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Nanofabrication and characterization of high-line-density x-ray

transmission gratings

Article in Journal of Micro/Nanolithography MEMS and MOEMS · August 2017

DOI: 10.1117/1.JMM.16.3.034503

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 Nanofabrication and characterization
of high-line-density x-ray
transmission gratings

Xiaoli Zhu
Hailiang Li
Leifeng Cao
Shenye Liu
Peixiong Shi
Changqing Xie

Xiaoli Zhu, Hailiang Li, Leifeng Cao, Shenye Liu, Peixiong Shi, Changqing Xie, “Nanofabrication and
characterization of high-line-density x-ray transmission gratings,” J. Micro/Nanolith. MEMS
MOEMS 16(3), 034503 (2017), doi: 10.1117/1.JMM.16.3.034503.

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 J. Micro/Nanolith. MEMS MOEMS 16(3), 034503 (Jul–Sep 2017)

Nanofabrication and characterization of high-line-density

x-ray transmission gratings
Xiaoli Zhu,a Hailiang Li,a Leifeng Cao,b Shenye Liu,b Peixiong Shi,c and Changqing Xiea,*
a
Institute of Microelectronics of Chinese Academy of Sciences, Key Laboratory of Microelectronic Devices and Integrated Technology,
Beijing, China
b
China Academy of Engineering, Research Center of Laser Fusion, National Key Laboratory of Laser Fusion, Mianyang, China
c
Technical University of Denmark, Danchip-Cen, National Center for Micro- and Nanofabrication, Kgs Lyngby, Denmark

Abstract. We report the nanofabrication and characterization of x-ray transmission gratings with a high aspect
ratio and a feature size of down to 65 nm. Two nanofabrication methods, the combination of electron beam and
optical lithography and the combination of electron beam, x-ray, and optical lithography, are presented in detail.
In the former approach, the proximity effect of electron beam lithography based on a thin membrane of low-z
material was investigated, and the x-ray transmission gratings with a line density of up to 6666 lines∕mm were
demonstrated. In the latter approach, which is suitable for low volume production, we investigated the x-ray mask
pattern correction during the electron beam lithography process and the diffraction effect between the mask and
wafer during the x-ray lithography process, and we demonstrated the precise control ability of line width and
vertical side-wall profile. A large number of x-ray transmission gratings with a line density of 5000 lines∕mm
and Au absorber thickness of up to 580 nm were fabricated. The optical characterization results of the fabricated
x-ray transmission gratings were given, suggesting that these two reliable approaches also promote the develop-
ment of x-ray diffractive optical elements. © 2017 Society of Photo-Optical Instrumentation Engineers (SPIE) [DOI: 10.1117/1.JMM.16.3
.034503]

Keywords: Au transmission gratings; electron beam lithography; x-ray lithography; x-ray spectroscopy.
Paper 17058SS received Apr. 30, 2017; accepted for publication Jul. 25, 2017; published online Aug. 19, 2017.

1 Introduction achieved by a single EBL step.23–25 For many specific appli-

Au transmission gratings (TGs) are invaluable optical cations, EBL continues its path to obtain features with
elements in numerous applications. More specifically, smaller dimensions and higher aspect ratios and can be com-
x-ray telescopes such as Chandra and the Solar and bined with other lithographic technologies to realize the
Heliospheric Observatory adopted a huge amount of x-ray desired elements.26 However, every above-mentioned litho-
TGs with a feature size of 100 and 200 nm.1–3 High- graphic method has strengths and weaknesses and still
aspect-ratio Au TGs were used for hard x-ray differential suffers from many challenges such as sophisticated deep-
phase-contrast imaging.4–7 In x-ray spectrometers, x-ray reactive-ion etching process, mask fabrication, and low
TGs with a high line density are key dispersing elements writing speed.12,16,19
for both spectral and imaging goals.8–11 The heavy demands Here, we report on our recent progress on nanofabrication
of x-ray TGs in scientific instruments with a compact size, and characterization of high-line-density x-ray TGs. On one
light weight, and high degree of design flexibility have moti- hand, to fabricate 6666 lines∕mm x-ray TGs, EBL was used
vated considerable research on nanofabrication techniques. to directly write patterns on the membrane of low-z material
Various performance goals of x-ray TGs pose an extreme and combined with ultraviolet lithography (UVL) to define
challenge to nanofabrication technologies. supporting frames. To meet the heavy demands of x-ray TGs
Currently, the methods for manufacturing high-line- with 5000 lines∕mm density, 100 nm bar width, and 580 nm
density gratings include interference lithography plus deep height, EBL, x-ray lithography (XRL) and UVL were
reactive ion etching,12,13 interference lithography followed combined to fabricate TGs in low volume production. Two
by anisotropic Si wet etching,14,15 nanoimprint and multistep combined approaches are capable of directly patterning
etching,16 ion beam lithography,17,18 etc. In addition, electron nanoscale resist structures with a vertical cross section,
beam lithography (EBL) and its combination with other avoiding the sophisticated etching process. Both of them
nanofabrication technologies are of great interest for are robust fabrication procedures under tight process control
fabricating x-ray diffractive optical elements including with a large process latitude. The former is able to fabricate
x-ray TGs.9–21 EBL tools have been developed with a fast finer gratings, and the later has higher yields. For the indi-
100-MHz line frequency and a beam diameter of several vidual combination, to precisely control the line/space ratio
nanometers.22 A remarkable progress has also been made and achieve a vertical cross section, some improvements
in which nanostructures with a high aspect ratio of up to have to be made such as writing patterns on membrane sub-
20 nm and patterns with 4.5-nm half-pitch have been strates in EBL, pattern correction on the mask, and mask/
wafer gap control in XRL. The subsequent characterization

*Address all correspondence to: Changqing Xie, E-mail: [email protected]

.cn 1932-5150/2017/$25.00 © 2017 SPIE

J. Micro/Nanolith. MEMS MOEMS 034503-1 Jul–Sep 2017 • Vol. 16(3)

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

" mπa#2   
of fabricated x-ray TGs has shown their satisfying optical sin 2π
p −4π
λ βz −2π
λ βz
performances. ηm ðλÞ ¼ 1þe − 2e cos δz ;
λ
EQ-TARGET;temp:intralink-;e002;326;752

mπ
(2)
2 Design of Self-Supporting X-Ray TGs
Figure 1 shows the schematic geometry of x-ray TGs, con- where m ≠ 0, a is the gap between grating bars, z is the
sisting of free-standing gold grating bars with a width of absorber thickness, λ is the wavelength of incident x-ray
down to several tens of nanometers supported by coarse light, β is the imaginary part of the refractive index, and δ
mesh or polyimide membranes. The diagram does not is the real part of the refractive index. On one hand, it
show proper proportions. The diameter of the supporting sil- can be deduced that when the ratio of gap to period (i.e.,
icon frame is 20 mm, and the grating area is from several to a duty cycle) is 0.5, the first-order efficiency reaches a maxi-
few tens of square millimeters, which can be patterned by mum, and all even orders disappear. If the duty cycle is up to
direct-writing electron beam lithographic tools. In the soft 0.75 or down to 0.25, the efficiency decreases to 50% of the
x-ray region from 0.1 to 2 keV, x-ray is intensively absorbed maximum. On the other hand, the efficiency of x-ray TGs is
in any known material.27,28 Therefore, x-ray must freely pass also determined by the thickness of gratings. According to
through gaps between gratings bars without any absorption. Eq. (2), the efficiency approaches its maximum when z is
In other applications where photon energy is above 2 keV, λ∕ð2δÞ and the phase shift is correspondingly π. To achieve
grating bars can be fabricated on x-ray transparent mem- enough diffraction efficiency, 300 to 600 nm of bar height is
branes of low-z materials.29 The refraction index of x-ray required in the x-ray region. In addition, the diffraction effi-
in any material can be written as n ¼ 1 − γ − iβ, where γ ciency decreases when the cross section deviates from the
and β are very small for all materials, resulting in much dif- rectangle.36
ficulty in deflecting x-rays and designing x-ray diffractive To achieve high spectral resolution, enough efficiency,
optical elements.30 When x-rays pass through fine structures and desired phase shift, nanoscale grating bars with nano-
of high-z materials, both the intensity and phase are modu- scale width, desired height of absorber, and precisely
lated simutaniously,31,32 offering a multifunctional and flex- controlled line/space ratio must be constructed to be free-
ible way to diffract or focus x-rays. standing or on membranes of low-z materials.
Spectral performance of gratings is mainly determined
by two factors: the period and the absorber thickness.37
3 High-Line-Density X-Ray Transmission Gratings
At normal incidence, the first-order diffraction angle of the
Fabricated by Electron Beam Direct Writing
grating can be expressed as
3.1 State-of-Art of X-Ray TGs Fabrication
θ ¼ sin−1 ðλ∕pÞ;
EQ-TARGET;temp:intralink-;e001;63;432 (1)
Until now, a variety of lithographic techniques have been
where θ is the diffraction angle, λ is the wavelength of developed to realize design targets of x-ray TGs. Both advan-
incident light, and p denotes the grating period.33 To obtain tages and tradeoffs exist for each lithographic technique.
a large diffraction angle (i.e., high spectral resolution), one Researchers at Massachusetts Institute of Technology and
needs to decrease the period of TGs to 150 nm for their Max-Planck-Institut fur Physik und Astrophysik (Germany)
applications in high spectral-resolution spectrometers. have accomplished the pioneering work and developed
Another crucial parameter of x-ray TGs is the efficiency, a huge amount of x-ray TGs with bar widths of 100 and
especially for their applications in x-ray spectrometers. The 200 nm using interference lithography.37–40 This process
diffraction efficiency of wire gratings with a rectangular can also be followed by wet anisotropic etching to achieve
cross section can be calculated as34,35 x-ray critical point TGs with extremely high aspect
ratios.41,42 Extreme ultraviolet (EUV) interference lithogra-
phy and its variants can scale the EUV gratings pitch down
to 50 nm and fabricate periodic structures smaller than
10 nm, but they suffer from the limitation of periodic patterns
and uniformity in large areas.43–47 Nanoimprint provides a
low-cost approach to fabricating gratings with high spatial
resolution. However, for many applications, there are still
many challenges such as defects and template patterning.48,49
In recent years, anisotropic Si wet etching in hydrofluoric
acid and hydrogen peroxide solutions enables to achieve
silicon nanostructures with an extremely high aspect ratio
of up to 120, but how to transfer patterns from silicon to
metal is challenging.50
In addition, EBL has shown its potential in fabricating of
high-line-density x-ray TGs due to its high resolution and
large penetration depth in the resist. An 100-keV electron
beam writer can directly pattern gold gratings with 1 μm
height and 45 nm width.20 50-nm-wide and 300-nm-thick
platinum grating structures were fabricated from a trilayer
Fig. 1 Schematic geometry of x-ray TGs with free-standing Au grating resist exposed by EBL and followed by reactive ion etching
bars supported by coarse gold frames. plus electroplating.21 The beam size can be focused within

J. Micro/Nanolith. MEMS MOEMS 034503-2 Jul–Sep 2017 • Vol. 16(3)

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

several nanometers to fabricate EUV TGs with a lines den- finished after removing the CrAu seed layer by argon plasma
sity of 10;000 lines∕mm and an absorber height of 80 nm.27 etching.
Although EBL is capable of patterning gratings with line In the above processes, PMMA coated on the polyimide
density of up to 10;000 lines∕mm in the EUV region, the membrane was exposed by an electron beam writer with
thickness of the absorber is several tens of nanometers. 100 kV accelerating voltage to decrease the proximity effect
Moreover, how to combine EBL with other lithographic due to two factors. One is that the membrane substrate can
techniques to manufacture x-ray TGs in high throughput effectively decrease the extradose caused by backscattered
has been challenging for several decades.38 Furthermore, electrons. Another is that the accelerating voltage of 100 kV
EBL can generate arbitrary patterns for more flexible designs makes it possible to prevent the obvious beam size broaden-
including variable gratings and binary optical elements.51 ing due to little forward scattering.52 To demonstrate the
To date, the nanofabrication of high-line-density x-ray TGs proximity effect in PMMA resist and the membrane, the
operating in the x-ray region is still technically challenging. distribution of absorbed energy in 400-nm PMMA on a
polyimide membrane coated with 5-nm Cr and 10-nm Au
3.2 Combination of EBL and Optical Lithography was calculated by the Monte Carlo simulation method
The desired 6666 l∕mm x-ray TGs consist of grating bars (Tracer, GenIsys). In the simulation, electron beam energy
with a 75 nm half-pitch and a 350 nm thickness on a of 100 keV and the electron number of 106 were used.
2.0-μm-thick polyimide membrane that is x-ray transparent Figure 3 shows the radial distribution of energy density
in a 2.0- to 4.0-keV region. In the fabrication process, the absorbed in 400-nm PMMA, 15-nm CrAu seed layer, and
combination of EBL and UVL was adopted to pattern the 2-μm polyimide membrane. The embedded zoom-in image
grating structures. EBL can be performed to directly pattern in the bottom-left shows the energy distribution near the inci-
grating structures, taking advantages of extremely high dent point. In the radial direction, when the energy density
resolution, acceptable writing speed, and large penetration decreases by two orders, the widths of energy distribution
depth of electrons. To our knowledge, few works have from the zero point on the top and bottom of the resist are
been able to realize x-ray TGs with line density of up to 2.37 and 2.48 nm, respectively. The simulation result dem-
6666 lines∕mm that can operate at a photon energy of up onstrates the ability to pattern high-line-density gratings with
to 4 keV. a vertical cross section and high aspect ratio, both of which
The process of the combination of EBL and UVL, which are crucial in the nanofabrication of x-ray TGs.
is shown in Fig. 2, consists of two main steps in which EBL By exposing 400-nm PMMA resist on a 2-μm polyimide
was used to pattern nanoscale gratings and UVL was per- membrane, extremely high contrast of resist can be achieved
formed to generate coarse supporting frames. First, the proc- in exposure. During the electron beam exposure, the calibra-
ess started by depositing of 15-nm CrAu on a polyimide tion of electron beam was automatically carried out every
membrane using electron evaporation; second, an extremely 5 min to avoid the writing field distortion caused by the sur-
fine electron beam with a 100 kV accelerating voltage and a face height fluctuation. After development and electroplat-
200 pA current (JBX6300FS, JEOL) was used to directly ing, the fabricated grating structures are shown in Fig. 4(a).
write patterns in polymethylmethacrylate (PMMA, 5% In addition, the polyimide membrane was used to support
2200k in anisole, resist 1 in Fig. 2) resist, followed by gold grating structures due to its robustness and excellent radia-
electroplating in the gaps of the resist structures. Third, to tion resistance. However, during UVL, the polyimide mem-
define supporting frames on the grating structures, a PMMA- brane becomes wrinkled, and patterns on the membranes
based resist of SX AR-N 4800/16 (resist 2 in Fig. 2) was get distorted when polyimide membrane is immersed into
exposed by an aligner, developed in the mixture of methyl- alkaline-based developer. Thus, SX AR-N 4800/16 negative
isobutylketone (MIBK) and isopropyl alcohol (IPA), and resist was used to define coarse supporting frames since it
rinsed in IPA. Fourth, electroplating was performed to can be dissolved in an organic developer mixed by MIBK
form coarse supporting gold fames. Finally, x-ray TGs were and IPA, which do not lead to wrinkled polyimide

Fig. 3 Simulated radial energy density absorbed in the stack of

Fig. 2 The combined process of EBL and UVL for fabricating x-ray 400-nm PMMA∕10-nm Au∕5-nm Cr∕2-μm polyimide, the energy of
TGs. incident electrons is 100 keV.

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

Fig. 4 Achieved high-line-density x-ray TGs consisting of (a) grating bars fabricated by EBL and electro-
plating and (b) coarse frame defined by UVL with SX AR-N 4800/16 negative resist.

membrane. The UVL was performed to pattern the coarse receive the diffraction pattern. Figure 5(a) shows the diffrac-
meshes on the grating bars, and the overlay accuracy of tion pattern that is symmetrically distributed on both sides of
EBL and UVL was kept within 2 μm. After exposure, the the zeroth-order when the photon energy of incident x-ray
resist structures were transferred to the Au layer by electro- was 2.9 keV. The second-order cannot be neglected, while
plating. Finally, the achieved device is shown in Fig. 4(b). any third-order is not visible. This is due to the deviation
Grating bars are perpendicular to the supporting bars. of the grating bar width from the original design. The mea-
Every opening area of grating is 150 μm × 92 μm and sup- sured grating bar width is 65 nm rather than the desired
ported by 21-μm wide bars. The grating area patterned by 75 nm in Fig. 4(a). Figure 5(b) shows the measured ratio
EBL is 450 μm × 92 μm, and the writing time was 15 min. of first-order to zeroth (i.e., relative diffraction efficiency)
The area could be several times larger if the trade-off at an energy range of 2.1 to 4.0 keV. The relative first-
between electron current and beam diameter has been made order efficiency is from 8.89% to 9.41%, which is acceptable
to optimize the lateral resolution and the writing speed. In for 150-nm period x-ray TGs operating at 4.0 keV. Because
addition, in the final step, the CrAu seed layer was removed of the 350 nm thickness of the absorber, the efficiency
by a maskless process of induced plasma coupling etching. gradually decreases at photon energy above 3.5 keV.
Using a high platen power, the 15-nm-thick CrAu seed layer
was etched and the width of the gold bars was hardly 4 X-Ray TGs Nanofabrication in High Throughput
changed.
4.1 Combination of EBL, XRL, and UVL
Although EBL can generate patterns with extremely high
3.3 Characterization of 6666 Lines/mm X-Ray TGs spatial resolution and a high aspect ratio, it suffers from
The diffraction pattern of fabricated 6666 lines/mm x-ray its serial writing strategy. The fabrication process of x-ray
TGs was obtained at a 4B7A beamline on a Beijing synchro- TGs is very time-consuming, and membrane-based x-ray
tron radiation facility, which covers the photon energy TGs are definitely fragile in their characterization and use.
range from 2 to 6 keV. The incident x-rays passed through To meet the heavy demands of x-ray TGs in their applica-
the shutter and the x-ray TGs and reached the detector. tions, the combination of EBL, XRL, and UVL was devel-
Behind the sample, an x-ray charge-coupled device with oped to manufacture nanostructures in high throughput.54–56
2048 × 2048 pixels and 13.5 μm pixel size was used to EBL has the ability to pattern structures with less than 5-nm

Fig. 5 Characterization results of 6666 lines∕mm x-ray TGs, including (a) diffracted pattern at 2.9 keV
and (b) the measured relative first-order efficiency in 2.1- to 4.0-keV energy range.

J. Micro/Nanolith. MEMS MOEMS 034503-4 Jul–Sep 2017 • Vol. 16(3)

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

critical dimension and generate arbitrary complex patterns. (Elevate gold RTU 7790). After that, PMMA was removed
XRL enables the efficient replication of nanostructures in an acetone solution, and the seed layer was etched by
with a sub-20-nm spatial resolution or a high aspect ratio argon plasma. To get a stable process in EBL, electrons
due to the short wavelength, large depth of focus, and low were focused to expose the resist on the Si3 N4 membrane,
x-ray absorption in resist.57 Although the fabrication of XRL which can eliminate the backscattering effect similar to
mask by EBL is costly and time consuming, once one or two that on polyimide membrane demonstrated in Sec. 3.2.
masks have been finished, a large number of specimens with Compared with backscattered electrons on bulk silicon sub-
a high aspect ratio in high fidelity can be promptly achieved strates, more electrons pass through the membrane substrate
without sophisticated induced coupling plasma etching. and less are scattered by the atoms in the substrate.
To fabricate x-ray TGs in high throughput, the combina- To achieve nanoscale Au grating bars with equal widths
tion of EBL, XRL, and UVL was developed to fabricate and gaps using XRL, pattern correction must be considered
5000 lines/mm x-ray TGs, as shown in Fig. 6. First, in when starting the fabrication of x-ray mask the EBL step.
the EBL process, a scanning electron beam with a diameter Based on previous empirical experience and theoretical
of several nanometers was focused to pattern resist structures analysis (presented in Sec. 4.3), to pattern grating bars
with low aspect ratios on silicon nitride or silicon carbide with a width of 75 to 100 nm, 5 to 10 nm bias of the grating
membranes covered by CrAu seed layers. After exposure, bar on the mask for XRL is needed. While for 150- to 250-
Au gratings were formed through spaces between resist nm wide grating bars, 25 nm bias of bar width on the mask
structures. Second, with the mask fabricated in the EBL for XRL is suitable. For example, grating structures of
process, XRL and electroplating were formed to replicate 110-nm wide lines and 90-nm wide spaces on the mask are
nanostructures with high aspect ratios on resist/AuCr/poly- required for replicating 100-nm wide line/space gratings by
imide/Si stacks. Third, in the UVL step, an aligner and Au XRL. The difference of bias for bars with different widths is
electroplating were performed to pattern supporting frames. mainly determined by the diffraction effect when x-rays pass
Finally, the backside silicon of substrate was removed by through the mask/wafer. In EBL, to achieve an optimal line/
fluoric acid-based solution; the seed layer and polyimide space ratio, the resist was exposed with different line-space-
were removed by argon and oxygen plasma, respectively. ratio patterns on the layouts at different doses. By exposing
layout patterns with 90-nm line and 110-nm spacing at
4.2 Pattern Correction of Master Mask 1800 μC∕cm2 dose, the desired grating patterns were
achieved, as shown in Fig. 7, with the line width of 110 nm
Before the replication of x-ray TGs by XRL, the EBL step on the mask. The bias of grating bars was precisely kept
started by vapor-coating a 5-nm Cr layer and a 10-nm Au as 10 nm. Generally, the error of bar width must be within
layer as a plating base on 2-μm-thick Si3 N4 membranes. 5 nm, which will benefit the replication of gratings with
The resist of 400-nm-thick PMMA (5% 2200k in anisole) equal widths of bars and gaps in the following XRL step.
was spin-coated and baked at 160°C for 30 min in an
oven. Then, the resist was exposed using a 100-kV electron
beam writer. The beam current was 0.2-nA, and the dose was 4.3 Simulation of Pattern Formation in XRL
1800 μC∕cm2 (JBX6300FS, JEOL). The length and width of Compared with other lithographic techniques, XRL has
grating area were 10 and 0.1 mm, respectively. Resist pat- advantages of high resolution, large depth of focus, insensi-
terns with an aspect ratio of 4 were obtained after develop- tivity to different substrates, etc. However, in printing 100-
ment in MIBK: IPA (1∶3) for 40 s and rinsed in IPA for 30 s. nm-wide gratings, the variation of patterns on the mask and
The 350-nm-thick gold structures were formed by a pulse the substrate cannot be ignored since the diffraction effect
reverse electroplating process in a gold sulfite solution between the mask and wafer becomes more evident with
smaller critical dimensions or larger mask/wafer gaps.58,59
Hence, pattern correction of the x-ray mask must be
considered.53 To predict the pattern variation at different
mask/wafer gaps, the propagation of x-ray between mask and
wafer was simulated by a one-dimensional beam-propagat-
ing-method program with fast Fourier transformation (1-D
BPM-FFT). The simulation consists of x-ray propagation,
x-ray Fresnel diffraction, and resist blur. In the simulation,
width and period of bars on the mask are 110 and
200 nm, respectively. The blur of resist is 10 nm, and the
working wavelength is 1 nm. Aerial image profiles with dif-
ferent gaps on the resist surface are shown in Fig. 8. The full
width at full maximum (FWHM) of lateral intensity distri-
butions with mask/wafer gaps from 1 to 5 μm are 95, 85,
79, and 55 nm, respectively. The FWHM is changed from
95 nm at 1 μm gap to 79 nm at 3 μm gap, demonstrating
Fig. 6 Process flow to fabricate x-ray TGs by the combined process of that XRL has the potential to pattern high aspect ratio struc-
EBL, XRL, and UVL. The first part contains e-beam evaporation seed tures with 100 nm feature size and 2 μm height. In the expo-
layer on Si3 N4 membrane, electron beam exposure, electroplating, sure, due to the transportation of secondary electrons and
and removal of the resist and seed layer. The second part includes
XRL, electroplating, resist removal, and backside silicon wet etching. photoelectrons, the width of exposed bars will be broadened
The third part consists of UVL, electroplating, and etching of silicon, by 10 to 20 nm, which can partially compensate for the pat-
seed layer, and polyimide. tern shrinkage caused by the diffraction of x-rays between

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

Fig. 7 Patterns with 10 nm bias on the master mask taken from (a) top view and (b) cross section tilted at
30 deg.

the mask and wafer. The above analysis indicates that, to rep- 4.4 Replication of Gratings with High Aspect Ratio
licate grating bars with 100-nm line/space, 110 nm width of The replication processes are very similar to those for fab-
bars on the mask is required and the gap of mask/wafer must ricating x-ray masks in the EBL step, as shown in Fig. 6.
be less than 3 μm. In the experimental setup, a magnetic A 600-nm-thick PMMA resist coated on 2-μm-thick polyi-
force was applied on the mask/wafer holder to achieve a mide film with plating base was exposed at a dose range of
gap of less than 3 μm, which can be detected by counting 6 to 8 J∕cm2 , developed in MIBK: IPA (1∶3) for 40 s and
Moire rings on the backside Si3 N4 membranes. rinsed in IPA for 40 s; resist patterns were transferred to a

Fig. 8 Simulated aerial image profiles with different mask/wafer gaps of (a) 1, (b) 2, (c) 3, and (d) 5 μm,
respectively.

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

Fig. 9 Replicated grating patterns including (a) resist patterns with rectangular cross section and
(b) smooth gold gratings with equal widths of bar and gap.

gold layer using electroplating. After that, UVL was carried To form x-ray grating bar gold structures, electroplating
out to define coarse supporting frames on the grating struc- rather than the lift-off process is more frequently used
tures with the overlay accuracy of 2 μm and was followed by because electroplating is able to transfer the resist pattern
Au electroplating. Finally, bulk silicon on the backside was to thicker metal layer than lift-off. In the above process,
etched by the solution of hydrofluoric, nitric, and acetic no adhesion layer was used to stabilize the lithographic
acids. The replicated gratings with equal bar and gap widths, process, since an adhesion layer can frequently lead to failure
smooth edges, and rectangular cross section are shown in in the following process. In this combined process, the
Fig. 9. The gold thickness in Fig. 9(b) is 580 nm. pattern generation process is straightforward and robust. The

Fig. 10 Measured angular distribution of spectra at different wavelengths of (a) 5, (b) 6, (c) 7, and
(d) 8 nm, respectively.

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 Zhu et al.: Nanofabrication and characterization of high-line-density. . .

combined process is able to produce a large number of x-ray production. The characterization results have implied that
TGs within a limited period for heavy demands. Moreover, the ratio of grating bar and space was controlled as 0.44,
due to extremely large penetration depth of x-rays in expo- definitely close to the optimal value of 0.5. More impor-
sure, it can generate nanopatterns with a high aspect ratio and tantly, both the former and the later combined methods are
rectangular cross section, which are desired in various x-ray able to not only construct nanoscale and high-aspect ratio
diffractive optical elements. structures but also generate arbitrary patterns, providing
more flexibility and design freedom for x-ray diffractive
4.5 Characterization of Replicated 5000 Lines/mm optical elements and promoting the development of x-ray
X-Ray TGs scientific instruments.
The characterization of replicated x-ray TGs was performed Acknowledgments
at U26 beamline, Hefei Synchrotron Radiation Light Source. We would like to extend our gratitude to Professor Gang Liu
The geometric position of gratings was controlled by a sam- (USTC) and Futing Yi (IHEP, CAS) for their help on x-ray
ple holder with 0.005 deg accuracy between the Si photo- lithography, senior engineer Hongjun Zhou (USTC) and
diode detector and filter plus slit. X-rays from the storage Professor Mingqi Cui (IHEP, CAS) for their help on testing,
ring were selected by the monochromator gratings (600 and and Mr. Matteo Todeschini (Danchip, DTU) for his a
1800 lines∕mm), and the contribution of higher diffraction ssistance in grammar. This work was supported by the
orders was limited by setting different filters. The 100-μm National Key Research and Development Program of
slit was used to collimate the light on the x-ray TGs, and China (2017YFA0206002) and China Scholarship Council
all measurements were performed with monochromatic (201504910112).
radiation normal to the gratings.
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