X Ray Lithography

X-ray lithography
Light source : X-rays (high penetration power, high aspect

ratio)
X-rays used are provided by synchrotron which allows high
throughput (high flux collimated rays shortens the exposure
time)

Popular photoresist : PMMA

Most masks are transparent to X-rays. Thus, a thin film of
gold is applied to block X-rays.
Mask used: Silver Nitride
X-ray lithography (XRL)
1. Overview
2. X-ray source ( electron impact and synchrotron radiation).
3. X-ray absorption and scattering.
4. X-ray lithography resist (PMMA and SU-8).
5. X-ray lithography mask (absorber on membrane).
6. LIGA process (for high aspect ratio metal structure).
7. Zone plate for focused x-ray beam array lithography.
8. Resolution enhancement
3
The Electromagnetic Spectrum
Cu-K
X-ray lithography history
D. L. Spears and H. I. Smith, High resolution
pattern replication using soft x-rays,
Electronic Letters, 8, 102 (1972).

H. I. Smith
(MIT)
5
X-ray Lithography
X ray lithography has been under development since 1972. As in E-beam
lithography, the wavelengths of x rays are much shorter than UV light. Thus they
hold the promise of sharper imaging during exposure of the resist. X ray are
difficult to focus during lithography. Consequently contact or proximity must be
used, and a small
X ray source must be used at a relatively large distance from the wafer surface in
order to achieve good image resolution through mask.
X-ray lithography with wavelengths between 0.2 and 2 nm provides a structural
resolution as good as 0.1 inn under optimized conditions even in the case of high
proximity gaps of 50 pm which are needed in practical applications

6
Wilhelm Conrad
Roentgen (1845-1923)
What is X-ray?
Roentgen discovered an unknown ray in 1895
(X-ray) that can cause barium platinocyanide-
coated screen to glow.
He won the first Nobel prize in physics in 1901.
AM
FM
Cell phone, PCS
Microwave
X-ray
7
Photo-electron
Photon
(fluorescent x-ray)
Electron
(Auger electron,
emitted from M-
shell)
Auger-electron
X-ray
atom
X-ray absorption: photoelectric absorption dominates at <10keV
The picture below is similar to electron bombardment x-ray source (see slide #13),
where core electron is kicked off by an incident electron. Here it is kicked off by x-ray.
In the relaxation process, the lower energy photon is a fluorescent x-ray, while the
lower energy electron is an Auger electron.
1. A high energy x-ray
photon impinges on
an atom
2. An inner-shell (here K-
shell) electron (photo-
electron) is knocked out of
the atom.
3. The atom relaxes to
its ground state by
emission of a
photon or electron
Photon (x-ray)
(fluorescent x-ray)
(Auger electron)
Electron (low energy)
o
k
is the energy level of the K-shell
8
High resolution resist structures by x-ray lithography
~50nm lines
R. Waser (ed.), Nanoelectronics
and Information Technology
~150nm lines
9
1. Overview
10
Types of x-ray sources:
Electron Impact X-ray source
Plasma heated X-ray source
Laser heated
E-beam heated
Synchrotron X-ray source

X-ray source
11
high power
laser
metal
tape
Same idea as laser produced plasma (LPP) EUV source, but shorter wavelength (a few nm).
High power-density laser pulses generate a hot and dense plasma, which emits x-rays
when free electrons recombine with ions, or bond electrons jump to a lower energy level.
More complicated than electron bombardment source, less powerful than synchrotron
radiation.
Laser produced plasma x-ray source
X-ray source and their irradiation power
(impact)
12
e
1
e
1
e
2 (photo-electron)
X-ray

X-ray generation by electron impact (bombardment)
( ) ( ) ) ( 1 17 . 10
2
1
1
1
1 56 . 13
2
2 2
2
eV Z Z E E E
L k
~
|
.
|
\
|
= = For K
o
line:
Here (Z-1) instead of Z due to screening effect of the other electron in n=1 level. More
generally, (Z-1) should be replaced by (Z-o), with o accounting for the screening effect.
When electron jumps from L to K-shell, it either
emits x-ray (as shown in the figure), or gives its
energy to an outer-shell electron that escapes
subsequently (Auger electron, not shown).
In atomic physics,
K denotes the shell/orbit
with n=1 (innermost
shell), L for n=2, M for
n=3, N for n=4

The energy level for atom
with atomic number Z is
given by:
E=-13.56 Z
2
/n
2
(eV)
13
Electron impact: sealed tube x-ray source (point source)
Developed by Coolidge (at GE) around 1912.
Electron accelerated at high energy to the anode.
Low power, tuned to maximize for narrow emission range (for
example, Mg or Cu K
o
).
For material characterization by x-ray diffraction and medical imaging
Hot filament emits electrons
e
X-ray
14
Synchrotron radiation x-ray source:
the choice for x-ray lithography
16
Shield Wall
Storage Ring
Synchrotron radiation (SR):
Electromagnetic radiation (light) emitted from electrons moving with relativistic velocities.
First observed in 1947 from a 70MeV electron accelerator at GE.
In earlier times, it was just considered as waste product, limiting accelerator performance.
However, other researchers soon realized that SR was the brightest source of infrared,
ultraviolet, and x-rays, very useful for studying matter on the scale of atoms and molecules.
Irradiation is highly polarized and pulsed (e.g. nanosecond pulse).
Observer sees only a small portion of electron trajectory. The pulse length is thus the
difference in time it takes an electron and a photon to cover this distance on the circle.
Advantages of synchrotrons for X-ray lithography
Extremely high intensity.
Extremely high brilliance - small effective source size
situated a long distance from the experimental station.
Very low divergence out of the plane of storage ring.
Tunable, specific energies can be chosen.
Highly polarized and short pulses.
It offers many characteristics of visible lasers but into
the x-ray regime: partial coherence, high stability.
22
1. Overview and resolution limit.
25
In addition to photoelectric absorption (producing photoelectrons and characteristic
x-rays or Auger electrons), the original x-rays may be scattered by electrons.
There are two kinds of scattering: coherent (Rayleigh, no energy loss) and incoherent
(Compton).
X-ray absorption / attenuation
X-ray
T
A
R
G
E
T
characteristic
(Rayleigh)
(Compton)
( ) t I I o = exp
0
Intensity I
0
t
o: absorption coefficient
1/ o: attenuation length
Intensity I

26
Coherent
Incoherent
(Compton scattering)
+A

Coherent scattering: happens when x-ray collides with
an atom and deviates without a loss in energy.
An electron in an alternating electromagnetic field (x-
ray) will oscillate at the same frequency and emitt in all
directions.
This is useful for understanding x-ray diffraction (each
atom is a new x-ray point source).
Incoherent scattering: incident x-ray loses some of its
energy to the scattering electron. As total energy
(=hc/) is preserved, the wavelength of the scattered
photon increases by:
(in )
(Here 0.0243=h/m
e
c, h=6.6310
-34
is Planks constant,
m
e
=9.110
-31
kg is electrons mass)

A =0.0243(1coso)
X-ray scattering
27
Photo-electron
Photon
(fluorescent x-ray)
Electron
(Auger electron,
emitted from M-
shell)
Auger-electron
X-ray
atom
X-ray absorption: photoelectric absorption dominates at <10keV
The picture below is similar to electron bombardment x-ray source (see slide #14),
where core electron is kicked off by an incident electron. Here it is kicked off by x-ray
(the incident x-ray is absorbed/lost).
In the relaxation process, the lower (than incident x-ray photon) energy photon is a
fluorescent x-ray, while the lower energy electron is an Auger electron.
1. A high energy x-ray
photon impinges on
an atom
2. An inner-shell (here K-
shell) electron (photo-
electron) is knocked out of
the atom.
3. The atom relaxes to
its ground state by
emission of a
photon or electron
Photon (x-ray)
(fluorescent x-ray)
(Auger electron)
Electron (low energy)
o
k
is the energy level of the K-shell
28
e
1
e
1
e
2 (photo-electron)
X-ray

X-ray generation by electron impact (bombardment)
( ) ( ) ) ( 1 17 . 10
2
1
1
1
1 56 . 13
2
2 2
2
eV Z Z E E E
L k
~
|
.
|
\
|
= = For K
o
line:
Here (Z-1) instead of Z due to screening effect of the other electron in n=1 level. More
generally, (Z-1) should be replaced by (Z-o), with o accounting for the screening effect.
When electron jumps from L to K-shell, it either
emits x-ray (as shown in the figure), or gives its
energy to an outer-shell electron that escapes
subsequently (Auger electron, not shown).
In atomic physics,
K denotes the shell/orbit
with n=1 (innermost
shell), L for n=2, M for
n=3, N for n=4

The energy level for atom
with atomic number Z is
given by:
E=-13.56 Z
2
/n
2
(eV)
29
1. Overview and resolution limit.
30
X-ray interaction with resist
Absorption of x-ray does not lead directly to resist modification.
Photoelectrons and Auger electrons are responsible for resist modification.
Therefore, x-ray lithography resist is similar to that for e-beam lithography.
That is, any e-beam lithography resist can also be used as x-ray lithography resist.
In general, high energy x-rays (e.g. =0.3-5) do not interact strongly with materials, so
very low absorption.
o The good news: x-ray resist will be uniformly illuminated (top to bottom) for not-so-
thick resist.
o The bad news: x-ray masks will be hard to make opaque (need many um Au).
o The worse news: powerful x-ray sources are needed (most energy just pass through
without exposing the resist).
o To reduce exposure time substantially, one can use chemically amplified resist (SU-8)
having high sensitivity.
31
Materials for photoresists
Requirements:
Sensitive to X-ray radiation
High resistance to dry and wet etching
Thermal stability upto 140 deg Celsius
Unexposed resist should be absolutely insoluble during
development
Good adhesion to substrate during electroplating
Optimal solution : PMMA
Limitations:
Low lithography sensitivity makes the process slow
Vulnerability to crack due to stress
Other materials suggested: Polyoxymethylene,
Polyalkensulphone, Polymethacrylimide .

PMMA (polymethylmetacrylate)
the most used.
High resolution.
Low sensitivity (2.5 kJ/cm
3
minimum dose).
Long exposure times.
Up to 100m thick 1-3 keV energy.
From 100m to 500m thick 3 - 7 keV energy.

SU-8 (epoxy based)
a promising material
Good resolution.
High sensitivity.
Short exposure times.
Difficult processing.
Resists for deep X-ray Lithography
33
X-ray absorption of PMMA Transmission of PMMA
For the same resist thickness:
Higher energy less absorption, more uniform
dose profile throughout the thickness, but low
resist sensitivity and needs longer exposure time.
So tradeoff must be made when choosing energy.
X-ray absorption by PMMA resist
Photon energy (eV)
Photon energy (eV)
Linear absorption coefficient o (1/um) Transmission of PMMA sheets of different thickness
100eV (12.4nm, EUV) ~0.23 um
1keV (1.24nm) ~3um
10keV (1.24) ~3mm
Medical imaging, need many cm, so s0.1
1.24nm
Attenuation length 1/o (penetration depth)
34
X-ray lithography resist: PMMA (poly(methyl methacrylate))
PMMA is the most commonly used resist (positive tone) for x-ray lithography
with good quality in accuracy and sidewall roughness, but
extremely insensitive.

PMMA: 500m thick
Scan length: 6cm
Synchrotron at CAMD: 1.3GeV
Storage ring current: 150mA
Exposure time: 6 hours
Chain scission in poly(methyl methacrylate)
35
Change of mean molecular weight in PMMA
Dissolvable by developer
Initial distribution of
high M
w
PMMA
(500kg/mol)

M
w
distribution at the
substrate (bottom
dose). (5.7kg/mol)

M
w
distribution at the
surface (top dose).
(2.8kg/mol)
Solubility of PMMA
in GG-developer, nearly ideal at
room temperature.
Exposure to x-ray (that generates Auger electrons) cut the PMMA chains,
leading to smaller molecular weight (M
w
) that dissolves faster in developers.
36
Characteristic doses: definition and their values for PMMA
37
High sensitivity x-ray lithography resist: SU-8
SU-8 is a negative tone chemically amplified (so high sensitivity but low
resolution) resist for optical lithography, x-ray lithography and e-beam
lithography.
Low absorption at >400nm or at deep x-ray, making high aspect ratio deep
resist structure possible by optical or x-ray lithography.
On the other hand, low absorption is disadvantages for thin resist process due to
low energy deposition in the resist layer (most energy just pass through).
One big problem with SU-8 is that, once cross-linked by exposure, SU-8 is
extremely difficult to remove by chemicals (RIE not practical for etching thick
>>1um polymers).
38
Summary: what wavelengths for what application
The selection of x-ray wavelength depends on resolution and resist height (aspect ratio).
Longer wavelength (1-5nm): shorter penetration depth, so thinner resist, thinner Au absorber, thinner
membrane (fragile). Long means more serious diffraction that limits resolution.
Shorter wavelength (0.3-5): thicker resist/absorber/membrane. Low absorption means low resist
sensitivity/longer exposure time.
Therefore:
o For high resolution applications, longer wavelength will be better, since it allows thinner absorber
(easier to pattern with high resolution) and thinner resist.
o For high aspect ratio application (resist thickness > 100um), shorter wavelength must be used. The
resolution is then limited by diffraction (since resist is very thick or gap is big), lateral diffusion of
photo-electron (less important), or non-vertical sidewall of the thick (>10um) Au absorber (difficult
to make deep vertical sidewall by e-beam/photo-lithography and electroplating).
Absorption in PMMA
Membrane mask
(Au)
(Si
3
N
4
)
M
a
s
k

R
e
s
i
s
t

39
1. Overview
40
X-ray lithography Mask aligner and Stepper
42
Xray mask aligner has 2 key components:
workstage system
alignement system
Workstage system keeps the gap between mask &silicon wafer
Alignment system move the stage to perform Step and repeat exposure.
This also termed as X-RAY STEPPER.

X-ray lithography Mask
43
Making the mask is indisputably the most difficult task in using x-ray
lithography.
IBM has successfully fabricated defect free masks with electroplated gold
absorber patterned using an internally developed EL-4 75 kV shaped-beam
ebeam
The mask consists of an X-ray absorber, typically of gold or compounds of
tantalum or tungsten, on a membrane that is transparent to X-rays,
typically of silicon carbide or diamond.
The X-ray masks consist of a thin membrane of low-Z material carrying a
high-Z absorber pattern.
The pattern on the mask is written by direct-write electron beam
lithography onto a resist that is developed by conventional semiconductor
processes
X-ray lithography is now performed on what is called the "sweet spot",
using local "demagnification by bias
Dense structures are developed by multiple exposures with translation.
The advantages of using 3x demagnification include, the mask is more
easily fabricated, the mask to wafer gap is increased, and the contrast is
higher. The technique is extensible to dense 15 nm prints

44
Xray masks must meet following processing, opticaland mechanical requirements.
(1) Transparency to X-ray and alignment wavelengths, filtration of soft X-rays and good
contrast.
(2) Durability and long-term stability to meet stringent alignment and overlay accuracies,
ability to withstand high tensile
stress.
(3) A smooth, defect-free substrate with 1 pm flatness, 0.2 pm features and 0.05 pm
placement error.

Mask materials. An X-ray mask blank is a single- or multilayer thin film membrane (of high
tensile strength) held in tension comfortably below its yield limit by a supporting ring. The
membrane could be formed either in an unsupported, slack form and mechanically
stretched over the blank frame or could be deposited onto a sacrifical substrate which once
etched leaves a taut membrane.

Mask patterning. EBL is typically used to write submicron patterns on resist applied over
either the absorber material for substractive process or the plating base for lift-off process.
45
Xray Mask fabrication :
Deposit supporting membrane
Fix the coated silicon substrate onto a supporting frame by epoxy gluing or thermal
fusion bonding
Remove the silicon substrate in the central region from backside by KOH chemical
etching
Deposit heavy metal onto the supporting membrane
Inspect the mask and repair any defects

20m thick UV-LIGA process.
Deep UV lithography on SU-
8.
Au platting.
Frame
25m thick Kapton Membrane
Plating Base
2m Au
20m SU-8
Kapton Mask
46
47
X-ray lithography
Materials for substrates
Substrate should be an electrical conductor to facilitate
electroplating. Insulators may be coated with electrically
conductive materials.

Eg : Austenite steel,
Cu plated with gold,Titanium and Nickel,
Si wafers with thin Titanium or Ag/Cr top layer,
Glass plates with thin metal coating

LIGA
German acronym: Lithographie
Galvanoformung, Abformung
1. Produce
lithographic mould
2. Electroplate to fill
mould with metal
3 . Mould
After: M. J. Madou, Fundamentals of
microfabrication 2nd ed. (CRC Press Boca
Raton, 2002)
LIGA
LIGA stands for X-ray LIthography, Electroforming (German:
Galvanoformung), and molding (German: Abformung).
A technology which creates small but relatively high aspect
ratio devices using x-ray lithography.
Relatively inexpensive than surface micromachining.
Suitable for applications requiring high aspect ratio.
Contd..
LIGA
LIGA stands for X-ray LIthography, Electroforming (German: Galvanoformung),
and molding (German: Abformung).
This technology allows defining high-aspect-ratio structures in nickel. The
process consists of exposing a sheet of PMMA bonded to a wafer using X-ray
lithography.
The PMMA is then developed and the exposed material is removed.Nickel is
then electroplated up in the open areas of the PMMA.
The nickel over-plate is removed by polishing, leaving highaspect- ratio nickel
parts. The PMMA is removed, and the nickel parts may remain anchored to the
substrate or be released.
Major fabrication steps
MEMS devices by LIGA process
Why LIGA?
Bulk micromachining and surface micromachining
techniques basically evolved from microelectronics
technology. So, the equipment used for fabrication of
microelectronics could be used for MEMS with a little
modification.

Drawbacks:
Low geometric aspect ratio
Use of silicon based materials
Problems
-On account of the finite size of the x-ray source and the finite mask-to-wafer gap, a
penumbral effect results which degrades the resolution at the edge of a feature.
-An additional geometric effect is the lateral magnification error due to the finite
mask-to-wafer gap and the non-vertical incidence of the x-ray beam. The projected
images of the mask are shifted laterally by an amount d, called runout. This runout
error must be compensated for during the mask making process.

Electroplating and Molding
Examples of LIGA manufactured
MEMS devices
67
X-Ray
Be Filter (125um)
Al Filter
100um thick SU-8 film
Si substrate
Au absorber (1.8um) 20um SU-8
Kapton mask Plating Base (0.2um Au)
5 - 15 keV spectrum after filtering
Deep X-ray Lithography
68
20m thick UV-LIGA process.
Deep UV lithography on SU-
8.
Au platting.
Frame
25m thick Kapton Membrane
Plating Base
2m Au
20m SU-8
Kapton Mask
69
LIGA process
LIthographie Galvanoformung Adformung
(Lithography/Electroplating/Plastic molding)

Developed during 1980s at Research Center Karlsruhe

Possible to produce microstructures with very high aspect ratios (up to 100),
very small structures (in the submicron range),
and with very smooth walls (surface roughness 50 nm)

To manufacture a tool in a molding step to replicate the microstructure of polymer

Processes : Basic LIGA
SLIGA (Sacrificial LIGA)
LIGA-like process
Basic LIGA process
Lithography/Electroplating/Plastic molding
LIGA process to produce polymer replica
X-ray lithography: resolution limit due to diffraction
Cerrina, J Phys D, 2000
Precise gap must be maintained: too close will damage membrane
mask, too far reduce resolution.
Although is very small, diffraction still present.
Resolution limit due to diffraction R=3/2[(g+t/2)]
1/2
, g: gap; t: resist
thickness.
(This is the same resolution equation as for photolithography)
E.g. 100nm feature size requires =1nm, g=4.4um (assume t<<g).
76
Resolution limit due to secondary effects
Secondary effects:
X-ray fluorescence of mask and substrate
that exposes resist.
Lateral diffusion of photoelectron and
Auger electron.
Thermal induced mask or resist motion or
distortion.
Non-vertical sidewall of the Au absorber
on mask.
It is found that the Auger electron (low energy)
is 10 more efficient to expose resist than
photo-electron (high energy); and the Auger
electron diffuse only <5nm.
Therefore, the photo-electron is not that
important in determining the final resolution,
and high resolution (<20nm) can be achieved
provided such a mask can be made (VERY
difficult).
77
X-ray lithography
Advantages:
No vacuum environment required (no charged particles involved)
Very small wavelength (< 14) - can produce 0.15 m features
High reproducibility (exposure independent of substrate type, surface reflections)

Disadvantages:
No optics involved limited to 1:1 shadow printing (no image reduction is possible)
Very expensive and complex mask fabrication (~10 days, cost is $4k-$12k)
Low sensivity of the resists
High cost of sufficiently bright X-ray sources
(e.g. Synchrotron)

X Ray Lithography

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X-ray lithography

Light source : X-rays (high penetration power, high aspect

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