PRODUCT ATTRIBUTES

MCC NANO PMMA and Copolymer

Submicron linewidth control PMMA (polymethyl methacrylate) is a versatile polymeric material that is well suited
Sub 0.1m imaging for many imaging and non-imaging microelectronic applications. PMMA is most
commonly used as a high resolution positive resist for direct write e-beam as well as
E-beam, X-ray & deep UV imaging
x-ray and deep UV microlithographic processes. PMMA is also used as a protective
Broad range of molecular weights & dilutions coating for wafer thinning, as a bonding adhesive and as a sacrificial layer.

Excellent adhesion to most substrates

Standard PMMA products cover a wide range of film thicknesses and are formulated
Compatible with multi-layer processes with 495,000 & 950,000 molecular weight (MW) resins in either chlorobenzene or
the safer solvent anisole. Custom MW products ranging from 50,000 - 2.2 million are
available upon request. In addition, we offer copolymer (MMA (8.5) MAA) products
formulated in the safer solvent ethyl lactate. All MCC PMMA and copolymer resists
APPLICATIONS are available in package sizes from 500ml to 20 liters.

Multi-layer T-gate processing courtesy M/A Com

Direct write e-beam lithography

Protective coatings for wafer thinning

Adhesive for X-ray LIGA processing

Sacricial layers

100nm gate profile imaged in 495K PMMA with 8.5 MAA Copolymer on top.

courtesy M/A Com

T-gate resulting from PMMA/Copolymer bilayer resist stack.

PROCESSING GUIDELINES

Substrate Preparation Typical process flow for bi-layer T-gate process

The substrate should be clean and dry. Solvent, O2 plasma, and O3 1. 2.
Spin Coat
cleans are commonly used and recommended. Prebake
Bottom Layer
PMMA
PMMA Resist
Coat
MicroChem PMMA resists produce low defect coatings over a broad
range of lm thicknesses. The lm thickness vs. spin-speed curves
displayed in Fig. 1 through 8 provide the information required to
select the appropriate PMMA dilution and spin speed needed to 3. 4.

achieve the desired lm thickness. Spin Coat

Remove Resist
Top Layer
Edge Bead
Copolymer Resist
The recommended coating conditions are:
(1) Dispense: STATIC 5 - 8ml for a 150mm wafer
(2) Spread: DYNAMIC 500 rpm for 5 sec OR
STATIC 0 rpm for 10 sec
(3) Spin: Ramp to final spin speed at a high acceleration 5. 6.

rate and hold for a total of 45 seconds. Expose and

Prebake
Develop
Copolymer
Resist Stack
Pre Bake
PMMA
Hot plate: 180oC for 60 - 90 sec OR
Convection Oven: 170oC for 30 min
7. 8.

Gate Etch and Strip/Remove

Copolymer
Deposition Resist Stack
Hot plate: 150oC for 60 - 90 sec OR
Convection Oven: 140oC for 30 min
*Vacuum oven bake can also be used
Expose Table 2 outlines helpful guidelines for a develop process.
PMMA can be exposed with various parts of the electromagnetic
spectrum. TYPICAL DEVELOPMENT PROCESS
ACTION SPRAY** SPRAY PUDDLE IMMERSION (21OC)
e-beam: Dose - 50 - 500 C/cm 2 depending on radiation
source/equipment & developer used. Dispense 500 rpm for 30-45 secs 500 rpm for 3-4 secs
Dispense 0 rpm for 2 secs
Energy 20-50kV; higher kV for higher resolution, e.g. 50kV for No Dispense 0 rpm for 25-40 secs 30 secs
0.1mm images. Rinse * 500 rpm for 30-45 secs 500 rpm for 3-4 secs 30 secs
Dry 500 rpm for 30 secs 5000 rpm for 30 secs Nitrogen blow dry
DUV(deep UV): Low sensitivity, requiring doses >500mJ/cm 2
* Recommended Rinse solution is MIBK to IPA 1:3 in order to reduce the possibility of scumming
at 248nm. ** Variables such as developer pressure, nozzle type & position, spray pattern, etc. should be optimized

X-ray: Sensitivity of PMMA is low, ~1-2 J/cm2 at 8.3. The

Table 2
sensitivity increases at longer x-ray wavelengths. Features of
<0.02m can be fabricated.
Postbake/Hardbake (optional)
To remove residual developer, rinse solvent, and moisture from the
Develop
resist image.
PMMA and copolymer resists are compatible with immersion
Hot Plate OR 100oC for 60 - 90 sec
(21oC), spray puddle, and spray process modes. Process variables
Convection Oven 95oC for 30 min
such as soft bake, exposure conditions, choice of resist
and developer should be optimized to achieve desired results.
Note: PMMA images will round/ow above 125oC.
For more process details see the PMMA and Copolymer DEVELOPER
data sheet. Table 1 lists commonly used developers and their
Remove
recommended usage.
Wet: Remover PG or ACRYL STRIP
Bath: time as required, ambient
NANOTM PMMA AND COPOLYMER DEVELOPERS ARE Spray: time as required, 500 - 1000 rpm
AVAILABLE IN THE FOLLOWING BLENDS
Dry: plasma O2
PRODUCT COMPOSITION RESOLUTION SENSITIVITY /
THROUGHPUT
PMMA and copolymer resists can be removed by using MCC's
M/I 1:1 1:1 MIBK to IPA high high Remover PG or standard cleanroom solvents, such as acetone,
M/I 1:2 1:2 MIBK to IPA higher medium photoresist thinner, or positive photoresist removers.
M/I 1:3 1:3 MIBK to IPA very high low
MIBK MIBK low high Resists that have seen higher processing temperatures and/or
hostile processes that have toughened the polymer will require
ACRYL STRIP or a more aggressive removal process. This can
Table 1
include Remover PG at elevated temperature followed by cleaner
baths to assure adequate material removal.
Rinse and Dry
To terminate the develop process and prevent scumming, PMMA See appropriate product data sheet for specic process recom-
and copolymer should be immersed or sprayed with 1:3 or 1:4 mendations and safety precautions.
MIBK:IPA, alcohol or DI water immediately following develop.
Substrates are normally spin dried at 3000rpm for 20 seconds or For additional questions or technical assistance please contact
N2 blow dried. Technical Services.
 SPIN SPEED CURVES FOR PMMA AND COPOLYMER RESISTS

The spin speed versus lm thickness curves displayed in gures 1-11 provide approximate information required to select the appropriate PMMA or
copolymer resist and spin conditions needed to obtain the desired lm thickness. Actual results will vary and are equipment, environment, process and
application specic. Additional resist dilutions to obtain other lm thicknesses are available upon request.

495PMMA C Resists 495PMMA A Resists

Solids: 2% - 6% in Chlorobenzene Solids: 2% - 6% in Anisole

10000 7000
9000
6000
8000

Film Thickness ()
Film Thickness ()

7000 5000
6000 C6
4000
5000 A6
4000 3000
3000 C4 2000
A4
2000
C2 1000
1000 A2
0 0
500 1000 1500 2000 2500 3000 3500 4000 4500 500 1000 1500 2000 2500 3000 3500 4000 4500
Spin Speed (rpm) Spin Speed (rpm)

Figure 1 Figure 3

495PMMA C Resists 495PMMA A Resists

Solids: 8% - 9% in Chlorobenzene Solids: 8% - 11% in Anisole

25000
23000
21000 20000
Film Thickness ()
Film Thickness ()

19000
17000 15000
15000
13000 C9 10000
A11
11000
9000 5000
A8
C8
7000
5000 0
500 1000 1500 2000 2500 3000 3500 4000 4500 500 1000 1500 2000 2500 3000 3500 4000 4500
Spin Speed (rpm) Spin Speed (rpm)

Figure 2 Figure 4

Copolymer Resists
Solids: 6% - 11% in Ethyl Lactate

12000

10000
Film Thickness, ()

8000

6000
EL 11
4000
EL 9
2000
EL 6
0
500 1000 1500 2000 2500 3000 3500 4000 4500
Spin Speed (rpm)

Figure 9
 Bi-Layer Process

PMMA PMMA
PMMA resists for T-gate and other imaging processes GaAs GaAs

PMMA is a high resolution positive tone resist for e-beam, deep UV 1. Coat and bake PMMA 4. Develop PMMA and Copolymer

(200-250nm) and X-ray lithographic processes. Although PMMA may

be used in a single layer resist process, it is most commonly used in Copolymer
PMMA
multi-layer processes such as in the fabrication of mushroom or GaAs GaAs

T-gates. Images are formed through the photo scission of the 2. Coat and bake copolymer 5. Deposition

polymer backbone and subsequent development process, which e-beam

>>
removes the exposed, lower molecular weight resist. Multi-layer,
PMMA
shaped resist proles are realized and inuenced through the careful GaAs GaAs

choice of PMMA molecular weight, lm thickness and other process 3. Expose resist stack, center scan dose, 6. Strip resist stack
then side scan dose
set points.

Tri-Layer Process

PMMA
Copolymer
In a typical bi-layer process, a combination of bottom and top layer PMMA PMMA
GaAs GaAs
resists are selected such that a large difference in dissolution rates
1. Coat and bake high MW PMMA 5. Develop tri-layer stack
of the layers at the developer step exists, leading to the desired
resist sidewall prole. This contrast may be further inuenced with a
PMMA
Copolymer Copolymer
variety of process strategies. Generally, dissolution rate increases as PMMA PMMA

GaAs GaAs
molecular weight decreases. However, soft bake conditions, which
2. Coat and bake copolymer 6. Deposition
affect residual solvent level and subsequent development rates will
inuence the bi-layer resist prole as will the exposure conditions.
PMMA
Copolymer
PMMA

GaAs GaAs
Please refer to our web site, www.microchem.com for applications
3. Coat and bake low MW PMMA 7. Strip resist stack
notes concerning non-imaging PMMA processes such as wafer
e-beam
>>

thinning, bonding and sacricial layers. PMMA

Copolymer
PMMA

GaAs

4. Expose resist stack, center scan dose,

then side scan dose
OTHER RESIST AND ANCILLORY PRODUCTS FROM MICROCHEM

PMGI and LOR for lift-off processing

SU-8 resists for MEMS and ultra thick resist processing
Remover PG resist stripper
EBR PG edge bead remover
Acryl Strip resist stripper for PMMA

NOTES
 HANDLING NANO PMMA
& COPOLYMER SERIES RESISTS (in Anisole or Chlorobenzene)
Use precautions in handling ammable PMMA solutions. Avoid contact with eyes,
skin, and clothing. Use with adequate ventilation. Avoid breathing fumes. Wear
chemical-resistant eye protection, chemical gloves (PVA for chlorobenzene
solutions) and protective clothing when handling NANO PMMA & Copolymer Series
Resist products. NANO PMMA & Copolymer Series Resists cause irritation in case
of contact with eyes, skin, and mucous membranes. In case of eye contact, ush
with water for 15 minutes and call a physician immediately. Review the current
MSDS (Material Safety Data Sheet) before using.

MATERIAL AND EQUIPMENT COMPATIBILITY

NANO PMMA & Copolymer Resists are compatible with glass, ceramic, unfilled
polyethylene, high-density polyethylene, polytetrauoroethylene, stainless steel, and
equivalent materials.

Chlorobenzene is a powerful solvent and will attack various elastomers such

as BUNA N, EPDM, HYPALON, and NEOPRENE. It will also attack PVC, CPVC and
polyester. VITON A is recommended for both O-rings and tubing.

PROCESSING ENVIRONMENT
For optimum results, use NANO PMMA & Copolymer Series Resists in a
controlled environment. 20 - 25o 1oC (68 - 77oF) is suggested.

STORAGE
Store upright in original containers in a dry area 50 - 80oF (10 - 27oC). Do not
refrigerate. Keepaway from sources of ignition, light, heat, oxidants, acids, and
reducers. Shelf life is 13 months from date of manufacture.

DISPOSAL
Each locality, state, and county has unique regulations regarding the disposal
of organic solvents such as NANO PMMA Series Resists. It is the responsibility of
the customer to dispose of NANO PMMA Series Resists in compliance with all
applicable codes and regulations. See MSDS for additional information.

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P HONE : 617.965.5511
The information regarding these products is based on our testing to date, which we believe to
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expressed or implied, regarding the information, use, handling, storage, or possession of these
E MAIL : [email protected] products, or the application of any process described herein or the results desired, since the use
and handling of these products are beyond our control.
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