X-ray reflectometry apparatus and method thereof for measuring three dimensional nanostructures on flat substrate

Abstract

This disclosure relates to an apparatus and methods for applying X-ray reflectometry (XRR) in characterizing three dimensional nanostructures supported on a flat substrate with a miniscule sampling area and a thickness in nanometers. In particular, this disclosure is targeted for addressing the difficulties encountered when XRR is applied to samples with intricate nanostructures along all three directions, e.g. arrays of nanostructured poles or shafts. Convergent X-ray with long wavelength, greater than that from a copper anode of 0.154 nm and less than twice of the characteristic dimensions along the film thickness direction, is preferably used with appropriate collimations on both incident and detection arms to enable the XRR for measurements of samples with limited sample area and scattering volumes. In one embodiment, the incident angle of the long-wavelength focused X-ray is 24, and the sample area is 25 m25 m.

Claims

1. An X-ray reflectometry apparatus for measuring a three-dimensional nanostructure on a flat substrate, comprising: an X-ray source for emitting an X-ray of one wavelength in a multi-wavelength range of 0.154 nm-20 nm; an X-ray reflector comprising multiple mirrors or a X-ray monochromator; a six-axis platform configured to control a focus distance of the X-ray reflector such that the focus distance is 150 mm, so that the X-ray is point focused on a sample surface from an incident angle 24 and a footprint of the focused X-ray is less than or equal to 10 m25 m; an incident slit disposed between the X-ray reflector and the sample surface, wherein the focused X-ray is controlled by the incident slit to change a divergence angle, and the incident slit is an aperture optical element or a slit element that is controlled in at least one direction; an X-ray detector configured to collect reflecting and scattering signals from the sample surface, which includes a 2-dimensional X-ray sensor inside a vacuum chamber and an analyzer outside the vacuum chamber; and a controller configured to control the 2-dimensional X-ray sensor to move along a z-axis with the incident angle of the focused X-ray for collecting the scattering and reflecting signals.

2. The X-ray reflectometry apparatus according to claim 1, wherein the multiple mirrors are equal to or more than 2.

3. The X-ray reflectometry apparatus according to claim 1, wherein the multiple mirrors are used as ellipsoidal mirrors, multi-capillary optical mirrors, or multilayer optical mirrors.

4. The X-ray reflectometry apparatus according to claim 1, wherein a diameter of Rowland circle of the monochromator is equal to or more than 500 mm.

5. The X-ray reflectometry apparatus according to claim 1, wherein the three-dimensional nanostructure is a two-layer grating nanostructure or a multi-layer nanostructure, and a line width and a line pitch of the three-dimensional nanostructure are measured.

6. The X-ray reflectometry apparatus according to claim 1, wherein a sensitivity angle is defined as the incident angle at which a reflection signal of an integrated light intensity has a largest change ratio, wherein the largest change ratio occurs when the sample surface has a critical dimension change of several nanometers.

7. The X-ray reflectometry apparatus according to claim 6, wherein the sensitivity angle has a range equal to or more than 10.

8. The X-ray reflectometry apparatus according to claim 1, wherein the divergence angle multiplied by the tangent of the incident angle is changed according to a wavelength dispersion /, wherein refers to the wavelength of the X-ray and refers to a spread of the wavelength of the X-ray after being reflected by the X-ray reflector.

9. A method for measuring a three-dimensional nanostructure on a flat substrate comprising: emitting an X-ray of one wavelength in a multi-wavelength range of 0.154 nm-20 nm; controlling a focus distance of an X-ray reflector including multiple minors or an X-ray monochromator such that the focus distance is 150 mm, so that the X-ray is point focused on a sample surface from an incident angle 24 and a footprint of the focused X-ray is less than or equal to 10 m25 m; controlling the focused X-ray by an incident slit to change a divergence angle, and the incident slit is an aperture optical element or a slit element that is controlled in at least one direction; collecting reflecting and scattering signals from the sample surface by an X-ray detector, which includes a 2-dimensional X-ray sensor inside a vacuum chamber and an analyzer outside the vacuum chamber, and a size of the sensor collects the scattering and reflecting signals completely; and controlling the 2-dimensional X-ray sensor to move on a z-axis with the incident angle of the focused X-ray for collecting the scattering and reflecting signals.

10. The method according to claim 9, wherein the multiple mirrors are equal to or more than 2.

11. The method according to claim 9, wherein the multiple mirrors are used as ellipsoidal mirrors, multi-capillary optical mirrors, or multilayer optical mirrors.

12. The method according to claim 9, wherein a diameter of Rowland circle of the monochromator is equal to or more than 500 mm.

13. The method according to claim 9, wherein the three-dimensional nanostructure is a two-layer grating nanostructure, wherein a line width and a line pitch of the three-dimensional nanostructure are measured.

14. The method according to claim 9, wherein a sensitivity angle is defined as the incident angle at which a reflection signal of an integrated light intensity has a largest change ratio, wherein the largest change ratio occurs when the sample surface has a critical dimension change of several nanometers.

15. The method according to claim 14, wherein the sensitivity angle has a range equal to or more than 10.

16. The method according to claim 9, wherein the divergence angle multiplied by the tangent of the incident angle is changed according to a wavelength dispersion /, wherein , refers to the wavelength of the X-ray and refers to a spread of the wavelength of the X-ray after being reflected by the X-ray reflector.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A shows an X-ray reflectometry apparatus according to an embodiment of the disclosure.

(2) FIG. 1B shows an X-ray reflectometry apparatus which moves on z-axis with the incident angle for collecting scattering and reflecting signals according to an embodiment of the disclosure.

(3) FIG. 1C shows an X-ray reflectometry apparatus according to another embodiment of the disclosure.

(4) FIG. 1D shows an X-ray reflectometry apparatus according to another embodiment of the disclosure.

(5) FIG. 2A shows a fan-shaped incident X-ray reflected on the sample.

(6) FIG. 2B shows a top-down view of FIG. 2A.

(7) FIG. 3 illustrates the incident wavefront ij is specularly reflected on sample surface and the reflected wavefront recorded on a 2D detector as a line ij.

(8) FIG. 4A illustrates a schematic diagram of 2D detector image from a 3D nanoporous thin film on a silicon substrate from a well collimated pencil incident beam.

(9) FIG. 4B shows a schematic diagram of 2D detector image from a 3D nanoporous thin film in FIG. 4A from a fan-shape incident X-ray shown in FIG. 2A.

(10) FIG. 4C shows a scattering intensity profile along line mn shown in FIG. 4B.

(11) FIG. 5 shows a method for X-ray reflectometry according to an embodiment of the disclosure.

(12) In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing.

DETAILED DESCRIPTION

(13) Details are given in the non-limiting embodiments below. It should be noted that the embodiments are illustrative examples and are not to be construed as limitations to the claimed scope of the present disclosure. The same/similar denotations are used to represent the same/similar components in the description below. Directional terms such as above, below, left, right, front or back are used in the following embodiments to indicate the directions of the accompanying drawings, not for limiting the present invention.

(14) The present disclosure relates generally to the measurement of characterization of three dimensional (3D) nanostructures on a flat substrate. More particularly, the present disclosure relates to an X-ray reflectometry applicable to samples with intricate 3D structures and a limited thickness or height, in the order of nanometers and concurrently with a limited sample area. In a previous invention (US patent 2016/0341674 A1) the challenge related to this minuscule sample volume, a product of thickness and area, has been addressed with a convergent XRR apparatus and method to enhance the incident beam flux, and hence improve the reflection signal strength. At the same time it maintains a desirable resolution in terms of the scattering vector Qz which is defined in its usual way as (4/) sin , stands for the wavelength of the X-ray and is the grazing incident angle between the sample surface and the incident X-ray. The angle is also the detection angle with respect to the sample surface since this previous invention is concerned only with the specular reflection. In this previous invention, convergent long wavelength X-ray is focused on the target area with a tightly controlled opening angle while keeping the divergence angle along the azimuthal direction widely open to allow sufficient incident X-ray flux for conducting XRR with a miniscule sampling volume. The purpose of the present disclosure is to extend the abovementioned XRR to measure 3D nanostructures supported on a flat substrate.

(15) In one embodiment of the application, a method for XRR includes the steps of: point focusing an X-ray with a wavelength selected from 0.154 nm-20 nm onto a surface of a sample at a preset incident angle 24 and a preset focus distance 150 mm by using multiple set of reflect mirrors or a monochromator; adjusting the divergence angle of the X-ray to control the footprint size of the incident X-ray10 m25 m on the sample surface and the angular resolution of the reflectivity while keeping a maximal allowable X-ray flux on the sample; and analyzing the XRR data to obtain the structure information of the sample.

(16) In one embodiment, when a conventional X-ray reflectivity technique using a short wavelength X-ray less than 0.154 nm, the miniscule sample area and the larger footprint size of incident X-ray at low incident angle is mismatched. When a typical X-ray source with the wavelength in a range of 0.154-20 nm is used for the XRR measurements, and the incident angle of the X-ray is greater than 24, the footprint size, denoted as p, on surface of the sample of incident X-ray beam is related to the beam size, denoted as f, by p=f/sin .

(17) For applications in IC chip fabrication, a typical sample area is in the range of 25 m25 m for advanced semiconductor process. It is therefore advantageous to use X-ray with long wavelength and a high incident angle such that the footprint size can be controlled under area of 10 m25 m.

(18) The wavelength dispersion is defined as /, wherein here refers to the wavelength of the X-ray emitted by the X-ray source, and here refers to the spread of the wavelength of the X-ray after being reflected by the X-ray reflector.

(19) The resolution of the wave-vector q, denoted as q/q, can be expressed as a sum of the X-ray wavelength uncertainty and angular uncertainty as shown in equation (1): q/q=cos */sin +/.

(20) It is shown that the resolution q/q is a function of the incident angle , the divergence angle , and the wavelength dispersion /. The above equation indicates that to achieve a constant resolution q/q, i.e. q/q=c, the incident angle and the divergence angle of the X-ray will be changed accordingly.

(21) It is should be noted that high incident flux and small footprint are the two major benefits by using a long wavelength X-ray source. There is an additional intrinsic benefit in applying long wavelength X-ray for XRR. That is, the integrated XRR intensity of any scattering peak is scaling linearly with . For a 3D object, its integrated scattering intensity is known to scale as .sup.3. The XRR measurement is along the axis perpendicular to the flat substrate, hence, it is a one-dimensional measurement, and the integrated intensity is scaled as .

(22) Please refer to FIGS. 1A to 1C, which illustrate a schematic diagram of an X-ray reflectometry apparatus 10 according to an embodiment of the present disclosure. The X-ray reflectometry apparatus 10 may include an X-ray source 100, an X-ray reflector 110, a six-axis platform (Hexapod) 120, an incident slit 200, an X-ray detector 300, an analyzer 302, and a two-axis controller 310. The X-ray source 100 is used to emit X-ray of one wavelength in a multi-wavelength range of 0.154 nm-20 nm. The X-ray reflector 110 includes multiple sets of mirrors 111, 112 (see FIG. 1A) or X-ray monochromator 113 (see FIG. 10). The six-axis platform 120 is used to control the focusing distance of multiple sets of mirrors 111, 112 or X-ray monochromator 113 150 mm, so that X-rays are incident from an incident angle 24 and focused on a sample surface, and the footprint size of the incident X-ray 1 m25 m. The focused X-ray can be controlled by a 2-axis controlled incident slit 200 to change the divergence angle . The X-ray detector 300 collects the reflecting and scattering signals, which includes a 2-dimensional X-ray sensor 301 in a vacuum chamber and an analyzer 302 outside the vacuum chamber, and the sensor size of the sensor 301 can collect the scattering and reflecting signals completely. The two-axis controller 310 is used to control the two-axis directions of the 2-dimensional X-ray sensor 310 to move on the z-axis with the incident angle of the X-ray for collecting scattering and reflecting signals.

(23) In one embodiment, the scattering and reflecting signals of different 3D nanostructures correspond to different initial incident sensitivity angles, and the sensitivity angle range is, for example, 10. The sensitivity angle is defined as the incident angle at which the reflection signal of the CD-XRR integrated light intensity with largest change ratio when the sample surface has a critical dimension change of several nanometers (for example, 10 nm). For example, within a predetermined range of incident angle , collect the above-mentioned reflection signal and the total intensity of the incident light, and select with the largest change ratio between the reflection signal and the total intensity of the incident light to obtain the sensitivity angle range.

(24) Please refer to FIG. 1B. In one embodiment, the X-ray with a long wavelength of 0.834 nm is used to measure a two-layer grating nanostructure of two-dimensional array. The line width of the nanostructure is 80 nm and the line pitch of nanostructure is 200 nm, for example. The sensitivity angle obtained by the simulation is 2.2-3.13 so the incident angle between the incident X-ray and the 12-inch wafer is measured from 2.2 to 3.13. The maximum opening angle of the incident slit 200 has a minimum value of 0.2 according to the simulation, and the divergence angle is the angle at which the periodic peaks of the reflection signal while keeping allowable. The two-dimensional sensor 301 on z-axis is adjusted with the incident angle . For example, the size of the two-dimensional sensor 301 is 60 mm60 mm, and the distance between the sensor 301 and the center of the sample is adjusted to 160 mm through the X-axis direction. According to the calculation of triangle geometry to make the reflection signal on the center of the sensor 301, when the incident angle rotates from 2.2 to 3.13 the z-axis of the sensor 301 needs to move up by 2.72 mm.

(25) In an embodiment, the mirror set 111 and 112 may include X-ray collimators, refractive X-ray optical elements, diffractive optics, Schwarzschild optics, Kirkpatrick-Baez optics, Montel optics, Wolter optics or mirror X-ray optical elements, etc., the mirror set 111 and 112 can be used as ellipsoidal mirrors, multi-capillary optical mirrors, multilayer optical mirrors or optical system. The 6-axis controller 120 can move to control the x, y, z moving axes and , , rotation axes of the mirror set 111 and 112 at the same time, so that the X-ray can focus on a sample surface 401 of 12-inch wafer; each mirror can be controlled with 2 axes, such as a rotation axis and a moving axis for optical focus.

(26) Please refer to FIG. 10, in one embodiment, the X-ray reflector 110 is, for example, a monochromator 113, and a diameter of the Rowland circle of the monochromator 113 is, for example, 500 mm. In addition, the incident slit 200 can be an aperture optical element or a slit element that can be controlled by a uniaxial piezoelectric. In addition, the focus distance (i.e., 150 mm) of the X-ray reflector 110 is the minimum distance for the flat substrate 410 such as 12-inch wafer to avoid interference with the mirror set 111 and 112 or the monochromator 113 when the flat substrate 410 rotates.

(27) When the wavelength dispersion / is changed, the incident angle and the divergence angle of the X-ray will be changed accordingly. For example, given that =0.68 nm, when the wavelength of X-ray is 0.834 nm, then /=0.68/0.834=0.815. When the wavelength of X-ray is 0.154 nm, then /=0.68/0.154=4.416. Since X-ray with different wavelengths are used, the maximum divergence angles at which the periodic peaks of the reflection signal while keeping allowable are also different. Taking the sample 400 with 12 nm SiO.sub.2 film as an example, the maximum divergence angle with a wavelength of 0.834 nm is 0.2, and the maximum divergence angle with a wavelength of 0.154 nm is 0.1, so that when the incident angle changes, the maximum divergence angle will be also changed accordingly.

(28) The essence of the present disclosure is to use a 2D detector to collect the specularly reflected and the off-specular or scattered X-ray during the reflectivity run and the off-specular contributions resulted from finite coherence length and finite lateral Qx and Qy will be determined and removed to obtain the specular reflection intensity.

(29) In applying XRR for nanostructured surface analysis, it is noteworthy that all the information available are along the thickness direction (z-axis given in the drawing); at a given depth the structural result deduced from XRR represents that from the lateral average over the coherence length. To obtain 3D information of the nanostructure from XRR additional input on a characteristic lateral length is needed. Such a length scale can be obtained from a single transmission small angle X-ray scattering (tSAXS) measurement at normal incidence. It is therefore advisable to have tSAXS data taken at normal incidence available together with the XRR data from the sample of interest.

(30) For 3D array of nanostructures the azimuthal placement of the samples can no longer takes advantage of the large projected coherence length along the y axis. In addition, in the convergent beam of XRR scheme depicted in this disclosure, the scattering magnitude of Qx and Qy from the angular width of the incident slit and the detector slit projected on the sample surface or the x-y surface. For simplicity, the openings for both incident and the scattering slits are chosen to be identical and denoted as as shown in FIG. 2B. From a straightforward geometrical consideration we have the ranges of Qx and Qy situated between 2(/) cos and .sup.2(/) cos respectively.

(31) Noting that is given in rad and is typically less than unity, e.g. with =0.26 or 15, Qx has a range of 0.52 (/) cos while Qy has a range of 0.068 (/) cos . In most convergent beam XRR set-up the angular slit opening in dictated by the focus optics, 15 to 20 is a typical upper range available. This leads to the condition that Qx>Qy in most convergent XRR measurements. For thin film samples, there is no lateral structural variation, the existence of finite Qx, Qy and lateral coherence length imposes no restriction in the application of convergent XRR. For line grating sample, it is desirable to align the line with the x-axis to mitigate the impact of large Qx invoked in the XRR measurements. This alignment is also desirable from the lateral coherence length consideration since the coherence length is rather small along the x-axis. For the consequence of misaligning the line gratings, it is also visible from conventional XRR measurements using a highly collimated ribbon incident beam.

(32) Even it is not the convergent incident beam discussed herein, all the discussions regarding coherence length and Qx, Qy are still valid since the only difference is the value of is 15 to 25 in the current case and the value of is about 1 or less for the case of the ribbon beam used in carrying out the work.

(33) For 3D nanostructures samples often there is no obvious lateral orientation to align with respect to the convergent XRR axes such as x-axis or y-axis shown in FIG. 2A to mitigate the side effects due to finite coherence length and lateral scattering vectors Qx and Qy. The objective of the present disclosure is to mitigate the shortcomings in using convergent XRR method to measure 3D nanostructures on a flat substrate.

(34) The present disclosure can solve this kind of problem on convergent XRR. Firstly, the method herein employs different incident angles which can analyze the depth information in the z direction of the sample. The focused light has integrated the xy information of the 3D sample with the reflectivity value. By analyzing the electron density along z direction correspond to the structural composition at different depths. Combining with known line widths or line space information, the 3D material composition and size can be resolved.

(35) The problem to be solved is that the conventional methods for detecting critical dimensions in the art include atomic force microscope (AFM) and scanning electron microscope (SEM), but they encounter the problem in measuring critical dimensions. The present disclosure provides a method for detecting the critical dimensions of 3D nanostructures on a flat substrate by using convergent long-wavelength X-ray reflectometry. By fan-shaped focusing, the light intensity can be effectively increased, the detection area can be reduced, and the signals along different azimuthal directions can be received at the same time. The integrated incident X-ray intensity is collected at each azimuthal angle to obtain the thickness and density information of the sample through EMA approximation. The depth map is analyzed with the electron density along z direction to detect the pattern thickness, the line width, the line spacing changes in high precision level and has high resolution (less than 0.1 nm).

(36) Referring to FIG. 1, an X-ray reflectometry apparatus 10 for measuring three dimensional nanostructures on a flat substrate according to an embodiment of the disclosure is provided, including an X-ray source 100, an X-ray reflector 102, an incident slit 200, a detector slit 201, an X-ray detector 300 and at least one analyzer 302. The X-ray source 100 is for emitting an X-ray with a wavelength larger than 0.154 nanometers (nm). The X-ray reflector 102 is for point focusing a fan-shape X-ray onto a surface 401 of a sample 400. The X-ray is point focused by the X-ray reflector 201 onto the surface 401 with an incident angle adjustable over a preset range. In an embodiment, the sample 400 is located on a flat substrate 410 and can be rotated 360 degrees by the sample stage 500. The flat substrate 410 is, for example, a semiconductor substrate.

(37) The incident slit 200 is disposed between the X-ray reflector 102 and the sample 400, the width of the incident slit 200 is aligned perpendicular to the reflection plane of the X-ray, and the width of the incident slit 200 is greater than its opening 202 by a factor 10 or above, but the disclosure is not limited thereto. In an embodiment, the divergence angle of the incident X-ray is controlled via the incident slit opening 202, and the divergence angle of the fan-shape incident X-ray is controlled via the width W of the incident slit 200. In addition, the detector slit 201 is disposed between the X-ray detector 300 and the sample 400 for controlling the divergence angle of the reflected X-ray.

(38) In addition, the X-ray detector 300 has a fine pixel resolution for collecting the X-ray reflected by the surface 401 of the sample 400, and the X-ray detector is preferably a 2 dimensional detector. In an embodiment, at each azimuthal position of the reflected X-ray collected on the X-ray detector 300, the off-specular contribution is determined and removed from the reflected X-ray intensity. The light beam reflected from the surface 401 of the sample 400 can be regarded as a divergent light beam emitted by a new point light source. Therefore, the size of the light spot received by the X-ray detector 300 is related to the distance of the reflected light beam to the X-ray detector. The longer the distance the reflected beam travels, the larger the spot size received by the X-ray detector; conversely, the smaller the spot size received by the X-ray detector. The X-ray detector with fine resolution referred to in the disclosure means a detector with sufficient resolution capability for distinguishing one reflected light spot from another in a pixel; that is, as long as the size of the light spot falls within a pixel of the X-ray detector, and do not cross to the neighboring pixels of the pixel. Those with ordinary skill in the art should know that a detector with an appropriate resolution can be selected according to the distance of the reflected beam to the X-ray detector.

(39) Referring to FIG. 2A, which shows a fan-shape incident X-ray reflected on the sample 400. The angle between the incident light and the xy plane is the same as the angle between the reflected light and the xy plane.

(40) Referring to FIG. 2B, which shows a top-down view of FIG. 2A. The angle is a divergence angle of the incident light and the reflected light. The term i represents a beam specularly reflected by the sample to i. Similarly, the term j represents a beam specularly reflected by the sample to j. Another example in the figure is m-beam which has an angle relative to y-axis reflected by the sample to m, ij line and ij line can represent the incident light wavefront and the reflected light wavefront, respectively.

(41) Referring to FIG. 3, which illustrates the incident wavefront ij is specularly reflected on sample surface and the reflected wavefront recorded on the 2D X-ray detector as a line ij. Each point m on line ij represents a specularly reflection from point m on the incident wavefront at an azimuthal angle shown in FIG. 2B, The specular reflection line can be interpreted as aggregate of numerous specular reflection spots m.

(42) FIG. 4A shows a representative 2D detector image from a 3D nanoporous thin film on a silicon substrate from a well collimated pencil incident beam. FIG. 4B shows a schematic view of 2D detector image from a 3D nanoporous thin film mentioned in FIG. 4A from a fan-shape incident beam shown in FIG. 2A.

(43) FIG. 4C shows a scattering intensity profile along line mn shown in FIG. 4B. The shade part represents the off-specular contribution and shall be removed from the intensity profile to obtain the specular part measure at an incident angle shown in FIG. 2A. Measuring the specular reflection intensities over a preset range of provides the reflectivity result.

(44) Referring to FIGS. 1 and 5, a method for X-ray reflectometry (XRR) apparatus 10 to measure three dimensional nanostructures on a flat substrate according to an embodiment of the disclosure is provided in FIG. 5. The method includes the following steps. In step S210, a fan-shape X-ray is point focused onto a surface 401 of a sample 400 with an incident angle , wherein the incident angle is adjustable over a preset range of angle and a wavelength of the X-ray is larger than 0.154 nanometers (nm). In step S220, the divergence angle of the incident X-ray is adjusted according to the incident slit opening 202 when the incident angle is changed. The divergence angle is, for example, a function of a tangent of the incident angle . In step S230, the divergence angle of the fan-shape X-ray is adjusted via the width W of the incident slit 200. In step S240, the fan-shape reflected X-ray is collected by using an X-ray detector 300 and in step S250, at each azimuthal position of the reflected X-ray collected on the X-ray detector 300, the off-specular contribution is determined and removed from the reflected X-ray intensity, as shown in FIG. 4C. In step S260, the specular component of the remained X-ray intensity at each azimuthal position is integrated to obtain the specular reflection intensity for each incident angle . In step S270, the ratio between the specular reflection intensity and the integrated incident X-ray intensity is collected over a preset range of incident angle to obtain structure information of the sample 400.

(45) In an embodiment, the wavelength of the X-ray is no more than twice of a characteristic length along the surface normal of a structure of the sample 400.

(46) In an embodiment, the characteristic length is selected from the group consisting of film thicknesses of the surface and heights of a nanostructure of the surface of the sample 400.

(47) In an embodiment, the X-ray reflector 102 is selected from a group consisting of single crystal monochromators and multilayer mirrors. For a multilayer mirror type, the wavelength dispersion of the X-ray reflector 102 is less than 0.01.

(48) In an embodiment, the divergence angle is a function of the incident angle . That is, the divergence angle can be changed with different incident angles .

(49) In an embodiment, the divergence angle is a function of a tangent of the incident angle multiplied by a constant K. (i.e., =K*tan ).

(50) In an embodiment, the X-ray source includes a fine focused aluminum anode.

(51) In an embodiment, the at least one analyzer 302 is for collecting an X-ray photoelectron spectrum (XPS) and/or an X-ray fluorescence (XRF) signals from the sample during the reflected X-ray is collected by the X-ray detector 300.

(52) In the step S230, the sample stage 500 can be rotated over 360 around the surface normal of the sample 400 such that the XRR measurements can be conducted at different azimuthal angles between a given axial line (such as y-axis) assigned on the 3D nanostructures of the sample 400 and the reflection plane of the X-ray.

(53) In the step S240, X-ray photoelectron spectrum (XPS) and X-ray fluorescence (XRF) signals can be collected concurrently during the XRR measurement, the combined XPS, XRF and XRR results will complement each other to enhance the accuracy in the analysis of surface structure information of the sample 400.

(54) The focus beam in this disclosure is confined by a slit in the z direction which makes the divergence angle very small and less than or equal to 1 degree. In the x direction, there is a divergence angle of 15 to 25 degrees which create a multiple-angle scattering diagram in this direction. A line cut can be performed at each angle on the scattering diagram to obtain the intensity value of the specular point. Then the intensities of the angle range are all integrated to obtain the reflectivity of the incident angle. Further, in the present application, the focus beam is chopped in the z direction; the information of the depth in the z direction of the sample can be analyzed according to different incident angles.

(55) According to the mentioned embodiments, an X-ray reflectometry apparatus and a method thereof for measuring three dimensional nanostructures on a flat substrate are provided by adjusting different incident angles , such that the critical dimensions of the sample in the z direction can be analyzed. Since the Qx and Qy signals integrates with the reflection signal Qz onto a surface of a sample, and only the light intensity in the Qz direction is taken, the analysis of critical dimensions in different depths can be successful by analyzing the electron density along the z direction vs. the depth map and combining with known line widths or line space information. In addition, the X-ray reflectometry apparatus of the present disclosure uses convergent long-wavelength X-rays, the wavelength of which is greater than a general commercial copper anode of 0.154 nm and less than twice of characteristic dimensions along the film thickness direction, and appropriate collimations on both incident and detection arms are provided to enable the XRR for measurements of samples with limited sample area and scattering volumes, such as a three-dimensional nanostructure sample on a flat substrate (i.e., a semiconductor substrate), to solve the problem of complex nanostructures along three coordinate directions being difficulty to measure by an X-ray reflectometry apparatus, and the complex nanostructures are such as rods or axis arrays with nanometer size.

(56) It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents.