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() (
) (
) (
)
(
) (
) (
)
where,
The desired time for a 3 silicon wafer with structural dimensions thickness of 35m was 1h at a
current of 150 mA.
4.5 Electroplating parameters:
There are several parameters which affect electroplating that we will discuss about them in the
following:
1-Current density
Current density can be calculated by dividing the plating current to the plating area (4-3).
According to Faradays Law increasing in the current density results in an increase in the rate of
plating. Furthermore, studies have shown that the deposited films with high current density are
smoother than the films plated with lower current density [67]. However, from train and error
increasing the current density drastically corrode the copper finish resulting in a dull plated
surface. Results were based on trial and error.
2- pH
pH depends on the chemical composition of the electrolyte but it must be kept in a range of 1.5
to 5 to have a good electroplating [68]. During electroplating, pH must always be controlled. If
52 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
pH is greater than desired value, drops of dilute hydrochloric acid are used to decrease the pH. If
pH is less than desired value, potassium hydroxide is used to increase the pH. [69]
3- Temperature
Temperature plays an important role in electroplating. It has been observed that at high bath
temperature, the surface finish is poor. The recommended temperature for copper electroplating
is 40C to 60C.
4-Agitation
When electroplating, the concentration of ions near the cathode will decrease. In order to
minimize the regions with low concentration, agitation is needed. Thus, during the process
agitation will remove hydrogen bubbles from the cathodes surface. It was reported that with
increase in agitation, surface roughness will decrease [71]. Therefore, agitation must be in a
proper value which prevents pitting and poor surface finishing.
5- Bath Composition
Electrolyte bath for copper electroplating is made from sulphate salts of copper and chloride.
Sulphate bath decreases the cathode efficiency but gives good surface finish on the other hand,
chloride bath increase cathode efficiency but gives poor surface. So, for having a good result,
sulphate salts and chloride are mixed together to create copper sulphate bath. Therefore, it must
be noticed that some additives are usually added to the copper sulfate bath such as polyethylene
glycol diacrylate and janus green B. This additives tend to change the properties of the copper
finish. Polyethylene glycol diacrylate will tend to give a reddish tint finish to a structure while
janus green B will give a turquoise or black colour. Table 4-1 shows the chemical concentration
for electroplating solution. Between all these chemicals, copper sulphonate (CuSO4) plays the
role of copper carrier during plating.
53 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
4.6 Equipment
Here is the list of equipment used in the electroplating process:
Current Source (Keithley 220 Current Source): Used to provide DC Current and has constant
current (CC). Its resolution is 100mA when it is set in constant current mode.
Hotplate magnetic stirrer: Used to raise the temperature of the solution to the desired value
which is needed for electroplating. A stirrer is used during the electroplating.
Multi-meter: Used to measure current output
SEM: Used to determine the thickness of micro-mould to calculate electroplating time.
[INSERT PICTURE HERE]
Figure 4-2 Set up for experiments
54 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
4.7 Experiment 1
In this experiment, the fabricated mould in chapter 3 was electroplated. In all experiments,
before electroplating, all the moulds were evaporated until they became conductive. The
condition of electroplating is listed in Table 4-3.
Table 4-3 Electroplating parameters
pH 4.0
Temperature 40C
Current 170mA
Duration 2 (hr)
Remark Not all holes were filled
Results and discussion
As can be seen in Figure 4-5, after a period of electroplating, the mould surface will be covered
and it is not possible for plating to continue and fill the mould. The reason for this phenomenon
is that when the current is high, the plating rate is high. So the surfaces which are nearer to the
anode get plated sooner than the other places. As a result, it does not allow time for other places
to be plated, especially the gaps. This issue is one of the main issues of high-aspect-ratio plating.
Solution
The simplest way to overcome this problem is using low current to decrease the rate of
electroplating.
55 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
4.8 Experiment 2- Electroplating (low current)
In this experiment, for overcoming the problem of incomplete filling of the mould, low current
was used. The condition of electroplating is in the Table ... As Table shows, the current and the
duration which were both calculated according to equation from section
Table 4-4 Electroplating parameters
pH 4.5
Temperature 45C
Current 10mA
Duration 24 (hrs)
Remark Excellent Plating
Results and discussion
As can be seen in Figure 4-6, the electroplating was improved, but still needed to be improved
further to decrease the pores inside the micro-structure.
56 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
5.1 Using PDMS
This is another indirect method for removing the plated metallic structure. In this method instead
of using KMPR as a mould for microstructures, PDMS (Polydimethysiloxane) is used. The
whole fabrication process is as follows:
Figure 5-1 Basic SU8 molecule, note the 8 epoxy groups [32]
PDMS elastomer is used most widely in the fabrication of nano-lithography, rapid prototyping
and various microfluidic devices. PDMS has several advantages including:
[94, 95]:
optically transparent
chemically inert
non-toxic
longer life and resistance to chemicals and decomposition
light
Aluminium
master mould by
milling
Aluminium master
mould with
PDMS, cured at
70C, 30 min
Inverted PDMS
master
Evaporation of metal to
make PDMS structure
cond uctive
Replica PDMS master
mould and
aluminium master mould
57 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
non flammable
durable and compatible to microelectronics
can be used in a wide range of temperature from -100C-100C,
high flexibility(the shear modulus is between 100kPa-3MPa)
very low loss tangent (tan <<0.001)
high dielectric strength (~14V/m)
low glass transition temperature (Tg ~ -125C)
can be made fast
Due to PDMSs properties, it has been used as inverse mould for high-aspect-ratio
microstructures [96, 97].
5.2 Advantages of using PDMS technique
Surface
This technique has a good smooth surface result. Metallic microstructure can be released from
PDMS simply, without using any chemical material which means no damage happens for the
surface of microstructure. This is a good advantage for this method in comparison with the other
methods of removing SU-8.
Cost
This method is a cheap and very simple method and the price of PDMS is also cheap. By a SU-8
master mould, easily we can fabricate a lot of PDMS replica in a short time.
Rapid
This is a rapid method for making high-aspect-ratio structures because this method omits most
part of the fabrication process.
Simple removing
Removing PDMS from microstructure is simpler and easier than removing SU-8 from
microstructure.
Non-clean-room process
Using PDMS does not need any cleanroom environment which decreases the need for special
equipment.
58 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
5.3 PDMS problem
Casting PDMS over PDMS is challenging, due to the strong adherence of both layers. De-
moulding is only possible with careful cutting and peeling [1]. A less troublesome, but rather
elaborate, method is the derivatisation of the first PDMS copy by silinisation in order to reduce
adhesive interactions [1]. Thermal aging is widely used in fabrication techniques as it modifies
the hydrophobicity of the PDMS surface [2] and it has been reported that low molecular weight
(LMW) chains are modified so that the surface is able to retain its hydrophilicity [3,4,5].
Two approaches to PDMS double casting have been proposed in this paper. The first method we
investigated was double casting PDMS onto PDMS, and the second method included an extra
step, where the surface of the inverse structure was thermal aged. All techniques are thoroughly
tested by repetitive moulding steps and the quality of the different copies are thoroughly
inspected and applied directly for electroforming [6, 7].
The aim of this technique is to achieve the same results as KMPR photolithography without
using the lithography process while still being cost effective and producing high aspect ratio
microstructures. For the two methods explored, a metal master mould imprinted with the features
was used for the initial mould. This master mould was fabricated by milling an array of holes, 5
mm in depth, into a rectangle aluminium block, 7 mm length, 1 mm in width (Fig. 1). Four extra
pieces of thin aluminium were used as frames for the master mould, where 2 pieces were 70 x 10
mm and 2 were 10 x 10 mm. The frames were attached onto the aluminium block and cleaned
with isopropyl alcohol and deionised water prior to use. Standard PDMS preparation technique
was followed for both methods, where the PDMS (Sylgard 182 Silicone Elastomer Kit, Dow
Corning, USA) was prepared in a 10:1 ratio of base to curing agent. The mixture was then
degassed in a vacuum oven for 15 mins, to remove air-bubbles, and then poured into the
aluminium mould and degassed for a further 10 min. The PDMS filled mould was then cured in
an oven at 70C for 30 min. The solid PDMS structure was then removed from the master mould
producing a structure with inverted features (Fig. 2).
59 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Figure 5-2 Basic SU8 molecule, note the 8 epoxy groups [32]
5.4 Experiment 1 PDMS on PDMS casting
Hypothesis:
By applying the PDMS double casting method we are able to create an inverted PDMS replica of
the PDMS master. The idea would be, to be able to easily remove the PDMS replica from the
master. The inverted structure will be used for electroforming.
Method:
The inverted structure was then fitted with the aluminium frames and more PDMS was poured
on top, degassed and cured for 70C for 30 mins.
Aluminium
master mould
Aluminium master
mould with
PDMS, cured at
70C, 30 min
Inverted PDMS
master
Inverted PDMS master
with PDMS, cured at
70C, 30 min
Thermal aged
inverted PDMS
master
with PDMS,
cured at 70C, 30 min
Inverted PDMS master,
thermal aged at 100C,
24-48 hrs
Replica PDMS master
mould and
aluminium master mould
(a) (b)
60 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Figure 5-3 Unsuccessful result after method 1 fabrication technique was used. PDMS
on PDMS casting failed due to strong bonding (inset: zoomed-in image of pins
encapsulated within the PDMS block)
Result:
In the first method, double casting was conducted onto normal PDMS. This method, although
time efficient, was not a successful attempt as the two structures could not be detached from one
another. The result of this method produced a solid block of PDMS, where the features (pins) of
the inverted mould could be seen inside the block (Fig. 3). The visibility of these features
indicates that the two structures did not merge or melt together, despite the difficulty in
disassembling the two structures. This attachment of the two PDMS structures can be attributed
to strong bonding forces at the interface of the two structures [1].
Discussion and Conclusion:
This bonding affinity may be due to the hydrophobic nature of PDMS surfaces, which has been
linked to the migration of low molecular weight (LMW) chains to the surface [3]. This migration
has been suggested to occur within cured PDMS to recover the hydrophobic surfaces by
covering up thermodynamically unstable hydrophilic surfaces [1]. Thus, if a surface of PDMS
were to remain hydrophilic for extended periods of time, the presence of LMW species needs to
be reduced.
61 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
5.5 Experiment 2 PDMS on PDMS casting Thermal Aging
Hypothesis:
To be able to create an inverted structure for electroforming by double casting PDMS on PDMS
with an added step of thermal aging. The result would be an inverted PDMS replica of the PDMS
master. The idea would be to be able to easily remove the PDMS replica from the master by
utilising thermal aging as the non-chemical release agent which evidently did not appear using
method 1.
Method:
Following the PDMS procedure aforementioned, the inverted structure was cured further
(thermal aged) at 100C for 24-48 hrs. The hardened structure was then fitted with the
aluminium frames and more PDMS was poured into the frames. The structure was then degassed
for 10 min and then cured at 70C for 30 min. The thermal aging process was repeated two
further times at 90 and 110C.
Result:
Thermal aging is a common technique that is used to modify the surfaces of PDMS structures.
This technique exposes the PDMS to high temperatures for prolonged periods of time. Thermal
aging causes gradual crosslinking of LMW chains and affects the rate of migration of the LMW
species, extending hydrophobic surface recovery from minutes to days. Eddington et al. has
shown that by varying the aging time (from 48 hours to 14 days), it is possible to eliminate the
hydrophobic surface recovery completely. While K. Zikowska et al. has proven that the
optimal temperature was between 90C and 120C. Therefore, the rate of hydrophobic recovery
is dependent on aging times, temperatures and volume. This extra step of thermal aging proved
valuable in our second method as detaching the two PDMS structures was successful. The two
PDMS structures were separated without difficulties and replicated the master mould seamlessly,
i.e. the pins from the inverted/thermal aged structure did not break (fig. 4). The thermal aged
structure was also abled to be used multiple times to create replica moulds with high
reproducibility and without the need for further thermal aging. Different exposure times were
applied in the range of 120C, 100C and 90C.
62 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Discussion and Conclusion:
Thermally aged masters, baked for 24-48 h, were used for replication. It was observed that 24 h
thermal aging was sufficient and provided over 95% replication accuracy; while 48 h did not
significantly improve the results. Therefore 24 h thermal aging was established as the optimal
time for PDMS double casting technique.
Figure 5-4 Successful result after method 2 fabrication technique was used. The
PDMS master was successfully inverted after the thermal aging step was added.
63 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
5.6 Experiment 3 Electroplating PDMS with seed layer 20nm
Chromium and 50 nm Nickel
Hypothesis:
By conducting copper electroplating on the PDMS double casting thermal aged sample method,
which has a seed layer (20nm Chromium and 50nm Nickel) we are able to create an inverted
metallic replica of the PDMS master. The idea would be, to be able to easily remove the PDMS
replica from the master.
Method:
The PDMS master became the anode and the copper substrate became the cathode.
The following electroplating parameters were used:
Result:
Substrate not conductive [Figure ..].
Figure 5-5 Basic SU8 molecule, note the 8 epoxy groups [32]
64 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Conclusion and Discussion
The result was a nonconductive substrate and this was due to the strong nickel oxide present on
the surface. A way to remove the oxide layer is to use an etchant, however, the result did not
produce a conductive substrate.
Figure 5-6 Basic SU8 molecule, note the 8 epoxy groups [32]
5.7 Experiment 4- Electroplating PDMS with seed layer 20nm
Chromium and 250 nm Gold
Hypothesis:
By conducting copper electroplating on the PDMS double casting thermal aged sample method,
which has a seed layer (20nm Chromium and 250nm Nickel) we are able to create an inverted
metallic replica of the PDMS master. The idea would be, to be able to easily remove the PDMS
replica from the master.
Method:
The PDMS master became the anode and the copper substrate became the cathode. The
following electroplating parameters were used:
65 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Figure 5-7 Basic SU8 molecule, note the 8 epoxy groups [32]
Result:
Figure . shows a layer of copper on top of the PDMS substrate which indicates that the
parameters used from the method were correct and that the substrate was conductive [Figure
.]. This was because gold unlike nickel does not contain an oxide layer on its surface which
meant that using chemicals to remove the oxide layer would not be necessary and would not
affect the results.
Figure 5-8 Basic SU8 molecule, note the 8 epoxy groups [32]
Discussion and Conclusion:
A seed layer of 20 nm chromium and 250 nm gold was evaporated onto the PDMS substrate.
This substrate was then used for copper electroplating. It was observed that the substrate was
66 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
conductive and it was found that it could be plated into and a result could be obtained. Therefore,
the seed layer of 20 nm chromium and 250 nm gold on a thermally aged PDMS substrate is
optimal to be plated into.
Figure 5-9 Basic SU8 molecule, note the 8 epoxy groups [32]
5.8 Experiment 5 Removing PDMS from metallic structure
Hypothesis
To easily peel off the hardened epoxy resin from the PDMS surface and produce an epoxy mould
with the metal over it.
Method
3M Scotch-Weld Epoxy Adhesive 2216 B/A Gray was used in the experiment because of its two
part room temperature curing with high peel strength and shear strength. The key characteristics
provided by the manufacturer are shown below:
67 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
The manufactures data sheet instructions were followed point to point. It specified that:
The metallic surface needed to be clean. This was done by using acetone and
Isopropanol.
Mix both the base and accelerator with a weight proportion ratio of 5 to 7.
Pour the epoxy adhesive over the metallic surface and cure at room temperature for 24
hours.
Peel off the epoxy adhesive mould.
Note: All tests procedures were followed in the clean room.
Result
The epoxy resin was poured on top of the PDMS structure and left to cure at room temperature
for 20 hours as specified by the data sheet. The result after curing show that the epoxy resin
adhered to the PDMS mould, firmly (Figure 2222).
Table 1. 3M Scotch-Weld Epoxy Adhesive 2216 B/A Gray key characteristics.
68 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Tape was used around the PDMS structure to hold the epoxy resin. This is shown below:
After peeling off the PDMS, the result is shown below:
Figure 1. Result after curing for 20 hours.
Figure 2. Result after curing for 20 hours.
Figure 2. Result after peeling off PDMS.
69 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
Discussion and Conclusion
The desired outcome was to easily peel off the hardened epoxy resin from the PDMS surface
and produce an epoxy mould with the metal over it however this was far from the case. It was
incredibly hard to peel off the PDMS and it is not possible to remove the excess PDMS from the
holes. However, the epoxy adhesive did successfully remove the metal from the PDMS surface
and this was shown in figure 3.
A solution to fix the peeling problem may be to heat the PDMS/Epoxy moulds before removal.
This may thermally expand the PDMS and we may see a better peeling result. A solution to
producing better results may also be to cure the epoxy resin at higher temperatures as specified
by the manufactures data sheet:
However this remains to be tested.
70 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
6 Conclusions and future work
6.1 Conclusions
In this project, a suitably developed KMPR mould by the top side exposure method, followed by
an electroplating process, and a sacrificial method, high-aspect-ratio metallic microstructures
have been fabricated. The parameters of mould fabrication are studied by which a set of
optimized parameters are identified to produce a KMPR mould without any cracks, delamination
and KMPR residue. We need to increase soft-baking time and temperature, post exposure baking
time and temperature and to have relaxation time after soft-baking and before development.
The next step after mould fabrication is to suitably electroplate it. It is found that the only way to
electroplate KMPR mould completely without any pores inside the structure is to use low current
by controlling electroplating parameters such as pH, temperature, agitation and bath
composition. KMPR resist was easily removed from the electroplated metallic structure by using
MicroChems Remover PG (NMP).
Lastly, an alternative in direct method of forming a structure, electroplated plating into the
structure and separating the metal from the structure easily, was studied. PDMS double casting
technique. This process has several advantages and disadvantages as follows:
PDMS on PDMS double casting technique:
This technique has been worked on by researchers, but needs to be studied further. It has several
advantages such as: Fabrication process is simple, rapid prototyping, no lithography technique
required, cost effective, and thickness can be controlled. A few problems with this technique
remain: Cannot simply cast PDMS on PDMS due to cross-linking and sufficient time and effort
is needed in order to produce an inverted structure with high aspect ratio dimensions.
PDMS on PDMS double casting with thermal aging technique:
This technique has also been worked on by researchers. It has same advantages as PDMS on
PDMS double casting. A problem with this technique remains: Thermal aging of at least 24 h is
needed in order to produce an inverted PDMS structure. Another inherit problem is that when the
mould is plated into, it is not able to be easily separated from the metal.
71 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
6.2 Recommendations for future work
There are several aspects in this project that can be investigated in the future:
In mould fabrication, we just spin-coat one layer of KMPR and able to achieve a maximum of
150m thickness KMPR mould. But there is potential to have thicker mould, the suggestion for a
method to have a thicker mould by spin coating KMPR after each electroplating process can be
achieved.
In mould fabrication, we created a structural dimension of 30m. There is potential to increase
and decrease this amount to produce a high aspect ratio greater than 1.
The evaporation of gold onto the silicon substrate produces a conductive substrate but does not
provide a reliable option when trying to remove KMPR photoresist from the silicon substrate
with the gold evaporated on it. An alternative seed layer such as titanium could be investigated to
provide the same conductive layer as gold.
In the part of fabricating structure by PDMS technique and electroplating into the mould, it
was found that removing the metal from the PDMS was not easy. Parameters to improve this
technique could be studied further to that the process is smooth.
72 Kashka Irani - Fabrication of High-Aspect-Ratio Metallic Micro-structures Using Photolithography
References