the inverse of the x-ray energy squared. This can be represented as follows:
In most embodiments, the optic is matched to one of the characteristic x-ray energies of the selected target material. For example, if the optic is matched for a higher x-ray energy, the critical angle is smaller and the reflecting surface of the optic will be shaped with a shallower slope. Some embodiments in which the NA is maximized for a high x-ray energy comprise a long x-ray optic with shallow slopes.
In some instances, the x-ray optics have an interior reflecting surface with at least a portion that comprises a quadric profile. The optics are positioned such that a focus of the quadric profile is coincident with the x-ray source spot. In some embodiments, where the quadric shape is ellipsoidal, the spot is at one of the two foci, and in other embodiments, such as paraboloidal or hyperboloidal shapes, the spot is at the single focus. Furthermore, the optics are matched to a characteristic x-ray energy of the x-ray generating microstructure material. This matching is defined such that the incident angle of x-rays with the characteristic energy of interest upon a portion of the reflecting surface are approximately equal to the critical angle of the characteristic x-ray energy of interest. In some instances, the reflecting surface profile of an optic is shaped such that x-rays with the characteristic energy of interest incident upon a portion of the reflecting surface have incidence angles that are between 30 to 100% of the critical angle. In some embodiments, the characteristic x-ray energy is a K-line of the x-ray generating microstructured material. In some other embodiments, this characteristic x-ray energy may be an L or M-line energy.
The energies and spectral properties of x-rays generated by striking an electron-beam on a target depend on the material of the target. In some instances, a target may be comprised of multiple thin strips of target material, for example in the form of a microstructure in which there is one long dimension (e.g., a length) and two dimensions <500 um (e.g., width and depth), deposited on a substrate of high thermal conductivity such as diamond or copper. X-rays generated by an electron beam striking a target material may be collected at a low take-off angle, such as between 0 degrees to +/−6 degrees to maximize brightness. The x-rays can be collimated or focused by optics designed to be matched to the target material. X-rays that are not reflected by optics 130 are blocked by beam stop 132. More information for wire targets is discussed with respect to
The present x-ray beam delivery system can have a source with one or more targets, with each target comprising one or more target materials, such that there are a plurality of target materials and a plurality of optics. Optics are matched to one or more target materials, as each material has unique spectra and characteristic emission lines, and therefore critical angles θc. The critical angle can depend on the interior surface coating of an optic. In particular, different interior surface coatings, such as a platinum coating, can be used to increase the critical angle.
The optics are matched to one or more target materials and can include total external reflection mirror optics. Each of the plurality of optics in an x-ray illumination beam system can be matched to the x-ray spectra produced by at least one of a plurality of microstructures. Each optic can also be positioned to collect x-rays generated by at least one of the plurality of microstructures when bombarded by a focused electron beam. Examples of optics that may be used to match different targets are discussed with respect to
The system of
In some instances, the target 120 is a rotating anode target. In some instances, the target is comprised of a substrate and discrete microstructures having at least two dimensions being <500 μm in contact with the substrate. In some instances, the microstructures are embedded within a substrate and in some instances, the microstructures are atop a substrate. In some embodiments, the microstructures are not directly in contact with the substrate and there is at least one layer of material between the microstructures and substrate. Such layers may serve as diffusion barriers to prevent the diffusion of the microstructure material into the substrate material or vice versa, and/or may serve as thermal boundaries to improve the thermal conductivity of heat between the microstructure and the substrate.
In some embodiments but not shown in
The critical angle of x-rays depends on the x-ray energy and reflecting surface material. Optics with different coatings, shapes, and focal lengths and/or source-optic entrance distances may be used. In some embodiments, the optic is axially symmetric, with an inner reflecting quadratic surface, such as: ellipsoidal, paraboloidal, hyperboloidal, etc. In some embodiments, the optic has an outer diameter of <10 mm.
Optics system 1030 may include multiple focusing optics 1032 and 1034. Each matched optic and target material may be chosen for a particular application such that the x-ray flux is optimized for x-ray spectra optimal for the application. X-rays collected by optics 1032 are focused to a point 1080. In some instances, the plurality of optics includes two quadric surface profiles
One or more mechanisms can be sued for moving the optics, the target, and the electron beam to provide different x-ray spectra. The mechanism may ensure the optics are parfocal and that different targets can be bombarded with electron beams to create different x-ray spectra.
The x-ray source (consisting of an electron emitter and a target having microstructures) can be used with a matching optic in several types of systems. Though
The collected x-rays are reflected by optic 3810, and the reflected x-rays 3815 are incident on a two-bounce monochromator. X-rays 3815 are first diffracted by crystal 3820, and the diffracted x-rays 3825 are directed to and diffracted again by a second crystal 3830. In some instances, other monochromators can be used, such as for example a channel cut, or a four-bounce monochromator. The monochromatized beam 3835 diffracted by the second crystal 3830 is received by a second optic 3840, also a paraboloid mirror lens. Optic 3840 focuses the monochromatized beam 3835 onto sample 3850. Fluorescence x-rays 3855 are then detected by a detector, such as a high efficiency SDD detector.
Once a selection is received, a target region and electron beam are aligned at step 3930. The motion is relative and may involve one or several of the components moving. The optic is positioned into the emitted x-ray path at step 3940 to collect x-rays at a low take-off angle. The optic may be positioned such that it collects the maximum flux of the x-ray energy(ies) of interest. In some instances, this is one of the characteristic x-ray lines of the selected target material. The optic may then provide a collimated or focused beam.
An electron beam is produced and strikes the selected target microstructure at step 3950 and generates x-rays. The generated x-rays are collected and focused or collimated by the matching optic at step 3960.
With this application, several embodiments of the invention, including the best mode contemplated by the inventors, have been disclosed. It will be recognized that, while specific embodiments may be presented, elements discussed in detail only for some embodiments may also be applied to others. Also, details and various elements described as prior art may also be applied to various embodiments of the invention.
While specific materials, designs, configurations and fabrication steps have been set forth to describe this invention and the preferred embodiments, such descriptions are not intended to be limiting. Modifications and changes may be apparent to those skilled in the art, and it is intended that this invention be limited only by the scope of the appended claims.
The Present patent application is a continuation-in-part of U.S. patent application Ser. No. 15/166,274, filed May 27, 2016 and entitled DIVERGING X-RAY SOURCES USING LINEAR ACCUMULATION, which is a continuation-in-part of U.S. patent application Ser. No. 14/999,147, filed Apr. 1, 2016 and entitled X-RAY SOURCES USING LINEAR ACCUMULATION, which claims the benefit of U.S. Provisional Patent Application No. 62/141,847, filed Apr. 1, 2015 and entitled ADDITIONAL X-RAY SOURCE DESIGNS USING MICROSTRUCTURED TARGETS, and U.S. Provisional Patent Application No. 62/155,449, filed Apr. 30, 2015, and entitled X-RAY TARGET FABRICATION, both of which are incorporated herein by reference in their entirety; and which in turn is also a continuation-in-part of U.S. patent application Ser. No. 14/490,672, filed Sep. 19, 2014 and entitled X-RAY SOURCES USING LINEAR ACCUMULATION, which claims the benefit of U.S. Provisional Patent Application Nos. 61/880,151, filed on Sep. 19, 2013, 61/894,073, filed on Oct. 22, 2013, 61/931,519, filed on Jan. 24, 2014, and 62/008,856, filed on Jun. 6, 2014, all of which are incorporated herein by reference in their entirety.
Number | Date | Country | |
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62141847 | Apr 2015 | US | |
62141847 | Apr 2015 | US | |
62008856 | Jun 2014 | US | |
61931519 | Jan 2014 | US | |
61894073 | Oct 2013 | US | |
61880151 | Sep 2013 | US |
Number | Date | Country | |
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Parent | 15166274 | May 2016 | US |
Child | 15783855 | US | |
Parent | 14999147 | Apr 2016 | US |
Child | 15166274 | US | |
Parent | 14490672 | Sep 2014 | US |
Child | 15166274 | US |