DuPont Pyrralin T9035 Thinner
/
ridyid KMeinfelcl.Room 6H-.424 ' '
ATT B e l l Laboratgri^;5i
600 Mountain Ayerilue '..
^Murray, H i l l , , N'» J»!. G7974 •
POLYIMIDE COATINGS FOR ELECTRONICS
Bulletin #PC-6 Rev. 4/82
T-9035 THINfNER
T-9035 is a highly purified thinner, filtered through
a 0.2 ju, absolute filter and controlled to less than 1
ppm sodium. It is designed to provide excellent
processing properties without unusual handling
problems.
processing advantages are:
• Thin Films 1500A - Pinhole free
• Minimizes edge crawlback
• Excellent surface wetting
• Good shelf stability even with high dilution ratios
• Compatible for use with all PYRALIN* polyamic
acid solutions.
TYPICAL USE
T-9035 thinner is used to reduce viscosity and solids
jontent of PYRALIN solutions to obtain desired
film thickness. Forexample, diluting 1 part PI-2555
with 2 parts T-9035 yields 1500A films on a
3" silicon wafer spun at 5000 rpm.
The thinned solution should be allowed to age 12
hours at 70°F before use. This time is needed for the
solution to reach equilibrium conditions. T-9035
does not need to be stored in a refrigerator, but
mixed solutions should be stored in a refrigerator
after the initial 12 hour aging period.
T-9035 is hygroscopic so it is critical that mixed
solutions be brought to room temperature before
'pening container to avoid moisture condensation.
.«ioisture can attack and degrade the polyamic acid
polymer in the PYRALIN formulations.
TOXICITY/HEALTH HAZARDS
Adequate ventilation must be provided and skin
contact should be avoided. Exposed areas should be
flushed with water immediately.
Rubber gloves resistant to the solvents in PYRALIN
olyimide Coatings can be procured as follows: for
Du Ponrs liability is expressly limited by Du Font's corxJitions of sale shown on Seller's price list or
Buyer's copy Ot Seller's order acknowledgment form (if used) and Seller's invoice. All tectinical advice,
recomrnendations and services are rerxJered by the Seller free of charge. While based on data
• D n P n n t Tpa«4o
general-purpose use, the "Buta-Sol" milled butyl
rubber glove (Norton Company, Safety Products
Division, P.O. Box 4367, Charleston, SC 29405); for
light service, the "Wil-Gard" No. 26-640 tan latex
industrial glove (Edmont-Wilson Division, Becton
Dickinson and Company, 1300 Walnut Street,
Coshocton, OH 43812); and for service requiring
greater resistance to wear, the Natural Latex Rubber
glove No. 2911 (B.F. Goodrich Engineered Systems,
500 S. Main Street, Akron, OH 44318).
Data supplied by the General Aniline and Film
Corporation indicate that animals exposed to air
saturated with N-methyl-2-pyrrolidone for six hours
daily for ten days tolerated the conditions of the
experiment and gained weight normally. Other
animals subjected to 20-day dermal toxicity studies
had no specific degenerative changes and did not
have a remarkable degree of skin irritation.
Note that this material also contains 2-ethoxyethanol (cellosolve).
AVAILABILITY
Available in one-half kilo, one-kilo or four-kilo
containers from:
Du Pont Company
F&F Department
85 Mill Plain Road
Fairfield, Connecticut 06430
Attn: B.T. (Brian) Lynch.
Phone: (203) 259-3351, Ext. 247.
For additional technical information, call:
V.S. (Vic) Bowers
(302) 774-0259,
Telex #83-5420
Cable address: FABFINISHES
believed to be retiatMe, ttiey are intended for use by skiired persons at ttieir own risk.Seller assumes no
responsibility to Buyer tor events resulting or damages incurred from their use. They are notto t>etaken
as a license to operate under or intended to suggest infrir>gement of any existing patent.
Print«riin tift &
POLYIMIDE COATINGS FOR ELECTRONICS
\
B u l l e t i n #PC-23
(E-52138)
4/82
PRODUCT SPECIFICATION
T - 9 0 3 5 THINNER
T-9035
TEST
Density
(25'C)
0.97 + 0.1
Solvent
System
NMP/Cellosolve
5 0 / 5 0 + 3%
Du P o n t TM I I D
4 . 0 ppm max,
Du P o n t TM I I C
Sodium C o n t e n t *
0 . 5 ppm max,
Du P o n t TM I I B
Potassium
0.3
Chloride
Copper
Iron
Content*
Content*
Content*
Content*
Filtration
*Based on t o t a l
g/cc
TEST METHOD
Du P o n t TM I I G
"
0.05 "
0.03 "
"
0.2 micron
abs.
sample.
Du Ponfs liability is expressly limited by Du Font's conditions of sale shown on Seller's price list or
Buyer's copy of Seller's order acknowledgment form (i(used) and Seller's invoice. All technicaladvlce,
recommendations and services are rendered by the Seller tree of charge. While based on data
believed to be reliable, they are intended tor use by skilled persons at their own risk. Seller assurrws no
responsibilitytoBuyerfor events resulting or damages incurredfrom their use. They arenottobetaken
as a license to operate under or intended to suggest infringement of any existing patent.
Printed In U.S7\.
nfeld
Room oH '^'=L- a b o r a t o r i e s
ftTT B e l l
ftvenue
600 Mountain
Hiii»
POLYIMIDE COATINGS FOR E L E C k . . ^ : ' . u r ^
Bulletin #PC-15 Rev. 4/82
CLEAN-UP PROCEDURE FOR
PYRALIN* FORMULATIONS
Polyamic acid may pose clean-up problems primarily
because it is not soluble in most common organic
solvents. The recommended solvent for clean-up is
NMP (N-methyl-2-pyrrolidone). NMP can be used
to clean up metal screens, metal catch basins and
glassware without harm to those items. It is recommended that after cleaning with NMP, a mixture of
50/50 NMP/acetone (or isopropyl alcohol) be used
to clean and dry the items.
NOTE: When using glassware with PYRALIN, simply place the glass item to be cleaned under running
tap water untU a milky white film develops. At this
point, pour off the water and lift out the conforming
film and deposit in a wastebasket. Caution: This
will not work with metal containers.
PYRALIN polyamic acid can be disposed of by
incineration. If the waste PYRALIN is mixed with
photoresist, as in a spinning operation using the same
spinner, the waste can be disposed of in like maimer.
It is not advisable to bury the waste because of the
possibility of solvent leakage into groundwater.
Glass, polyethylene, polypropylene and stainless
steel are suitable container materials when NMP
solvents are involved.
TOXICITY/HEALTH HAZARDS
Adequate ventilation must be provided and skin
contact should be avoided. Exposed areas should be
flushed with water immediately.
Du Font's liability is expressly limited by Du Font's conditions of sale shown on Seller's price list or
Buyer's copy of Seller's order acknowledgment form (itused)and Seller's invoice. All technical advice,
recommendations and services are rendered by the Seller free of charge. While based on data
Rubber gloves resistant to the solvents in PYRALIN
Polyimide Coatings can be procured as follows: for
general-purpose use, the "Buta-Sol" milled butyl
rubber glove (Norton Company, Safety Products
Division, P.O. Box4367, Charleston, SC 29405]; for
light service, the "Wil-Gard" No. 26-640 tan latex
industrial glove (Edmont-Wilson Division, Becton
Dickinson and Company, 1300 Walnut Street,
Coshocton, OH 43812); and for service requiring
greater resistance to wear, the Natural Latex Rubber
glove No. 2911 (B.F. Goodrich Engineered Systems,
500 S. Main Street. Akron, OH 44318).
Data supplied by the General Aniline and Film
Corporation indicate that animals exposed to air
saturated with N-methyl-2-pyrrolidone for six hours
daily for ten days tolerated the conditions of the
experiment and gained weight normally. Other
animals subjected to 20-day dermal toxicity studies
had no specific degenerative changes and did not
have a remarkable degree of skin irritation.
NMP can be obtained from local chemical supply
houses or in larger quantities from GAF Corp.,
Dyestuff & Chemical Division, 140 West 51 Street,
New York, NY 10080.
believed to be reliable, tt>ey are intended for use by skilled persons at their ownrisk.Sellerassumes no
responsibility to Buyer for events resulting or damages incuned from their use. They are notto be taken
as a license to operate under or intended to suggest Infringement of any existing patent.
P r i n t a r i in II Q A
•
DuPont
E. I. du Pont de Nemours & Co. (Inc.)
Pnotosystenns & Electronic Products Department
Electronic l\^atehals Division
Barley Mill Plaza, Reynolds Mill Building
Wilmington, DE 19898
Tel: 1-800-441-7543
TWX: 835420
Dear C u s t o m e r :
As r e q u e s t e d , enclosed are copies o f Material
Data Sheets for specific p r o d u c t s .
Safety
If you have any q u e s t i o n s , please call on 8 0 0 - 4 4 1 - 7 5 4 3 ,
Very truly y o u r s .
^y^'
Jc/oi^^k^y
L. M. Schafer
LMSiivd
E n d osure
DQvid K l e i n f e l d
Room 6H-424
ATTv.Hell Laboratorn.e<:i
600 Mountain ^ J ' ^ ; ' ' ' ' ' ^
Murray H i l l V N.J» 0 7 P . ^
VL
,
S A F E T Y
^
S ME E T
' TO OSHA-20)
04/23/82
PI
2555
SECTION I *****
.u)E NAVE/SYNO.VYMS
W.A.
*»A.\ JF . A : T J S = ^
e . I . i.;«J^P:.)NT C£ NEM')J-iS A C O . , INQ
F K f J £ r .K^Zf'.zUT
WILMINGTON, DE 1 9 8 9 3
T£LEPHf;.*»H
( 3 0 2 ) 774 2 4 2 1
L..CMICAL FAMILY
FORMJLA
BROMN
POLYIMIDE RESIN
PI
2553
601024
***** SECTION I I - HAZARDOUS INGREDIENTS *****
SOLVENT
APPROX irr X
TLV <PP«)
AROMATIC PET i)IST
16
JOG
METHYL PYRROLIDONE
65
25
***** SECTION I I I - PHYSICAL DATA • * * * * ,
APPROX BOILING RANGE ( F )
302-395
V/.^'OR PRESSURE PRINCIPAL SOLVENT (MM HG)
<1.0
VAPOR DENSI-n i>RINCIPAL SOLVENT ( A I R - 1 )
3.40
SOLUBILITY I N ^ A T E R
Miscible
APPEARA.^CE AND OU)R
SEMI-VISCOJS LIQUID dITH CHARACTERISTIC DOOR
SPECIFIC GRAVITY (MATER>J)
1.049
i>ERC£NT VOLATILE BY VOLUME
65.86
:
POR ATI ON AATE
SLOWER THAN ETHER
***** SECTION IV • F I R E & EXPLOSION HAZARD DATA *****
FLASH POINT (METHOD)
APPROX FLAMMABLE LI»>ITS
BETWEEN I O O - J 4 0 F fCC)
r-TlNGUISHINC MEDIA
FOAM, CARBON DIOXIDE, ORY CHEKICAL
SPECIAL FIRE FIGHTING PROCEDURES
MATER FROM FOG NOZZLES MAY BE USED TO COOL
CLOSED CONTAINERS TO PREVENT PRESSURE B U I L D - U P .
LEL
J.IO
• UEL
7.00
M A T E R I A L
S A F E T Y
D A T A S H E E T
(SIMILAR TO aSHA-20)
04/23/82
PI
2555
PRfJTECTIVE GLOVES
PROLONGED UR REPEATED CONTACT
EYE PROTECTION
USE SAFETY EYE#»EAR
I. ,E? PROTECTIVE t^'JIPMENT
USE APPROP^I.i.TE INDUSTRIAL HYGIENE PRACTICES
* « « « * SECTION IX - SPEC,IAL PRECAUTIONS * • • • *
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING
KEEP AMAY FROM HEAT, SPARKS AND OPEN FLA'AE.
CLOSE CONTAINER AFTE.? EACH USE. DO NOT STORE ABOVE 120 F .
0*dER P.RECAJTJONS
MASH THOROUGHLY AFTER HANDLING AND BEFORE EATING OR SMOKING
OBSERVE LABEL PRECAUTIONS. CONTAINERS SHOULD BE GROUNDED MHBW POURING.
NOTICE FROM DUPONT
THESE DATA RELATE ONLY TO THE SPECIFIC.KATERIAL DESIGNATED HEREIN A.'4D
DO NDT RELATE TO USE IN COMBINATION MITH ANY OTHER MATERIAL
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Room .:6H:7424^^.^^;^^'^ :; , .;,
•ATT'.Bell' Laboratories
600 Mountain Avenue
Hurray? Hill V N>J. 07974.
-
PHOTODEFINEABLE P0LYI.1IDES:
CHE^IISTRY AND PROCESSING
R. S . BENTSON AND J , I.. MARKHAM
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APPLICATIONS FOR POLYI.^IDES
PROPERTIES OF POLYIW.IDES
POLYIMIDE CHEfllSTRY
POLYIMIDE PROCESSING
r
m
APPLICATIONS OF POLYIMIDES
cx PARTICLE PROTECTION
PASSIVATION
MECHANICAL PROTECTION
MOISTURE BARRIER
INTERLAYER DIELECTRIC
DIE BONDING
PLANARIZATION
7
PROPERTIES OF POLYIMIDES
FILM FORMATION
HIGH TG
HIGH THERMAL STABILITY (^OO^C)
LOW DIELECTRIC CONSTANT (3.5)
GOOD CHEMICAL RESISTANCE
PURITY
RELIABILITY
r
THREE TYPES OF POLYIMIDES
ADDITION POLYIMIDES
CONDENSATION POLYIMIDES
PRE-IMIDIZED POLYIMIDES
BISMALEIMIDE
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POLYAMIC ACID
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POLYIMIDE
CIBA-GEIGY
POLYIMIDE XU 218
CONVENTIONAL POLYIMIDE PROCESSING
SPIN ON POLYIM DE PRECURSOR
t
DRY
CURE (TO DEGREE MATCHING SUBSEQUENT PROCESSING)
APPLY NEGATIVE PHOTORESIST
1
APPLY POSITIVE PHOTORESIST
EXPOSE
EXPOSE
DEVELOP
DEVELOP PHOTORESIST AND
ETCH POLYIMIDE
WET ETCH
POLYIMIDE
DRY ETCH
POLYIMIDE
STRIP
PHOTORESIST
STRIP
PHOTORESIST
FINAL CURE
OF POLYIMIDE
FINAL CURE
GF POLYIMIDE
i
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STRIP
PHOTORESIST
I
FINAL CURE
OF POLYIMIDE
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CONVENTIONAL POLYIMIDE
PATTERNING
COAT ANO ORr
POLYIMIDE
PRECURSOR
I
PHOTOSENSITIVE POLYIMIDE
PATTERNING
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rwi rzu
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METAL ON
SUBSTRATE
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CURE TO GIVE
POLYIMIDE
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COAT NEGATIVE
PHOTORESIST
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ED
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UV EXPOSE
PHOTORESIST
DEVELOP
PHOTORESIST
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sa.
METAL ON
SUBSTRATE
JE3.
COAT AND DRY
POLYIMIDE
PRECURSOR
L-L-l—L
UV EXPOSE
PRECURSOR
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ETCH
POLYIMIDE
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STRIP
PHOTORESIST
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DEVELOP
PRECURSOR
yZl
CURE PRECURSOR
TO GIVE
POLYIMIDE
PHOTOSENSITIVE POLYIMIDE PROCESS SEQUENCE
ADHESION PROMOTER
COAT POLYIMIDE PRECURSOR
PREBAKE TO REMOVE SOLVENTS
UV EXPOSURE
DEVELOPMENT
CURE
COMPARISON OF PHOTOSENSITIVE POLYIMIDES
MATERIAL
HITACHI
PL-1000
SENSITIZER
AZIDE ( N T )
EM
SELECTILUX
HTR-2
DUPONT
PIH 71710
TORAY
PHOTONEECE
UR 31^10
ADHESION
PROMOTER
ALUMINUM
OXIDE
SOLVENT
NMP
DEVELOPER
NMP
ACRYLATE &
INITIATOR
NMP/
CYCLOPENTANONE
1:1
CYCLOPENTANONE
ISOPROPANOL
ACRYLATE &
INITIATOR
NMP/
CELLOSOLVE
BUTYROLACTONE/ AMINO
TOLUENE 1:1
SILANE
NMP/METHYL
CELLOSOLVE
DV-500
^
VINYL
SILANE
AMINO OR
EPOXY
SILANE
ADHESION PROMOTERS
EM CHEMICALS SELECTILUX HTR-2:
VINYL SILANE; SPIN COAT; AIR BAKE 3 130^0 FOR 15 MIN.
DUPONT PIH 71710:
AMINO SILANE; SPIN COAT
HITACHI PL 1000
ALUMINUM CHELATE; SPIN COAT; AIR BAKE a 350% FOR 30 MIN.
STORE UNDER N2
DELIVERY TO SUBSTRATE THROUGH FILTER UNDER LOW PRESSURE
N2
PL 1000: SPIN SPEED vs THICKNESS
0
8
-
7
-
0
0
el-Thickness
(/vm)
0
5 -4
uncured
0
0
-
o
3
o
2 --
1 1
1000
1500
1
1
1
1
1
2000
2500
3000
3500
4000
Spin Speed (RPM)
SUBSTRATE COATING
THICKNESS COATED DEPENDANT ON:
SPIN SPEED
VISCOSITY
VISCOSITY CAN BE ADJUSTED WITH SOLVENT BUT
NOT ALWAYS STABLE
PL 1000 VISCOSITY STABILITY
CD
^
^
CD
I
l _
\0
20
Storage Period (Days)
Fig.
n
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r.
5. Storage stability of PL-1000
r.V ',
3U
PREBAKE METHODS
OVEN HEATING
IR HEATING
HOTPLATE HEATING
PREBAKE CONDITIONS TO ACHIEVE
A DRIED FILM ^ U M THICK OF:
EM SELECTILUX HTR-2
PREBAKE 2 HOURS AT 650C
DUPONT PIH 71710
PREBAKE 90 MIN. AT 55^0
HITACHI PL 1000
PREBAKE i|5 MIN. AT 70°C
UV EXPOSURE
EM CHEMICALS SELECTILUX HTR-2
80 Mj/cM^/uM THICKNESS
DUPONT PIH 71710
FOR A ^MM THICK COATING ^ 30 SEC. a 5 M W / C M ^
HITACHI PL 1000
FOR A i|MM
THICK COATING =^ 12 SEC. 3 5 M W / C M ^
fl
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. \ r -:
^:y
PL TOGO UV ABSORPTION
100
10
F/Jm
Thick n e s s
( jjtn j
THE UV m o m i o t i OF PAL..
15
fl
J
100
90.
80
3
UV ABSORPTION OF SELECTILUX HTR1.2yM THICKNESS AFTER SOFTBAKE
(DRY)
70.
LU
^
60
I—
^
50
•a;
^0
cm
30
20
10
WAVELENGTH (Nf^)
PATTERN DEVELOPMENT
FOR ^ m DRIED FILMS
SELECTILUX HTR-2
CYCLOPENTANONE AND ISOPROPANOL
^ 20 SEC.
DUPONT PIH 71710
BUTYROLACTONE AND TOLUENE
^ 15 SEC.
HITACHI PL 1000
N-METHYL PYRROL IDONE
^ 8 MIN.
THICKNESS LOSS DUE TO
DEVELOPMENT
SELECTILUX HTR-2
^ 5%
PIH 71710
PL 1000
^12%
DAT^ PREPARED
SPEAKER
SPEAKER
MEETING
MEETING
DATE
DATE
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CURE CONDITIONS FOR
PHOTOSENSITIVE POLYIMIDES
200°C IN AIR 30-60 MIN.
^00°C IN No 60 MIN.
THICKNESS LOSS DURING DEVELOPMENT
AND CURE
SELECTILUX HTR-2:
DEVELOPMENT LOSS
- 5%
CURE LOSS
^ 60%
PL 1000:
DEVELOPMENT LOSS
CURE LOSS
"10%
^- ^0%
TOTAL
:^62%
OF DRIED
THICKNESS
TOTAL
- ^5%
OF DRIED
THICKNESS
PL 1000: SPIN SPEED vs THICKNESS
o
8
7 ^^
0
6 -
Thickness
(/im)
o
uncured
•
cured
o
•
5 -
0
4 -
0
•
0
•
3 —
•
0
•
•
2 -
•
1
1
1000
" 1
1
1
1
1
1500
2000
2500
3000
3500
Spin Speed (RPM)
1
4000
CAREFUL PROCESS CONTROL IS NECESSARY TO OBTAIN:
UNIFORMITY OF DESIRED COATING THICKNESS
PREBAKE UNIFORMITY
DEVELOPMENT UNIFORMITY
Bulletin #PC-7
VM-651 ADHESION PROMOTER
VM-651 is an organosilane which is used to
improve the adhesion of all types of PYRALIN*
polyimide coatings to wafers (Si or Si02
surfaces). VM-651 is easy to apply and effective
at very low concentrations. Among all the
organosiianes that possess either amino or
epoxy groups, alpha-amino propyltriethoxysilane was found to give the best and most
consistent overall results.
Table I shows the experimental results when
this silane compound is used as the adhesion
promoter. These results show that the adhesion
is not affected when the concentration of silane
varied between .01% and .1%. No difference in
adhesion was observed between air drying the
silane or prebaking it at 130°C.
TABLE I
VM-651 CONCENTRATION RANGE
.01%TO-.1%
WAFERS
15 mil thick, 3" diameter (381 microns, 76MM)
P-Type boron doped
1,1,1 polished, any resistivity
PYRALIN CONTROL
(No Adhesion Promoter)
1 min. boiling water
0% peelH)
5 min. boiling water
50% peel
10 min. boiling water
88% peel
30 min. boiling water
100% peel
PYRALIN OVER AIR DRY VM-651
1 min. boiling water
0% peeH^'
10 min. boiling water
0% peel
60 min. boiling water
0% peel
30 min. Pressure Pot(2)
o% peel
120 min. Pressure Pot(2)
0% peel
PYRALIN OVER VM-651
BAKED AT 130°C FOR 10 MINUTES
60 min. boiling water
0% peel
120 min. Pressure Pot
0% peel
NOTES:
(1) Peel Test Method: 1/8" cross-hatch and peeled with
"MYLAR" pressure sensitive adhesion tape
(2) Pressure Pot conditions; 250° F, 15 psi
(121°C, 104 X 10^ Pascals)
Du Font's liabiltly is expressty limited tjy Du Ponfs conditions of sale shown on Belter's price list or
Buyer's copy of Seller's order acknowledsment form (if used) and Seller's invoice. All tectinicBladvice,
recommendations and services are rendered by the Seller free of charge. While based on data
VM-651 may also be used to promote adhesion
between PYRALIN and glass and a variety of
inorganic substrates.
Experimental results indicate that only a
monomolecular layer is needed to promote
adhesion. These results indicate that a Si-0
bond is formed with the substrate.
When the PYRALIN solution is applied to the
surface, ionic bonds are formed between the
PYRALIN and the amine groups in the VM-651.
Although these bonds may not survive
subsequent processing steps, they have already
served the purpose of bringing the PYRALIN
coating into intimate contact with the substrate,
intimate contact is essential to developing good
adhesion.
SOLUTION PREPARATION
VM-651 as received must be diluted to
effectively react with the wafer surface. The
following steps are suggested.
1. Prepare a mixture of 95% methanol and 5%
deionized water.
2. Add VM-651 to obtain .1 to .01% solution of
VM-651 in mixture of Step 1. (In 1000 milliliter
MethanoI/Water, add .5 milliliter VM-651.)
3. Stir until niixed.
4. Close container and let stand for 12 hours
before use.
5. Mark date on container.
6. Discard after 20 days and prepare fresh
batch. Do not use material older than
20 days — poor adhesion will result.
APPLICATION
Flood surface of wafer with the diluted solution
of VM-651. It is suggested that the solution be
filtered through a 0.2 micron filter at the time of
application. Spin for 20 to 50 seconds to allow
air drying. Spin time will vary with spin speed
and wafer size. A 3" wafer at 5000 rpm will
require 20 seconds of spin time. No bake is
required. The wafer is now ready for application
of the desired PYRALIN polyimide coating.
believed to be reliabie, they are intended for use by skilled persons at their own risk.Seller assumes no
responsibility to Buyer for events result! r)o or damages irKurred from their use. They are notto betaken
as a license to operate urxler or intended tn RiinnRAt inirinnf.m<.nt ni anu aviatinn naiont
B
RESULTS
The photo shown above illustrates that the
adhesion promoter changes the surface characteristics of the wafer and helps to obtain a
uniform, blemish-free coating. The coating in
"A" shows the effect of using PYRALIN* PI-2555
diluted 5 parts PYRALIN to one part of T-9035
thinner. The wafer in "A" is not treated with
VM-651. You will note some edge pull back and
surface blemishes.
The picture "B" shows the same PYRALIN
formulation coated on a wafer that was treated
with VM-651. This wafer shows no edge pull
back or surface blemishes. Coating thickness
on both wafers shown is 1 micron.
SPECIFICATIONS
Color — Water white
Specific Gravity — 0.945 25/25°
Flash Point — 160° F (closed cup)
Percent Volatile by Volume % — <1.0
SHIPPING
VM-651 is classified as a corrosive material by
the Department of Transportation. The material
is packaged in a 500 gram DOT 2E plastic
container. This container is then packaged in a
'Du Pont trademark.
metal can and surrounded with vermiculite. A
metal cup with six safety clips seals the metal
can. A DOT 12A cardboard container holds the
metal can. This package meets all DOT regulations for shipping by air, rail, or truck.
SAFETY
VM-651 adhesion promoter can cause eye
damage and skin burns. In case of skin contact,
flush with water and then wash thoroughly with
soap and water. In case of eye contact,
immediately flush eyes with water for 15
minutes. Consult a physician.
Use in a well ventilated area. Rubber or plastic
gloves should be worn as should a face shield
or eye goggles.
Keep container tightly sealed — water will cause
VM-651 to polymerize slowly.
AVAILABILITY
Available in 500 gram containers from the Du Pont
Company, F&F Department, 85 Mill Plain Road,
Fairfield, Connecticut 06430, Attn: B.T. (Brian)
Lynch. Phone: (203) 259-3351, Ext. 247. For
additional technical information, call V.S. (Vic)
Bowers, (302) 774-0259. Telex #83-5420. Cable
address: FABFINISHES
POLYIMIDE COATINGS FOR ELECTRONICS
\
B u l l e t i n #PC-24
(E-52139)
4/82
PRODUCT SPECIFICATION
VM-651 ADHESION PROMOTER
VM-651
TEST
Density
0.946 + 0.1
(25*C)
g/cc
TEST METHOD
Du P o n t TM I I G
6 . 0 ppm max.
Du P o n t TM I I C
Sodium C o n t e n t *
1.5 ppm max,
Du P o n t TM I I B
Potassium
0.5
"
0.5
"
Chloride
Copper
Iron
NOTE:
Content*
Content*
Content*
Content*
0.05 "
I t i s recommended t h a t f i n a l f i l t r a t i o n be done a t t h e
dispensing point.
VM-651 i s used a t c o n c e n t r a t i o n s of
0.01% t o 0.1% i n a s o l u t i o n of 95% methanol and 5% d e i o nized water.
F i n a l f i l t r a t i o n should be done a f t e r t h e
s o l u t i o n i s p r e p a r e d t o be s u r e t h a t t h e methanol and
water i s a l s o f i l t e r e d .
*Based on t o t a l
sample.
Du Ponfs liability is expressly limited by Du Ponfs conditions of sale shown on Seller's price list or
Buyer's copy of Sellers order acknowledgment forni (if used) and Seller's invoice.Alltechnicaladvlce,
recommendations and services are rendered by the Seller free of charge. While based on data
believed to be reliable, they areintended tor use by skilled persons at their own risk.Seller assumes no
responsibility to Buyerfor events resulting or damages incurredfrom meir use. They arenottobetaken
as a license to operate under or intended to suggest infringement of any existing patent.
Dav.L(.l Kiein-fGld
Room 6H-424
ATT Bell Laborator:LL^s
600 Mountain Avenue
Murray Hill, H..U 07974
f9
Polyimides
in Semiconductor
Manufacturing
Polyimides are finding a broad, new rcuige of
applications in the manttfacture of integrated circuits.
By Ron Iscoff, West Coast Editor
Fbrmerly used chiefly in the printed
circuit industry, new polyimide formulations are being incorporated into the
fabrication and packaging cycles of
integrated circuits.
Major applications for polyimides
^oday include their use as alpha particle
arriers, coatings for passivation and
mechanical protection, interlayer dielectrics and self-patterning passivation and
high-temperature photoresists.
Alpha particle barrier coatings
A significant and growing use for
polyimides is their application as an
alpha particle barrier. The barrier
consists of a 75 to 80 jmi polyimide
coating applied to the die and cured just
before packaging.
Alpha particle protection is necessary
for hig^-density memory devices to
prevent soft errors. High-density
ievices may suffer soft errors when
ilpha particles, which are emitted from
trace quantities of thorium or uranium
in packaging materials, strike the active
surface.
High-purity polyimides are virtually
free of radioactive emitters, and can
withstand the IC packaging process
without deterioration, according to Dr.
J.C. Chevrier of E.I. DuPont in
Wilmington, Del.
Chevrier, product manager for Semiconductor Materials, maintains that
incorporation of the polyimide barrier
can reduce the constraints of circuit
design in the development and manufaccure of smaller size dynamic memory
devices.
While overall use of polyimides in the
integrated circuit industry is quite low,
the use of the polyimides for alpha
llft^EMICONDUCTOR INTERNATIONAL,
Coating the ujqfer u>ith polymide.
particle protection could represent a
high percentage of its use, according to
Chevrier.
"The main suppliers of 64K dynamic
RAMs use polyimides extensively for
alpha barrier protection of the plastic
packages. I would almost say for this
application, polyimides have become
recognized as an industry-accepted
solution," Chevrier reported.
Passivation coatings
The most popular use for polyimides
today is to passivate integrated circuits,
according to Chevrier.
OCTOBER 1984
"Applied to wafers, polyimides provide excellent moisture barriers and
protect devices from mechanical damage. The latter is especially important in
automated packaging lines which can
prove hazardous for fragile inorganic
coatings.
"A thin but tough layer of
polyimide, applied over inorganic layers, seals any cracks or pinholes that
may form during inorganic deposition,"
according to Chevrier.
DuPbnt claims that polyimides also
trap sodium ions migrating from
packaging materials or other sources,
The actual pattem, in photo resist, on the wafer.
Overlay showing the relationship of the original CAD design
geometry to the corrected CAD and the actual photoresist pattem.
VISION
Geometric analysis for reliable defect detection
Reliable defect detection is the key to in-situ reticle qualificationthat means finding all the defects, and identifying killers. The WaferVision
30CI0 system reliably detects 0.5 micron defects on 1.5 micron features,
with the highest degree of confidence.
Rather than stretching existing technology beyond its design limits,
Contrex has capitalized on recent advances in information systems technology and machine vision to build a new generation of quality assurance
systems. The WaferVision 3000 is a geometric inspection machine that
looks at the actual geometry ofthe printed wafer image, not at individual pixels. Defects are detected as a function of geometric relationships, not as pixel deviations. So the WaferVision 3000 system
not only finds defects, but knows where they are and what they are,
and makes precise measurements as well.
As the industry moves toward one micron geometries and
below, where defect detection requirements are at 0.3 or 0.2
microns, WaferVision systems will continue to provide reliable
defect detection and measurement. If you'd like to know more
about the WaferVision 3000 system, write for our brochure.
Contrex, Inc., 43 Manning Road, Billerica,
MA 01821. (617)273-3434.
CONTREXjj
Por information circle 45
lntelliger\t systems for quality assurance
in wafer fabrication.
-«*-
and offer good moisture absorption, as
well. "It has been shown that devices
passivated with polyimide — compared
with those protected only with inorganc coatings — perform better in
humidity testing," Chevrier added.
The passivation layer may work as a
moisture getter and prevent condensation of water molecules, thereby
preventing corrosion.
Yield improvement
Integrated circuit manufacturers are
now applying a thin polyimide coat over
che die as a buffer against stresses that
build up during thermal cycling,
according to Chevrier. Of)en circuit
failures can be reduced by the
application of a thin coat of high-purity
polyimide. The polyimide acts to protect
the wire bonds against the rigors of
packaging and thermal cycling. The
secondary passivation of the polyimide,
i.e., a polyimide passivation layer over
standard inorganics, can improve the
yields of packaged devices by as much
as 10%, according to Du Pont.
William N. Bolster of M&T Chemicals, Rahway, N.J., agrees that polyimdes are gaining acceptance as a
passivation medium for integrated
circuits. Bolster, a commercial development specialist for the polyimide
producer, said that in terms of
economics, polyimides probably represent "either a wash or a slight savings
over silicones" when used as a
replacement.
Not everyone agrees that polyimides
are becoming a popular replacement for
silicones and other materials, however.
Ken Uchihara, marketing director for
Sumitomo Plastics in Santa Clara,
Calif., reported, "About three or four
vears ago, many people were working
n multilayer metalizations using polyimides. However, now it seems that
nitrides or other inorganic chemicals are
dominating the market for metalization."
In Japan, junction coatings using
either silicones or polyimides are not
popular, according to Sumitomo's Uchihara. He said the major applications for
olyimides in Japan are for power
.ransistors and power linears, primarily
to enhance moisture performance in the
encapsulation step.
Uchihara added that although the
"ompany produces and distributes
)lyimides in the U.S. and Japan,
molding compoimds represent a larger
market. He feels that silica-epoxy
molding compounds, which Sumitomo
produces, can offer alpha particle
Cross-sectional View of Polyimides Being Used
^ :^s Alpha Particle Barrier Coding
Alpha particle barrier,
thermal stress buffer
^
'
^^y,
nd
Lead frame
Die attach
adhesive
SiOz 8,000 A
Polysilicon
6,000 A
*Phosphosilicate glass
(PSG 7,000 A
^
This area
, silicon ^
Polyimide
•• Phosphosilicate
glass (PSG)
'Polyimide can be used as a dielectric in place ol PSQ.
" * Photosensitive polyimide can be used as a self-patterning, high temperature photoresist to produce any of the
dielectric or conductor layers in the wafer.
protection equal to the polyimides.
DuPont's Chevrier concedes that
overall use in the semiconductor
industry of polyimides is small and that
increased usage depends heavily on
educating the industry about the
benefits of polyimides.
He pointed out that polyimides are
commercially available in very high
purity forms, are extremely stable and
have "excellent electrical, chemical and
mechanical properties. Their thermal
and electrical characteristics are superior to previous low-molecular-weight
addition and silicone polyimides."
Interlayer dielectrics
Another application where polyimides are finding favor is their use
as the interlayer dielectric in multilayered integrated circuits.
Chevrier noted that, "As the size of
components gets smaller, it becomes
extremely difBcult to maintain adequately planar surfaces with inorganic
dielectrics such as chemically vapor
deposited silicon dioxide.
"Sharp surface relief at via sites and
at metal lines can cause thinning of
subsequent insulator and metal layers,
leading to increased failures due to
OCTOBER 1984,
SEMICONDUCTOR INTERNATIONAL/117
-rr
Polyimides
inadequate coverage."
Polyimide films, which are less than
1.5 p.m thick, can be made as planar as
necessary because they are dispensed as
liquids and spincoated, according to
Chevrier.
He said they make ideal interlayer
dielectrics because of their high
dielectric strength, low defect density,
ease of etching and controllable via
profiles. Lower residual stress in
polyimides allows the use of thicker
layers without cracking. The defect
density is typically less than seven
defects on a 100 mm wafer, according to
Du Pbnt.
Andy Nakayama, sales manager for
the Hitachi Chemical Co., New York,
N.Y., reported that the leading
applications for polyimides are as
Table 1. T3rpical Process
for Patterning 2 Micron Cured Film
1. Clean and dry wafer surface.
8mW/cm* at 365 nm for 15^20 sec.
2. Surface preparation adhesion
6. Developing: 1/1 Butyrolactone/Xylene
Dip for 15-20 sec.
promoter coating: 4000 rpm, 30 sec.,
0.1% VfWl-651
7. Rinsing: Xylene dip, 25°C, 10 sec.
spin dry in air 4000 rpm 20 sec.
3 PSPI coating: 5 gm/wafer 3000 rpm,
30 sec.
8. Post Bake: 250°C, 30 min. in air
400°C, 30 min. in air or Nj
4. PSPI prebake: 55°C, 45 min. (in air)
Rim thickness after prebake 4 pm
5. UV exposure: (contact aligner)
Rim thickness after cure 2.0 \im
r
l«rt«.--
- -*-""
W' « #
^
^
^
A semiconductor test p a t t e m , made with a 1 3 |xm coating oJDupont
photosensitive polyimide, shows clearly defined 3.75 a n d 5J0 \im lines
and spaces.
118/SEMICONDUCTOR INTERNATIONAL,
OCTOBER 1984
interlayer dielectrics and for passivation
uses.
Hitachi is the largest producer o
polyimides in Japan, and the second
largest in the U.S. Du Pont is the leader
domestically.
Arthur M. Wilson of Texas Instruments, Dallas, Texas, has reported that
polyimide films, used as high-temperature planarizing insulators for multilevel interconnection systems, may be the
key to high-yielding bipolar and MOr
VLSI circuits.'
Wilson, of Tl's Linear Circuits
facility, noted that, "The small feature
size now possible in silicon, and in other
semiconducting phases in which the
active component is built, has placed
severe pressure on the design rules of
interconnection systems in particular,
and on thin-film engineering and
processing personnel in general.
Connection of a large number of
components on an integrated circuit
with single-level (final thermal oxide/
conductor/passivating overcoat) interconnection systems consumes more chir
area for interconnections than for acti\
components. If we recognize highlydoped silicon tunnels as part of the
passive interconnection system, the
active semiconductor area is even
smaller: about 10% or less of the total
chip area in bars of very large area
(greater than 4x10-"' in").
So that advanced lithography tools
can be used to produce chips with small
feature sizes, a planar ized interconnection process must be used, and
polyimide insulation technology provides the interconnection systems with
planarizing capability, according to
Wilson.'i
Photosensitive polyimides
A photosensitive polyimide, which Du
Pont introduced at Semicon West this
year, has properties which make it
suitable for passivation and hightemperature masking. Because it eliminates processing steps, it is said to
increase yields and productivity whU'
reducing semiconductor fabricatic
costs.
In passivation applications, the mask
is placed directly on the negatiyeworking photo-definable polyimide film,
eliminating the photoresist step. T"
cured polyimide becomes a mechanical,
toug^ film which provides reliable
electrical, mechanical and moisture
protection as well as stability and
«..
*-fl'
rigidity to the wafer, according to Du
Pbnt.
The company claims the material has
mechanical properties which are superior to those found in inorganic materials.
A typical process for patterning 2 jxm
cured film is shown in Table 1.
Du Pbnt points out that unlike some
inorganic films, polyimides have very
low residual stresses, and can be
deposited over a wide range of
hicknesses, from a 0.8 jrni layer for an
.nterlayer dielectric, to a 3.0 jtm
passivation film, to a 75 nm coat for
alpha particle protection. Figure 1
shows a 1.8 ^i.m coating of photosensitive polyimide.
Scientists at the Massachusetts
Institute of Technology Lincoln Laboratory have been working with polyimides
for high resolution ion implantation
masking for several years.'
T.O. Hemdon, et al, reported that "in
evaluating alternatives (for high energy
ion implants) we found that photoresist
masks could provide reasonably good
''esolution, but that the mask profile
jgraded at implant doses as low as
xXlO'' cm"^ and that the resist was
difficult to strip after higher dose
implants.
"Plasma etched aluminum was foimd
to provide good resolution and masked
profiles did not degrade. However,
control of undercutting during aluminum etching has been a probleni. In
response to these difficulties, reactive
ion etched polyimide was evaluated as a
reliable, high-resolution implant mask
process.
"Reactive ion etching can provide
negligible undercutting," Hemdon con'nued. Furthermore, since polyimide is
high-temperature material, it should
withstand the large temperature rise
which occurs during heavy dose
implantations, responsible for the
degradation observed in photoresist."^
Hemdon concluded that oxygen
plasma etched polyimide, using a
photoresist etch mask, provides a
-'mple process for masking geometries
the order of 3 microns or larger,
tteactive ion etched polyimide, using a
thin aluminum etch mask, provided
reproducible masking of micron and
submicron geometries.
"In contrast to photoresist masks
iere profile degradation was observed
at implant doses as low as 1 x 10"* cm~^
polyimide mask profiles exhibited very
little change after implants of 1x10"
Table 2 . Polyimide Uses a s
Substituted/Complementary Chemicals
Polyimides Uses
Replacing/Complementing
On Wafer
Passivation
Silicon dioxide or PSG
Silicon nitride
Sputtered quartz
Silicon dioxide
Silicon nitride
Sllteones
"CoM" epoxy mokling compounds
Dielectric
(Interlayer)
Alpha Particle
banner
(memories)
Thermo mechank^l
isolation from package
Multlchlp Interconnects
Passivation
Glass (thin film hybrid
technology)
Glass (thin film hybrid
technology)
Dielectric
(Interlayer)
IC Packaging
Die-attach
(Silver-filled polyimides)
Gold eutectics
Silver epoxles
IC Process Aids
Ion-implant mask
Metal lift-off mask
Support for X-ray mask
cm-2 at 200 KeV," Hemdon reported.
Screenable polyimide
Several companies, including DuPont
and M&T Chemicals are working on a
silk screenable polyimide which will
allow users to employ applications such
as alpha particle protection coating at
the wafer stage, as opposed to applying
the protection at the die dispense mode
at the packaging station.
"That may provide an economic
advantage for the customer," DuPont's
Chevrier said.
M&T Chemicals is sampling a version
of its siloxane polyimide resin for use in
screenable applications for passivation
and alpha particle barrier coating.
The chemical producers are watching
with interest as polyimides displace
silicones and other material. (See Table
2.)
M&rs Bolster feels that polyimides
will not replace most older applications,
but rather new applications, in areas
where there are problems with the
current materials. "Historically, this is
where changes take place," he
remarked.
D
References:
1. A.M. Wilson, "Polyimide Insulators for
Multilevel Interconnections," Thin Solid
Films, 83 (1981) p. 145.
2. Ibid, p. 147.
3. T.O. Hemdon, et al, "Pblyimide for High
Resolution Ion Implantation Masking, unpublished paper," p. 1.
4. Ibid. p. 5.
For more Information direct from the
manufacturers of basic polyimides,
circle the appropriate number found on
the reader service card In this Issue.
Company
CIBA-Qelgy
Du Pont
Hitachi Chemical Co.
M&T Chemical Co.
Sumitomo Plastics Co.
Reader Interest Review
Please help our editors evaluate your
interest in this article. Circle number
indicated on the Reader Service card.
Higli489
Medium 490
Low 491
OCTOBER 1984,
r-A
Circle No.
235
236
237
238
239
SEMICONDUCTOR INTERNATIONAL/119
•
• lei^^i
Allied Corporation
and Diffusion Technology
are now one company
for all of your liquid
spin-on requirements
^UIED
For information circle 46
120/SEMICONDUCTOR INTERNATIONAL,
OCTOBER 1984
^
,
IMHI
.JP
Rrjorf, 6H-474
•^TT B e l l Lobo,
'.Totor\ie<:i
6O0 M o u n t a i n
rtvenue
M u r r a y Hi i -i •., , •^'^;
POLYIMIDE COATINGS FOR ELECTRONICS
^ 1 1
i^
^
Bulletin #PC-1
(E-47943)
Rev. 4/82
PYRALIN* SEMICONDUCTOR GRADE PRODUCTS
The product line involves a number of different chemistries. All
are polyamic acid solutions which convert to fully aromatic
polyimide coatings when exposed to heat. The cure properties,
adhesion, solubility, and application conditions vary slightly
with each product.
The viscosity/solids characteristics are unique for each product.
All are high-purity formulations, controlled for metallic ion
content (sodium less than 2.5 ppm) and filtered through 0.1
micron nominal medium. In additional, PI-2545, PI-2555, and
PI-2562 are filtered through 0.2 micron absolute filters, as is
the PYRALIN* thinner, T-9035.
Other products include PI-2540, PI-2550, and PI-2560 which are
higher solids/higher viscosity versions of their counterparts
listed above.
PI-2566 is an optically clear solution and
PIH-61454 is a thixotropic formulation, suitable for application
by screening.
Processing
The basic process is to dilute the polyimide coating (if necessary), filter, spin dry, apply photoresist, develop, etch, strip,
and cure.
The following steps apply directly to PYRALIN* products PI-2540,
PI-2545, PI-2550, and PI-2555. See product bulletins PC-3, PC-4,
and PC-5 for processing modifications concerning PYRALIN*
PI-2560, PI-2562, PI-2566, and PIH-61454.
Du Font's liability ts expressly limited by Du Fonts corxJrtions oi sale shown on Seller's price list or
Buyer's copy of Seller's order acknowledgment form (ifused) and Seller's invoice. All technical advice,
recommendations and services are rendered by the Seller free of charge. While based on data
believed to be reliable, they are intended for use by skilled persom at their own risk.Seller assumes no
responsibility to Buyer for events resulting or damages incurred from their use. They are not tobetaken
as a license to operate under or intended to suggest infringement of any existing patent.
-2• Apply Adhesion Promoter
The adhesion of PYRALIN* coatings to Si02 can be greatly
enhanced by the use of an adhesion pJ^onioter. Du Pont
recommends its VM-651 adhesion promoter.
This material
must be reduced to a 0.1% to 0.01% solution in water/methanol before applying to the wafer. Allow the solution to
normalize for 12 hours before using. The use of too weak
or too strong a solution can cause problems. To prepare a
0.05% solution in a methanol/water system, mix 200 ml of
95% methanol and 5% deionized water. To this 200 ml, add
one drop of VM-651. Once reduced, the adhesion promoter
should be discarded after twenty days.
Puddle onto wafer and spin at 5000 rpm for 30 seconds.
This will air dry the material.
Tests have shown that
baking is not required.
See PYRALIN* Bulletin PC-7 (Du
Pont Bulletin E-45525) for more details.
• Apply PYRALIN*
Apply the PYRALIN* to the wafer and spin. The type 2540
and 2550 will yield a film thickness of about 2.5 microns
at 5K speeds for 30 seconds, while the 2545 and 2555 will
yield thicknesses of about 1 micron.
Thickness can be
controlled by varying the spin speed or diluting the
PYRALIN* with Du Pont's T-9035 thinner.
The spinning should be done in an environmentally controlled room just as photoresist is handled. Changes in
humidity can cause variations later in the process. See
PYRALIN* Bulletin PC-2 (Du Pont Bulletin E-45524) for more
details.
• Partially Cure
The polyimide film etches more easily in a dry, partially
cured state. The rate and profile depend on the degree of
cure or imidization which, in turn, is a function of
temperature. The greater the imidization, the slower the
etch rate. Note that PI-2550 and PI-2555 imidize more
quickly at the same temperature than PI-2540 and PI-2545.
Experimentation will determine the best cure. To start,
try 135*'C for 30 minutes.
If the process calls for plasma etch instead of a wet
etch, the polyimide film should first be cured at least
one hour at 300*C after the lower temperature bake.
-3-
• Apply Photoresist
Use normal procedures. Make sure the partially cured
polyimide film has returned to ambient temperature after
bake. If applied to warm film, some reaction between
certain resists and the film will occur.
Many users
prefer a positve photoresist because it contains fewer
steps than negative photoresist. The positive photoresist
and the PYRALIN* can be developed and etched in one step.
• Align & Expose
Normal procedures, depending on your photoresist, should
be followed.
• Develop Resist and Etch
Several types of materials have been successfully used to
etch the partially cured polyimide film.
When positive photoresists such as AZ-111, AZ-1350J,
and AZ-1375 are used, development of the photoresist and
etching of the polyimide are accomplished simultaneously.
Developers such as AZ-351 or MF-312 are used.
Other
etchants for polyimide film include NaOH, KOH, and tetra
alkyl ammonium hydroxide. The developer or etch solutions
should be maintained at 0.25N and 30*C for best results.
Negative photoresists have also been used successfully.
The same etchant is used as for positive photoresist. An
intermediate bake (200"C for 30 minutes) may be necessary
to imidize the polyimide sufficiently to withstand the
strong strippers used.
A spin spray or straight spray
developer system should be used to develop and etch.
If plasma etch is used, oxygen is the preferred gas. The
polyimide must, in this case, be fully cured before application of the resist.
The resist thickness must be
greater than the polyimide because it will etch faster
during the plasma treatment.
• Via Clean-Up
After wet/dry etching, it may be necessary to clean the
vias to remove residual material which results in high
ohmic resistance. The following methods of clean-up are
listed in order of effectiveness:
-41. Reverse sputtering.
2. If Si02 or Si^N. is used over metal in the via before
polyimide deposition, removal of the glass will
provide clean vias.
3. Clean-up may also be obtained by use of chemical
means, i.e. sulfamic acid/phosphoric acid followed by
a heat treatment of 450*C for 5 minutes.
4. Low pressure O2 plasma.
• Neutralize
Depending on the etching process, it may be good practice
to neutralize with a 1% acetic acid solution and deionized
water rinse. Titration of the rinse water will show
length of rinse time needed to remove all traces of the
acetic acid.
• Strip Resist
Typical positive photoresists are stripped using butyl
acetate/isopropanol or other strippers. Negative strippers often contain phenol and sulfuric acid. A spray
system is recommended.
• Final Cure
A final cure is required to develop maximum properties.
This can be accomplished by baking for one hour at 350''C
or 30 minutes at 400*'C.
PI-2550 and PI-2555 can also be cured at temperatures as
low as 180*0 in some extreme cases. Films of 25 microns,
cured for 2 hours at 180*>C, exhibit tensile strengths and
elongation equivalent to films cured at higher temperature
conditions. The dissipation factor of films cured at
180*0 is higher, typically 0.003-0.004 due to small residual amounts of NMP retained in the film. Curing conditions will vary for different applications. For best
results, a convection oven should be used. Cures above
400*C should be done in non-oxidizing atmospheres.
• Metallization
For multilayer metallization designs, the process is
repeated.
When applying polyimide over polyimide, use
PI-2550 or PI-2555 as the first coat and the same or
PI-2540 or PI-2545 as the second coat. No adhesion promoter is required between coats.
/•
/
-5If two coats of PI-2540 or PI-2545 must be used, the first
coat should not be completely cured or the second coat
will not adhere well.
If full cure between coats is
necessary, an oxygen plasma roughening of the surface will
enhance adhesion.
Storage Stability
PYRALIN* polyimide coatings are sensitive to heat and should be
refrigerated at 4*0 maximum. Freezer storage (-18"C) will practically eliminate any viscosity drift and prolong shelf life
significantly. When exposed to heat, PI-2540 and PI-2545 will
first drop in viscosity, then increase and eventually gel.
PI-2550 and PI-2555 polyimide coatings are more stable.
Viscosity curves are found on Page 9.
Moisture contamination is detrimental to stability and must be
avoided. Containers should be brought to room temperature before
opening to avoid moisture of condensation.
-6-
TABLE 1: LIQUID PROPERTIES**
PI-2540
PI-2545
PI-2550
PI-2555
Solids
(2 gms, 2 Hours
@ 200^0
15%
14%
25%
19%
Viscosity
(LVF #3
@ 12 RPM)
40-70 poise
4.7 Pascal second
10-12 poise
1-1.2 Pascal second
40-70 poise
4-7 Pascal second
12-16 poise
1.2-1.6 Pascal second
Solution Density
1.06 g/cc
1.05 g/cc
1.08 g/cc
1.06 g/cc
Solvent
NMPl/aromatic
hydrocarbon
NMP ^/aromat ic
hydrocarbon
NMPl/acetone
NMP ^/aromatic
hydrocarbon
Flash Point
(Closed Cup)
640C
640C
-70C
640C
Filtration
0.1 micron
nominal
0.2 micron
absolute
0.1 micron
nominal
0.2 micron
absolute
^NMP: N-methyl-2-pyrrolidone
**Typical properties, not to be used for specification purposes.
bulletins.
See product specification
TABLE II: FILM PROPERTIES **
When fully cured, Pyralin* polyimide films are extremely heat resistant, mechanically tough,
chemically resistant, and possess good electrical properties.
PI-2540 (PI-2545)
Physical
Tensile Strength (ultimate)
Elongation
Density
Refractive Index
(Becke Line)
Flexibility
PI-2550 (PI-2555)
17,000 psi (1.17 X 10^ Pascal) 19,000 psi (1.31 x 10^ Pascal)
25%
10%
1.42 gms/cc
1.39 gms/cc
1.78
180° bend, no cracks
1.70
180° bend, no cracks
Melting Point
Weight Loss @ 3160C in air,
after 300 hrs.
Final decomposition temperature
Coefficient of thermal expansion
Coefficient of thermal conductivity
None
None
4%
560°C
2.0 x 10~5/oc
37 x 10"^ cal
(cm) (sec)(OC)
4%
560OC
4.0 X 10-5/oc
35 X 10-5 cal
(cm) (sec) (OQ)
Flammability
Specific heat
Self-extinguishing
0.26 cal/gm/oc
Self-extinguishing
0.26 ca1/gm/oc
.002
4000 volts/mil
10^^ ohm-cm
10^5 ohm
3.5
.002
4000 volts/mil
lO-'-^ ohm-cm
1015 ohm
3.5
Thermal
Electrical
Dissipation Factor (IKHz)
Dielectric Strength
Volume Resistivity
Surface Resistivity
Dielectric Constant (iKHz)
*Du Pont Trademark
**Typical properties, not to be used for specification purposes.
See product specification bulletins.
. /
/
. /
y
, / •
/:•
.•'•'
-•>>''
'V
-8IMIDIZATION RATES
t 'Imidization
00
W/////y. VW/M'y^///////A
•
^150X
80
riso'c/
60
y^
y
las'c
1/
40
20
^
-J/
io^--"^
Y^
"
n
10
20
^
.
^
PI-2550 Type
•
^
^
1 2 0 ^
^
30
1
1
1
40
50
60
Time (Min)
%Imidization
100
•»
'•^^ii^:::^^////^
^
^
^
^
^
^
^
^ ^ ^ ^ ' ^ 180X
80
^150"C
60
V
PI-2540 Type
40
¥^
20
y ^^^—^""T—r
20
30
10
Note;
•
__^
II
40
135X
50
1
60
Time (Min)
These curves were generated using IR scanning techniques. This
method does not adequately identify imidization levels above 90%.
The electrical dissipation factor test should be used to determine
if complete imidization has occurred.
-9VISCOSITY STABILITY
Poises
90
PI.2550
O = ll.oom Temp. 25°C
• = R e f r i g . Temp. 4°C
50
40'
J
20
I
40
\
\
60
80
I,
100
120
140
Days
Poises
90
0» Room Temp. 25°C
•- Refrig. Temp. 4°C
•KJ
401
J
L
20
40
1
J
60
80
Days
I
100
»
L
120
140
-10TOXICITY/HEALTH HAZARDS
Adequate ventilation must be provided and skin contact should be
avoided. Exposed areas should be flushed with water immediately.
Rubber gloves resistant to the solvents in PYRALIN* Polyimide
Coatings can be procured as follows: for general-purpose use,
the "Buta-Sol" milled butyl rubber glove (Norton Company, Safety
Products Division, P.O. Box 4367, Charleston, SC 29405); for
light service, the "Wil-Gard" No. 26-640 tan latex industrial
glove (Edmont-Wilson Division, Becton Dickinson and Company, 1300
Walnut Street, Coshocton, OH 43812); and for service requiring
greater resistance to wear, the Natural Latex Rubber glove No.
2911 (B.F. Goodrich Engineered Systems, 500 S. Main Street,
Akron, OH 44318).
Data supplied by the General Aniline and Film Corporation indicate that animals exposed to air saturated with N-methyl-2-pyrrolidone for six hours daily for ten days tolerated the conditions
of the experiment and gained weight normally. Other animals
subjected to 20-day dermal toxicity studies had no specific
degenerative changes and did not have a remarkable degree of skin
irritation.
VM-651 adhesion promoter can cause eye damage and skin burns. In
case of skin contact, flush with water and then wash thoroughly
in soap and water. In case of eye contact, immediately flush eye
with water for 15 minutes. Consult a physician.
Use in well ventilated area. Rubber or plastic gloves should be
worn as should a face shield or eye goggles.
Keep container tightly sealed - water will cause VM-651 to polymerize slowly.
AVAILABILITY
Available in one-half kilo, one kilo, or four kilo containers
from Du Pont Company, F&FP Department, 85 Mill Plain Road, Fairfield, Connecticut 06430, Attn: B.T. (Brian) Lynch. Phone (203)
259-3351, Ext. 247. For additional technical information, call
V.S. (Vic) Bowers, (302) 774-0259.
Telex #83-5420. Cable
address: FABFINISHES.
yy^'-^^f^
David K l e i n f e l d .
ATT B e l l L a b o r a t q i l e . .
' o o Mountain « - - ^ ; , , , , ,
Murray Hillv_ ' ^ ' ' , • ur i i
POLYIMIDE COATINGS FOR ELECTRONICS
B u l l e t i n #PC-10
(E-52127)
10/20/81
PRODUCT SPECIFICATION
PI-2555
PI-2555
TEST
TEST METHOD
Solids
19 + 1%
Du P o n t TM I I A
Viscosity
12-16
Du Pont TM I I H
(#3 s p i n d l e 12 rpm)
% Ash
0.1%
max.
1.06
+ 0.1
Density
(25°C)
poises
Du Pont TM I I F
g/cc
Du P o n t TM I I G
Infrared
Identification
Compare a f t e r 30
m i n u t e bake @ 200°C
(See R e v e r s e
Solvent
N-Methyl-2-Pyrrolidone/
Aromatic Hydrocarbon
8 0 / 2 0 + 5%
Du P o n t TM I I D
Chloride Content**
10 ppm max,
Du P o n t TM I I C
Sodium C o n t e n t * *
Potassium Content**
Copper C o n t e n t * *
Iron Content
2 . 5 ppm max,
1.0
"
"
1.0
"
"
1.0
"
"
Du P o n t TM I I B
Total
10 ppm max.
Du P o n t TM I I
System
Metals
Filtration
**Determined on t o t a l
0.2 micron
Side)
J
abs.
sample.
Du Ponfs liability is expressly limited by Du Ponfs conditions ol sale snown on Sellers price list or
Buyer's copy ol Seller's ordet acknowledgment form (it used) and Seller's invoice. All technical advice.
recommendations and services are rendered by the Seller tree ol charge. While based on data
believed to be reiiaoie.tney are miended lor use IDy skilled persons at iheir own nsk.Seller assumes no
responsibility to Buye'tor events resulting or damages incurredfrorr their use. They are not to betaken
as a license to operate under or intended to suggest infringement ol any existing patent.'
Piinted In U.S.A.
o
o
INFRARED IDENTIFICATION
•
o
CJ
o
o
•
o
o
o
o
•
o
DU PONT
PI-2555
30 Min. @ 200C
lijCD
u
CO
z oo
aoc
•
HO
o
o
. •
o
CJ
o
o
«lO0O
36bQ
32b0
28b0
2^55 20b0
MRVENUMBERS
16b0
12b0
800
WO
David Kleinfeld
RoDii. 6H~424
ATT Bell Laboratories
AGO Mountain Avenue
POLYIMIDE COATINGS FOR ELE
Murray n i i i .
N.J.
O7<?74
Bulletin #PC-4
(E-47945)
Rev. 4/82
PYRALIN* PI-2566
PYRALIN* PI-2566 is a formulation designed to yield cured
coatings of greater optical clarity than those obtained with
other PYRALIN materials.
The index of refraction (Becke Line) is 1.56 vs. 1.78 for
the PI-2540 series and 1.70 for the PI-2550 series.
Potential applications where clarity is required include;
• Opto Couplers and Isolators
• Alignment coatings for Liquid Crystal Displays
as well as special integrated circuit devices where quality
control inspection must be done through the coating.
PI-2566 processing and cured film properties are similar to
the PI-2550 series described in Bulletin PC-1; however, special
techniques and conditions are required for consistent wet processing.
PI-2566 offers
moisture absorption.
excellent
Du Ponfs liability is expressly limited by Du Ponfs conditions of sale shown on Seller's price list or
Buyer's copy of Seller's order acknowledgment form (if usecO and Seller's invoice. All technical advice,
recommendations and services are rendered by the Seller free of charge. While based on data
electrical
properties
and
low
believed to be reliable, they are intended lor use by skilled persons at their own risk. Sellerassumes no
responsibilitytoBuyerfor events resulting or damages incurred from their use. They are not to betaken
as a license to operate under or intended to suggest infringement of any existing patent.
Printed In U.SA
-2LIQUID PROPERTIES**
PI-2566
Solids
(2 gms, 2 hours
§ 200»C)
18%
Viscosity
(LVF #3
e 12 RPM)
Weight
per gallon
per liter
50-70 poise
5-7 Pascal second
8.80 lbs.
1.06 kg
Solution
Density
1.06 g/cc
Solvent
NMP /aromatic hydrocarbon
Flash Point
(Closed Cup)
64«>C (147»F)
Filtration
1 micron
NMP: N-methyl-2-pyrrolidone
••Typical properties; not to be used for specification
purposes.
STORAGE STABILITY
PYRALIN* polyimide coatings are sensitive to heat and should
be refrigerated at 4*'C maximum.
Freezer storage (-18**C) will
practically eliminate any viscosity drift and prolong shelf life
significantly.
TOXICITY/HEALTH HAZARDS
Adequate ventilation must be provided and skin contact
should be avoided. Exposed areas should be flushed with water
immediately.
Rubber gloves resistant to the solvents in PYRALIN* polyimide coatings can be procured as follows: for general purpose
use, the "Buta-Sol" milled butyl rubber glove (Norton Company,
Safety Products Division, P.O. Box 4367, Charleston, SC 29405);
for light service, the "Wil-Gard" No. 26-640 tan latex industrial
glove (Edmont-Wilson Division, Becton Dickinson and Company, 1300
Walnut Street, Coshocton, OH 43812); and for service requiring
-3greater resistance to wear, the Natural Latex Rubber Glove No.
2911 (B.F. Goodrich Engineered Systems, 500 S. Main Street,
Akron, OH 44318).
Data supplied by the General Aniline and Film Corporation
indicate that animals exposed to air saturated with N-methyl-2pyrrolidone for six hours daily for ten days tolerated the conditions of the experiment and gained weight normally. Other animals subjected to 20-day dermal toxicity studies had no specific
degenerative changes and did not have a remarkable degree of skin
irritation.
AVAILABILITY
Available in one kilo or four kilo containers from:
Du Pont Company
85 Mill Plain Road
Fairfield, Connecticut 06430
Attn: B.T. (Brian) Lynch
Phone: (203) 259-3351, Ext. 247
For additional technical information, call V.S. (Vic)
Bowers, (302) 774-0259.
Telex: 83-5420.
Cable address: FABFINISHES.
:.%•
Bdvid Kleinfeld Room 6H-424
.•_ .
ATT Bell Laborator-.Le<:>
600 Mountain '^'-•^"'•"^^„.,.
POLYIMIDE COATINGS FOR ELECTRON Murray HiUv N.J. 079M
Bulletin #PC-3
(E-47944)
Rev. 4/82
PYRALIN* PI-2560 AND PI-2562 SEMICONDUCTOR GRADE
PYRALIN* PI-2560 is a polyamic acid solution designed to
provide thicker coatings with one application than is normally
possible with other PYRALIN solutions. The product combines a
high solids content (37%) with a moderate viscosity.
PI-2562 is a diluted version of PI-2560 which has undergone
0.2 micron absolute filtration.
Typical potential applications include die bonding, mechanical protection, and/or alpha protection coating.
These coatings also offer:
• Excellent step coverage for metallization systems.
• Pinhole and crack-free, mechanically tough films.
• Compatibility with semiconductor fabrication and
packaging.
• Controlled metallic ion content; sodium less than 3
ppm.
Du Ponfs liability is expressly limited by Du Ponfs conditions of sale shown on Seller's price list or
Buyer's copy of Seller's order acknowledgnwnt fonn (if used) and Seller's invoice. All technicaladvice,
recommendations and services are rendered by the Seller tree ol charge. While based on data
believed to be reliable, they areintended for use by skilled persons at theirown risk.Sellerassumes no
responsibility to Buyerlor events resulting or damages Incuned from their use. They arenottobetaken
as a license to operate urxjer or intended to suggest infringement ol any existirtg patent.
-2LIQUID PROPERTIES^^^
PI-2560
PI-2562
37%
25.5%
Viscosity
(LVF #3
@ 12 RPM)
15-30 Poises
1.5-3.0 Pascal Second
75-200 Centipoises
0.075-0.2 Pascal Second
Solution
(Density)
1.13 g/cc
1.07 g/cc
NMP^^Vxylene
NMP/Xylene/Cellosolve
Solids
(2 gms, 2 hours
§ 200'C)
Solvent
Filtration
40*C
40*C
Flash Point
(Closed Cup)
0.2 Micron Absolute
0.1 Micron Nominal
FILM PROPERTIES (1)
PI-2560 and PI-2562
Physical
Tensile Strength (ultimate)
Elongation
Density
Refractive Index (Becke Line)
Flexibility
Thermal
Melting Point
Weight Loss @ 316*0 in air,
after 300 hours
Final decomposition temperature
Coefficient of thermal expansion
Coefficient of thermal conductivity
Flammability
Specific Heat
19,000psi (1.31x10^ Pascal)
9%
1.39 gms/cc
1.70
180* bend, no cracks
None
4%
560*C
c
4.0 X 10'V*C
35 x 10-5
^ cal
(cm) (sec) (*C)
Self-Extinguishing
0.26 cal/gm/*C
(1) Typical properties; not to be used for specification purposes. (See PC-11 and PC-12)
(2)
^ ' N-methyl-2-pyrrolidone
-3FILM PROPERTIES^^^ (cont'd)
Electrical
Dissipation Factor (IKHz)
Dielectric Strength
Volume Resistivity
Surface Resistivity
Dielectric Constant (IKHz)
.002
4000 volts/mil
10
ohm-cm
10
ohm
3.5
PROCESSING
PI-2560 and PI-2562 are similar to the PI-2550 PYRALIN*
series in rate of imidization. The processing conditions described in Bulletin PC-1 Hill generally apply to PI-2560 and
PI-2562 for dry etch only.^ ' However, the coating thicknesses
derived from this material may be of the order of 1 mil, greater
in most instances than with other formulations, so that an increase in prebake or final cure is necessary to deal with the
extra thickness.
Prebake before etch should be 30 minutes at 80*C, 30 minutes
at 105*C, and 30 minutes at 125*C. A final cure of 30 minutes at
180*C and 30 minutes at 300*C or higher is needed to achieve full
imidization. Bubbles appearing during or after the final 300*C
cure indicate a longer exposure at 180*0 is necessary.
STORAGE STABILITY
PYRALIN* polyimide coatings are sensitive to heat and should
be refrigerated at 4*C maximum.
Freezer storage (-18*0) will
practically eliminate any viscosity drift and prolong shelf life
significantly. Viscosity stability of PI-2560 is similar to
PI-2550. Viscosity curves are found on Page 9 of Bulletin PC-1.
Moisture contamination is detrimental to stability and must
be avoided.
Containers should be brought to room temperature
before opening to avoid moisture of condensation.
Typical properties; not to be used for specification purposes. (See PC-11 and PC-12)
(3)
PI-2560 is difficult to wet process consistently with known
etchants. Therefore, wet processing is not recommended
T
-4TOXICITY/HEALTH HAZARDS
Adequate ventilation must be provided and skin contact
should be avoided. Exposed areas should be flushed with water
immediately.
Rubber gloves resistant to the solvents in PYRALIN* polyimide coatings can be procured as follows: for general purpose
use, the "Buta-Sol milled butyl rubber glove (Norton Company,
Safety Products Division, P.O. Box 4367, Charleston, SC 29405);
for light service, the "Wil-Gard" No. 26-640 tan latex industrial
glove (Edmont-Wilson Division, Becton Dickinson and Company, 1300
Walnut Street, Coshocton, OH 43812); and for service requiring
greater resistance to wear, the Natural Latex Rubber Glove No.
2911 (B.F. Goodrich Engineered Systems, 500 S. Main Street,
Akron, OH 44318).
Data supplied by the General Aniline and Film Corporation
indicate that animals exposed to air saturated with N-methyl-2pyrrolidone for six hours daily for ten days tolerated the conditions of the experiment and gained weight normally. Other animals subjected to 20-day dermal toxicity studies had no specific
degenerative changes and did not have a remarkable degree of skin
irritation.
AVAILABILITY
Available in one-half kilo, one kilo, and four kilo containers from:
Du Pont Company
85 Mill Plain Road
Fairfield, Connecticut 06430
Attn: B.T. (Brian) Lynch
Phone: (203) 259-3351, Ext. 247
For additional technical information, call V.S. (Vic)
Bowers, (302) 774-0259. Telex: 83-5420. Cable address: FABFINISHES.
Bavld KleinfeldRoom 6H'-4?4-
- •"
^
600 Mountain Avenue
Mu irroy Hill
POLYIMIDE COATINGS FOR ELEiinuN. uw
07974
DuiiBiiii -ir, V/-2 Rev. 3/82
PRELIMINARY INFORMATION BULLETIN
SPIN COATING TECHNIQUES
PYRALIN can be applied to semiconductor wafers
using standard photo resist spin coating techniques.
Spin coating provides uniform, pinhoie-free coatings
and can be controlled in thicknesses between 1000
Angstroms and 35,000 Angstroms.
Most development work done to date has used
3 inch wafers. Data are being generated using
larger diameter wafers.
Each of the following variables will affect the uniformity and overall quality of the final film and should
be controlled to obtain consistent results:
1. Wafer preparation
2. Adhesion promoter
3. Dispensing
4. Spin speed
5. Cure
of spinning equipment offer pumps for PYRALIN
solutions which control accurately the amount
dispensed.
Variations in the amount of solution dispensed can
cause variation in average film thickness at any given
spin speed. In general these variations will show up
more at spin speeds below 4000 rpm and will be
minimized as speeds approach 6000 rpm.
The best results have been obtained by dispensing
onto a wafer at rest and then bringing the wafer
up to speed as rapidly as possible. A final filtration
of PYRALIN as the material is dispensed is
recommended.
2. ADHESION PROMOTER (VM-651)
Spin apply as detailed in PYRALIN Bulletin PC-7
(Du Pont Bulletin E-41093).
4. FINAL SPIN SPEED
For best control, final spin should be maintained
between 4000 and 6000 rpm. The PYRALIN solution
viscosity can be adjusted with T-9035 thinner so that
operations can be maintained in this speed range. If
PYRALIN is thinned, it should be allowed to stabilize
at least 12 hours before using.
The film as deposited on the wafer is a wet film and
will shrink about 75% during cure.
Chart 1 (on page 2) shows the relationship between
spin speed of a 3 inch wafer and final dry film
thickness of PYRALIN 2555 after curing at 400°C.
Charts 2 through 7 show the percent solids vs.
viscosity of all commercial PYRALIN solutions. Solids
content are listed on the product sheet. To use Charts
2 through 7, start with the original solids of the material, multiply by the original volume and divide by the
reduced volume. This calculation will give the reduced
solids content. This reduced solids figure on the charts
will give the reduced viscosity.
3. DISPENSING PYRALIN*
A three-inch wafer was used for tests. Similar
infonnation must t»e developed by the user for wafers
four inches or larger.
Dispense 1 cm^ of PYRALIN on 3 inch wafer. It is
very important that the amount of material dispensed
remain constant for each wafer. Most manufacturers
The final film thickness of any of the PYRALIN
solutions should t>e close to those figures shown on
Chart 1. There will be some difference due to solids
content; however, this will serve as a guide or starting
point in developing the exact film thickness desired.
The best results have been obtained by spinning for
60 seconds. This length of time partially dries the film
and minimizes edge pull back and eyeholing.
1. WAFER PREPARATION
The purpose is to provide a clean, dry surface. One
process which yields good results is:
• Degrease in Freon® for 1 to 2 minutes with agitation.
•Air dry
• Rinse in deionized water at room temperature for
3 minutes.
• Rinse in isopropyl alcohol for 20 seconds.
•Air dry
• Bake for 20 minutes at 300°C to insure dryness
and cleanliness.
•Cool wafer to room temperature.
Du Ponfs liability is expressly limited by Du Ponfs conditions ol sale shown on Seller's price list or
Buyer's copy ol Seller's order acknowledgment forni (ifused) and Seller's invoice. All technical advice,
recommendations and services are rerxlered t>y the Seller free of charge. While based on data
believed to be reliable, they are intended lor use by skilled persons at their own risk.Seller assumes no
responsibility to Buyer lor events resulting or damages Irtcurred from their use. They are not to betaken
as a license to operate under or intended to suggest lnfrir>gement of any existing patent.
./If
5. FILM CURE
detemnined, wafers may be coated and the other
operating variables studied.
To obtain an accurate thickness measurement, the
wet film on the wafer should b>e fully cured. A typical
method would be 30 min. take at 135°C, one hour at
SOCC and 10 min. at 400°C. Details on curing
methods are listed in PYRALIN* Bulletin #PC-1.
Refefoncm
1. F.L Givens antj WJ. Daughton - Recent News Paper 381
presented at the Electroctiemical Society Meeting, Pittsburgh,
Pennsylvania, October 15-20,1978.
2. Bulletin #PC-7 Du Pont Bulletin 41093.
3. Du Pont Bulletin, PYRALIN PC-1. Adhesion Promoter (VM-651).
Once the desired dried film thickness has been
obtained and the operating spinning parameters
CHART'#1
PI-2555
FULLY CURED AT 400°C
Using VM651
3" Wafer
T9035 Thinner
to
c
o
Viscosity = 11 poise
1-- Part P!:2555 - 1 Part T o n J " " ^ PartT9035
1K
CHART #2
PI-2555
2K
3K
4K
Spin Speed - RPM
REDUCED WITH T-9035
5K
6K
CHART #3
PI-2550
REDUCED WITH T-9035
100
80
60
1UU
80
60
Viscosity = 2.1 poise
Viscosity = .55 poise
,
40
40
30
30
20
20
10
8
1
10
/
/
1'
/
/
I
6
2- 3
1 2
0.6
/
0.4
/
/
/
1.0
0.8
0.6
//
0.4
/
0.3
1
0.2
0.1
12
16
% Solids
20
24
28
0.1
12
16
% Solids
20
24
28
/
HART #4 PI-2560 REDUCED WITH T-9035
TOO
100
80
60
80
40
40
30
30
1
60
20
j
20
10
8
11
/
10
8
/
/
/
/
'
6
I
=
CHART #5 PI-2566 REDUCED WITH T-9035
3
6
^
3
J '
1.0
0.8
1.0
0.8
1
0.6
0.6
/
/
/
0.4
0.4
0.3
0.3
/
0.2
0.2
0.1
16
24
32
% Solids
40
0.1
44
CHART #7 PI-2545
CHART #6 PI-2540 REDUCED WITH T-9035
12
16
% Solids
20
24
28
REDUCED WITH T-9035
100
80
80
60
60
.
j
40
40
/
30
30
/
20
20
/
_
6
^
3
::
2
10
8
1/
j
10
8
1
6
/1
'
I
£•
3
>«
2
1.0
1.0
0.8
0.6
/
0.8
/
/
0.6
/
04
0.4
0.3
0.3
0.2
0.2
0.1
12
16
% Solids
E-45524
4/82
20
24
28
0.1
12
16
% Solids
20
24
28
Printed in U.SA
-I, •
* ^
PROCESSING DIRECTIONS
PI-2555 - 1.5 MICRONS THICK
PASSIVATION LAYER
1.
Clean Wafer - Blow clean using nitrogen for 4 seconds at
2500 RPM.
2.
Apply 3 ml VM-651 adhesion promoter solution.
Mix (every two weeks) a solution of 95% methyl
alcohol and 5% DI H.O. To this, add O.lt VM-651
adhesion promoter. Mix by shaking or stirring.
Allow mixture to normalize 12 hours before using.
(See Bulletin PC-7 for further details.)
3.
Spin wafer 30 seconds at 3000 RPM.
4.
Adhesion promoter is used only over Si, Si02r or CVD surfaces, not on a previous polyimide coating.
5.
PI-2555 can be dispensed as received or it can be thinned
with T-9035 Thinner (8 parts PI-2555 to 1 part T-9035).
Apply 3 ml to center of the wafer (4") while wafer is
stationary. Bring spinner up to full speed (3500 RPM)
immediately.
(See Bulletin PC-2, Rev, 3/82, for further
details.)
IMPORTANT:
PI-2555 removed from freezer or refrigerator
should be allowed to equilibrate to room temperature before
the container is opened.
\
6.
Soft bake wafer for 30 minutes at 140*C. A hot plate or
recirculating air oven is preferred. Infrared may be used,
but remember IR is absorbed and the temperature of the film
may exceed the temperature setting of the oven and cause
poor results.
7.
Let wafer cool for 10 minutes.
8.
Wafers should be coated with photoresist within 24 hours.
9.
Blow clean with N. for 5 seconds at 3500 RPM.
10.
Apply HMDS adhesion promoter for photoresist if desired.
11.
Spin apply Shipley AZ1350J, AZ4210, or equivalent.
12.
Soft bake resist 20 minutes at 90*C.
13.
Expose in any standard contact, or proximity printer.
Length of exposure will depend on light energy available
from equipment.
David Kleinfeld
Room 6H-424
ATT Bell Laborator.Les
600 Mountain Avenue^
Murray Hilly N»J. 07974
\-
-214.
Use Shipley MF312 or other desired developer to develop the
photoresist and at the same time etch the PYRALIN*. The
developer should be diluted with DI H2O so that it has a
normality of .25N to .3N. We suggest a spin spray develop
for best results. Second choice is a spray, then agitated
dip, and last choice is a straight dip.
15.
Etch should be complete in less than 30 seconds in a spinspray piece of equipment.
Slightly higher temperatures
(30*C) will speed up etch rate.
16.
Strip photoresist with 60% butyl acetate, 40% isopropanol
solution at room temperature. Spray stripping is best. If
any cracking of the PI is seen, increase the soft bake
(Step 6) in 5*C Increments until cracking is no longer
present.
17.
Rinse for 30 seconds at 1000 RPM with DI H2O.
18.
Blow dry in N. for 30 seconds at 3000 RPM.
19.
Full cure 30 minutes at 300*C)
30 minutes at 400*C)
In Nitrogen
PROCESS FOR DEPOSITING A 1.5 MICRON PYRALIN* FILM ON A 4" WAFER
AND OPENING VIAS BY A NEGATIVE WET ETCH PROCESS
1. Clean wafer. Use RCA or Pirannah clean or a Freon* Method. Bake at IBO'C
for 10 minutes.
2. Prepare and apply adhesion promoter in accordance with Bulletin #PC-7, Rev. 4/82.
3. Apply approximately 3cc of PI-2555 (PI-2545) thinned with T-9035 (8 parts PI-2555
to 1 part T-9035) to center of wafer on spinner. Note: Dilution should be made
24 hours in advance of use. Wafer should be at rest. Bring to full 3500 RPM
immediately. Spin for 60 seconds. See Bulletin #PC-2, Rev. 3/82, for further
details.
4. Soft bake wafer 30 minutes at 125''C. We suggest a hot plate or recirculating
air oven. Infra-red may be used but remember that polyimide absorbs infra-red
and the temperature of the film may exceed the temperature setting of the oven
and cause poor results.
5. Let Wafer cool for 5 minutes.
c
6. Apply HMDS adhesion promoter for resist if needed.
7. Spin apply a negative resist such as 747 Kodak. Caution: To achieve a 45' via
wall slope, the photoresist should be applied, developed, and the polyimide etched
within one hour. Long delays bwtween application of the photoresist and developing
' and etching can cause change in the slope of the via walls.
8. Soft bake the photoresist 30 minutes at SO'^C.
9. Expose in any standard contact or proximity equipment. Length of exposure will
depend on photoresist used and light energy available from equipment.
10. Develop following photoresist manufacturing instructions.
11. Hard bake resist for 20 minutes at 135'C.
12. Use Shipley MF312 to etch PYRALIN*. The MF312 should be diluted with deionized
water so that it has a normality of .25N to .3N. We suggest a spin spray etch
for best results. Second choice is spray, and last choice is straight dip.
c
13. Etch should be completed in about 30 seconds in a spin spray piece of equipment.
Vias can be held to 3-4 microns. Slightly higher temperatures {30*C) will increase etch rates.
:
David Kleinfeld
Room 6H'-424
ATT Bell Laboratoriieti
600 Mountain Avenue',. '' .• .
•: Murray. Hill, N.J»,. 07974 •• .^
-214. Bake for 30 minutes at 160"C.
4
15. Strip photoresist with standard stripper like 712D or JlOO at 80-85'C. If the
stripper attacks the PYRALIN*, increase the bake in Step 14 by 10*C Increments
until attack disappears.
16. Rinse with deionized water - 5 minute dip, 5 minute spray for 2 cycles.
17. Fully cure at: 30
30
10
5
minutes 300**C)
minutes 400'C) <_ km-^-ominutes 450»C ^" Nitrogen
minutes 500*C)
18. Neutralize with a 1-3% acetic acid solution. Then rinse as In Step 16.
This should provide an adequate film that will withstand second layer metal
deposition temperatures.
Back sputtering or low pressure oxygen plasma clean^should be used to clean
vias before second metal deposition.
>^
^
If second layer metal adhesion is poor, a 5 minute low pressure oxygen plasma
will roughen the PI surface and improve adhesion.
VSB/lgb
8/20/82
V
i
t'avid Kleinfeld
Room 6H'4?4
600 Mountain Avenue
Hurray H i n , N.J. 07974
DRY ETCHING PYRALIN^
Attached are two excellent papers covering both plasma etching
and Reactive, ion etching of polyimide films. I believe one word of caution
is necessary whenever plasma or RIE is discussed. No two etch reactors
behave exactly the same even though they are the same size, model number, or
share the same specifications. Infonnation on dry etching techniques can and
should be used as a guide, but exact results probably cannot be duplicated
on similar equipment.
A Guide to 0^ plasma etching fine line geometries follows:
VSB/m-nc
Attach.
1.
Best results are obtained etching fully cured, PI films.
2.
For etching small vias, a mask other than photo resist should
be considered. This mask can be a metal mask, silicon nitride,
or a spin on-glass. T. 0. Herndon's paper reports good results
using spin on glass. This may be more economical than the
other alternatives.
3.
After mask imaging a neutralization rinse in 1% to 3* acetic
acid is suggested to neutralize any sodium ions which if allowed
to reTisin on the surface, can cause non uniforir, etch rates across
the wcfer surface. The neutralization is followed by a DI wcter
rinse.
4.
To etcb almost straight walls, in a single wafer parallel plete
etcher, a power of 100 watts and 50 millitorr can be used with
straight O2 gas. Etch rate will be about 900 A/rrin.
5.
Fester etch rates may be obtained by using higher power,
pressures, and temperatures. 3500 A/rr,in. etch rates have beedeiTion St rated at 300 watts and 50 millitorr. If, at 300 wctts,
pressure is allowed to rise to 2000 millitorr and temperature
to IBO'^C, the etch rate is too fast to control.
6.
Another approach being used is to etch at high power (300 watts)
and high pressure (1500 millitorrs) to obtain an isotropic etch.
halfway through the PI film. The pressure and power is then
lowered to 50 millitorr and 50 watts to obtain an anisotrooic
etch speed, a 45" angle through part of the film and straight
walls through the remaining film for good metal step coverage.
gasagggi^g«*g»^'g^
Inten&etal Polyimide Via Coodltlonlng and Plasma Etching Techniques*
T.O. Eemdon, R.L. Burke, V.J. Landoch
MIT Lincoln Laboratory, Lexington, KA
02173
Polylolde has nuj&erous advantages as an intennetal insulator for
Integrated circuits Including self-levelling, lev defect density, a
large range of useful thicknesses and ease of application. The high
resolution required for the via openings utilized In VLSI has stlisulated
the study of factors vhlch directly affect via dimensions and via
contact resistance Including: etching power and pressure, photoresist
characteristics, premetal cleanup and thermal curing. In these
experiments the polyimide used was DuPont PI2555 and Che vias were etched
by 0. plasma in a 7" diameter parallel plate reactor with aluminum
electrodes spaced 1.5" apart.
The standard procedure for eliminating so-called "Invisible shield"
Involves etching 80Z of the P.I. thickness at 250 millitorr and
finishing the etch at 50 millitorr, both at 50-100 watts . This final
etch at low pressure eliminates the redeposltlon vhlch Is found to occur
at higher pressures. Attempts to simplify this schedule by etching the
full P.I. thickness at 50 millitorr, using 300 watts R.F. power In order
to increase the etch rate, has been found to cause several problems.
The standard schedule etches both the P.I. and the Shipley AZ photoresist
at 1,000 %/mln. This rate drops to 250 X/mln. for the 50 watt, 50
millitorr condition. Etching at 300 watts, 50 millitorr Increased the
polyimide etch rste to 3,000 A/aln., but the photoresist etch rate
increases even more to 4,300 X/min. A second undesirable effect cf
Increasing power from 50 watts to 300 watts is that the etching of the
P.I. and photoresist, which are anisotropic at the low power, become
isotropic at high power. Thus, the via dimensions enlarge at a considerably
greater rate at the high power level with the sldevall in the P.I. via
becoming rough and tapered at approximately a 45 angle due to che
photoresist erosion. Furthermore, che amount of residue left In Che
bottom of the completed vias is considerably greater than in the case of
etching at 30 watts and 50 millitorr. This residue vhlch is clearly
visible In SEX Images, can be removed by continuing Che etch at 50 vatts
and 50 millitorr, and It can be removed in buffered EF. SDt studies of
Che reslst/P.I. layers etched at the 300 watt, 50 millitorr pressure
conditions Indieste the high etch rates and pronounced roughening of the
resist surface/ P.I. via sldewalls are probably due Co sputtering vhlch
Is augmenting the normal O^/polyner chemistry. This sputtering is also
thought CO be responsible for che residue left at Che bottom of the vis
openings vhlch is caused by knocking off chunks of reslst/P.I. It is
concluded that successful plasma etching of P.I. using photoresist
SAsking requires completing the etch at low r.f. power and low pressure
Co eliminate these problems.
This work vts sponsored by the Departaent of the Air Force
The U.S. Covcrnsent asEuaes no responsibility for the information presented.
Positive photoresist on polyimide requires long exposure times due
CO Che absence of back-reflecdon from che light absorbing under layer.
It Is also limited as a nask for 0, plasma ecching since che resisC
erodes ac lease as fase as Che P.I. The use of aluminum or chromium as
a non-erodable mask for P.I. has been demonscraCed but Che added complexity of deposlclng meCal Is a drawback. Ve have Investigated spin-on
glass as an easily applied and removed nonerodlng mask. In this case,
Slllcaflla from Emulslcone Co. Is spun on fully cured P.I. aC 10,000 rpm
and baked for 15 minutes at 250 C. This produces a pinhole free glass
layer approximately 1300 A Chick. AZ reslsc is spun on Co a Chlckness of
1 to 1.2 microns, exposed and developed using normal Cechnlques. The
glass is Chen plasma ecched In CF, + 0. ac 250 millicorr pressure and 50
vaCCs power In a parallel place reaccor vlch an eCch race of 450 j^/min.
Ihis etch is reasonably selective, relative Co Che phocoresisc, and
does noC ecch Che P.I. at all. Following the glass definition, Che P.I.
can then be eCched in 0. plasma during vhlch time the phoCoreslsC is
coaplecely reiboved. The spin-on glass can be scripped elcher vlch CF, •f
0^ plasma or in 100:1 HF. The beneflcs of Che spin-on glass are its
ease of application and removal, its complete resistance to 0. plasma,
vhlch permits etching thick P.I. sections, and Che absence of residue in
Che via after etching regardless of plasma pover.
A third major faccor affecdng via yield Is surface preparation
prior Co metallization. The use of buffered HF laroediately prior Co
second level metal has been described . However, some applications
cannot tolerate HF, and ve have found Chat a 90 second dip in a 1:1 mix
of Shipley KF 312 and water is a reasonable substitute for HF to effect
aluxslnua oxide removal. On the other band Che use of argon sputter
cleaning after resist removal, vhlle it gives consistently low via
contact resistance, leads to very poor adhesion of metal to P.I..
Examination of SUi photos indicates that Che argon sputter process
breaks up the P.I. surface into either a very fine powder or loosely
bo\ind particles, vhlch causes such poor adhesion that Che top metal may
fall off nearly spontaneously. If argon sputter cleaning is used, it
must be prior to resist removal to prevent Chis problem.
A final area of difficulty has been bubbling of Che overlying metal
during 450°C sinter. This occurs only in large (100 SEQ ) , unpattemed
areas such as those vhlch re&aln at Che outer edges of DSV exposed
wafers. Experiments have vtrifled chis is due Co ouCgassing of Che
P.I., probably caufed by absorbed liquid from EF dip and^rlnse steps.
It has been demonstrated chat baking Che P.I. aC 300-400 for half an
hour prior Co application of metal eliminates chis bubbling. However,
ic has also been found chat baking the P.I. at Cesperetures above 150 C
prior Co metallization leads Co very poor via concaccs. There is Auger
evidence Chat putgassing from Che vis sldewalls or surface of Che P.I.
deposlcs an insulating carbonaeous material at Che bottom of the via.
elimination of metal bubbling can be achieved without this deleterious
premetallization bake by increasing Che sinter Cespereture gradually in
15 minute-long increments at 150
300 - 400° - 450°C.
76
——"^
t
REFERENCES
1.
T.O. Hemdon and R.L. Burke, "Inter-Metal Polyimide Insulation
for VLSI, "Kodak Microelectronics Seminar, Kev Orleans, LA,
Ccc. 1979.
2.
D.R. Day, R. Vhlccen, S.D. Senturla, "Invisible Shield in
Polyimide Vias - An Auger Analysis," E.C.S. Meeting, Denver,
CO, Oct. 1981.
3.
T.O. Hemdon, R.L. Burke, J.A. Tasaitls, "Use of Polyimide in
VLSI Fabrlcadon," E.C.S. MeeCing, Denver, CO, Occ. 1981.
77
DRY ETCHING; REACTIVE ION ETCHING
The processing of semiconductor devices Involves the use
of a variety of organic films. Mainly these films are photoresists used for masking purposes. More recently, organic - films
such as polyimide are being used as insulators. Therefore, the
•tching characteristics of organic films is of Importance. The
literature has mainly dealt with the stripping of resists in an
oxygen plasma. This part of the course will deal with the
reactive ion etching of organic films in both 0^ ftnd CFn plasmas.
The organic films investigated are AZ1350J, KMR, PKMA,
polyimide and polysulfone. Etch rate data as a function of
system paraneters are presented. Despite the structural differences
in these organic films, all the materials with the exception of
PKKA etch at the same rate under the same conditions.
Many differences were observed in the etching of organic filr.s
in a 02Plasr.a compared with a CF^ plasma. In general the etch
rates are lower in CF^ th&r. in an 0. plasma. Loading effects
occur in both plasmas but to different degrees. In a CF4 plasr.£,
a large decrease in the etch rate of the organic film is observed
as the cathode is loaded with either organics or Si. A small
loading effect is seen in an O2 plasma with the addition of
organics only. The influence of loading on etch rete unifornity
will also be discussed.
Prcfiles of organic films etched in an O2 plasma with a
non-erodible mask are considerably different from profiles
obtained in a CTn plasma. In an O2 plasma, undercutting is
observed as a function cf pressure. Under the same conditions
in a CIu plasma only vertical profiles are observed.
Siurface rougher.ing and residue are exanined as a function
of etching conditions, since the functional organic films are
left in place. For the thermally stable organic materials such
as polyimide, surface roughening and residue formation are related
and are a fxu^ction of pressure. Residue is produced by backscattering of sputtered inorganic material and also by inorganic
particles in the organic films. Generally, as the pressure is
increased more backscattering occiurs. However, in en O2 plasr.a
the amount of luidercutting which increases with the pressure,
results in a smoother surface.
A process fcr fcming vias in polyimide by reactive icr. erchir.c
.vill also be discussed.
13.56 MHx
0.ie3Watt»/cm2
1400
1200
1000
I 800
o
. / ^
S 600-
E
/
<0C
*
PolyifTiide
c A21350J (310=C-N2 Baked)
o PNmu
200
20
40
60
80
O2 Pressure (Millitorr]
ICO
0
OPEN SYMBOLS: ^0.68 KHZ
CLOSED SYMBOLS: 13.55 MHZ
0 0 . 6 5 3 WAH/CM^
1=
O 0.A89
250-
326
163
200^
UU
i
150-
LU
100—
50-
r,
20
^0
OXYGEN PRESSURE
Fig.10
50
80
( MILLITORR )
100
•^.I
• • ^
••
•/•-••
u.
u
o 8102'
o ITrvTRilOO^C Baked)*!
• A'Z135'0J (Slb^C-N^Baked);
A AZ1350J (90OC Baked)!'
•
5
c
»-
50 Milltorr CF4
cc
LLU
E
• "t*
_c
•-; -v .:• v .
(J
ICCO
TEiVIESCAL
0.25 Watts/cm2
80 Millitorr O2
— 3.
.0—0-
I 2CCC w
1CCC
rr'-
£v
40
60'
0 I iw./ IwWv/i.'l,
80^
iCO
(
Ul
1
JCOOr
TSMESCAL " \
0.25 Watts/cm2 \
100 Millitorr O2 >
100 SCCM Fiow O2
Si02 Plats
c
c
1CCC
10
2C
30
40
if .'='civirr.ics Covered Wafers (STnrn)
I
rr
T
RESIDUE
.AS A FUNCTION OF GAS
(
c
50 MILLITORR 0-
50 MILLITORR CFz,
U.
U.
c
ph3
AFTER RIE I?! O.XYGE"
.RESIDUE RLMOVAL A R E R - D I P IN BHf
c
r
•'yjia.'ignvjnimii^^m^imsifmmmmiMmmmfMCt^ixi^^
>;•
^"^
^»«i»>ii(w^'^^UU'*«^.- •-
. L l J i V l i . i • ? '•
RIE of Vias in Polymide
RcsistI
I AlCuj I
''^'y"^'^"'
r-Aicdi
^^'^"^^^"' F M C ^
1. Apply Polymide
and Fully Cure
2. Apply Thick Layer
of Resist (Must
bo Thicker than
Polymide Layer)
3. Define Via Pattem
In Resist "'
4. Post-Bnkelfor 30
Minutes at 130<'C|
5. RIE In O2 Plasma
6. Strip Resist In
NMP al 60°C
TRM-nF- 17
y c^;30 t^^
^ ' ^
A
r^-^.v^i r ^
References
Adhesion
1. X. L. Kittal, Electrocosponent Sei ( Tech., Vol. 3,
21-U2, (1976)
2. K. Kendall, J. Adihesion, Vol. 5, 179-202 (1973)
3. K. D. Bascom, Macromolecules, Vol. 5, No. 6, Nov.-Dec. (1972)
4. L. B. Rothnan, J. Electrochem. S o c , Vol. 127, No. 10,
Oct. 1980.
Planarity
1. K. Sato, S. Earada, A. Saiki, T. Kimura, T. Okubo, and
K. Mukai, IEEE Trans. Parts, Hybrids, Packag., Ph p-9
176 (1973)
2. A. Saiki, S. Earada, T. Okubo, K. Mukai and T. Kimura,
J. Electroche.-. S o c , 12«, 1619 (1977)
RIE
1. G. C. Schwartz, L. B. Zielinski, T. Schopen, Proceedings
Vol.- Etching for Pattern Definition" J. Electrochem S o c
(1976)
2. J. K. Ecllahan C A. J. Bell (Editors) , "Tech.-iques and
Apolications of Plasma Chemistry," John Wiley, New York
19*7a.
• TYPICAL OPERATING CONDITIONS:
• 35 X 10"' TORR PRESSURE
t 0)CYGEN GAS
§ 500 WATTS R.F. POWER
• 2 TO 5 niNUTES
t ftUFFEfOl MF IIP TO REHOVE At OXIBE
• WHY THIS nETHOO IS USED:
f QUICK
• RELATIVaY CLEAN
0
AL S I K T E R I K S P » ) 5 A 5 L Y
f^T S E E Z O
• EXCELLENT IF PLASMA ET<CHI«G P I
• CAM BE USED 0» SOfii DEVICES tftCRE SPOTTERIRG CAKKOT BE
ISO).
• IDST CUSTOf^RS HAVE V E EOUIPfCNT
m
i.
•u;#r» rSv
David Kleinfeld
Room 6H~A24
ATT Be.!. 1 Laboratories
600 Mountain Avenue
Murray Hill, N.J. 07974
PHOTOREACTIVE
POLYIMIDE
PAL
PRECURSOR
,^ V
I
• ^••••^ w i f f l u « M i f •..%'. .T:...-.T-.T
•«;.;
'!>:'
i. THE UTILITY OF PHOTOREACTIVE POLYIMIDE PRECURSOR IN MICROFABRICATION OF THE ELECTRONIC DEVICES
1) SHORTENING THE POLYIMIDE LAYER PATTERING PROCESSES
2) No NEED TO USE POLYIMIDE ETCHANT SUCH AS HYDRAZINE HYDRATE^WHICH HAS A CONSIDERABLE TOXICITY
PREVIOUS WORKS FOR PHOTOREACTIVE POLYIMIDE PRECURSORS
1) R. H. KERWIN E T AL.7 POLYMER ENG. AND SCI., U . '126 (1971)
2) R. RUBNER, SIEMENS FORSCH^ U, ENTWICKL., 5> 92 (1975)
3) T. HIR MOTO E T AL.> DENSHIZAIRYO. f\7 (1981)
I ••
I
I
Paccerning of Al
layer
1. PI. precursor
coating
2. ThernaL curing
1. Photoresist
coating
2. UV ray exposure
Patterning of Al
laver
-PI.
Photoresist
/
1. Photoreactive PI.
precursor coacing
2. UV ray exposure
Photoreactive
P I. Precursor
1 Development
2. Post-baking
PI.
1. Development
2. Thennal curing
etching
Removal of che
phocoresisc
Formation of upper
Al l a y e r
a) Paccerning of an o r d i n a r y
polyimide l a y e r
PI = Polyimide
Formation of upper
Al l a y e r
b) Paccerning of a polyimide
l a y e r by u c i l i z i n g i c s
phocoreaccive p r e c u r s o r
FIGURE I . A COMPARISON OF THE POLYIMIDE PAHERNING PROCESS UTILIZING AN ORDINARY
PRECURSOR WITH THE NEW PROCESS UTILIZING A PHOTOREACTIVE PRFrMR<:no
!»««<«•• * • > • «
Ii. CHARACTERISTICS OF THE PHOTOREACTIVE POLYIMIDE PRECURSOR " PAL ".
( PAL = PHOTOREACTIVE POLYAMIC ACID FOR LITHOGRAPHY )
,
1)
HIGH SENSITIVITY:
10-12 MJ/CM2
2)
HIGH CONTRAST: V «
3)
EXCELLENT FINE PATTERN PRODUCTIONABILITY
AT
365 NM ( THICKNESS: 3-5^m)
1.1-1.6
RESOLUTION FOR LINES AND SPACES PATTERN IN 1.1pm
RESOLUTION FOR THROUGH-HOLE PATTERN IN 1.1pm
1)
THICKNESS:
3nm
THICKNESS: 5 pm
ALMOST COMPLETE REMOVAL OF THE PHOTOREACTIVE GROUPS OR COMPONENTS AND
CONCOMITANT IMIDIZATION WITH A THERMAL CURING TREATMENT
•IS
Table
Liquid Properties of
Item
Viscos 1 ty
Sol i d C o n t e n t
I m p u r 11 les C o n t e n t
PAL
Unit
Property
CPS
2500
%
1 4.2
Ppnn
Na
1.8
K
0.1
Fe
0.8
Cu
<0.1
F i1tratIon
A/m
1.0
•
'
^
'
:
'
-
'
V.
"G LAMP EMISSION
• *^ *
>
4-»
>»
u
(0
u
If)
y
c
0)
<u
CO
1.
^«
200
400
^ ^ ^ « Length
F/GURE
SPECTRAL SEIMSITIVITY FOR PAL
-L-
450
(nmj
500
550
.r
1
1.0
1 I i I i ii|
p
i
c
u
=
i
1
i i i i i i
-
.o^
0)
i I I i il|
0.8
-
0.6
-
^
•o—o—o-
Jid
i=E
in
•a
N
E
u
O
0.4
^ D o t t e d line is an ordinary
negative photoresist.
-
1
• • ^ -
0.2
LocDr
-
LOGDO
SENSITIVITY ( DQ.J )
0
-
Z
1
I i l i l i l
10
10
Exposure
FIGURE
I
Dose
I
I
I
10
( mJ/cm^
I i i i i.
10
at
EXPOSURE CHARACTERISTIC FOR PAL WITH UV RAY IRRADIATION.
3 6 5 nm )
]5T
1.0
(0
tn
c
Exposed f i l m ( exposure dose; 100 m J / c m ^ )
0.8
o
IE
i-
T3
. 0)
N
E
u
O
0.6
0.4
0.2
— \ -»- Unexposed f i l m
2
\
J-J
JX
0
8
Development
FIGURE
Time
10
12
I min )
DEPENDENCE OP DEVELOPMENT TIME FOR TIIE REMAINING FILM THICKNESS.
14
\.
•.• FIGURE
PATTERNS IN 1,1 pm THICK PAL MADE WITH CONTACT PRINTING. '
I
. t
I
i!
'V
I
100
0)
u
c
ni
E
in
c
(0
Film
FIGURE
Thicl^ness
(H"^)
DEPENDENCE OF FILM THICKNESS FOR THE UV ABSORPTION OFfAL-i
I
•
* . •
III. CHARACTERISTICS OF TIIE POLYIMIDE PRODUCED FROM " PAL ".
1)
RETAIN THE * PAL * PATTERNS SATISFACTORILY
2)
HIGH HEAT RESISTIVITY
I
3)
GOOD ELECTRICAL AND MECHNICAL PROPERTIES FOR THE APPLICATION
OF THE MICROELECTRONIC DEVICES
'
A'
0
FIGURE
;:36P0
32PP
F T T I R TRABSHISSIOM
28
+2Dbo;j. hi 600-1 !.!1200
ftvrENUhBeRSi i m i h T'-ri :. I
t
11 I
^400;
SPECTRA FOR THE POLYIdlDE PRODUCED FROM EfiL.
600
|.|.r
7oo
!.:_.
r
0
in
0)
c
o
CoRRESPOflDIMG TO THE
0.8
ELIMINATED PHOTOREACTIVE
GROUP(S) AND VIATER
Ic
0.6
u.
0)
N
0.4
DEHYDRATION AND ELIMINATION
^ ( POLYAMIC ACID )
( POLYIMIDE )
OF THE PHOTOREACTIVE GROUP(S)
."(5
E
i: 0.2
o
0
100
200
,
Temperature
300
( °C )
FIGURE 7. REMAINING FiUI THICKNESS AFTER HEATING AT EACH lEMPERATURE FOR 30 MINUTES.
400
•Js^-.-
i.-1.
t
'I
•J
• —
pi,
FIGURE
PATTERNS OF pbLyiMlDE OBTAINED DIRECTLY B
BY HEATING THECAL PATTERNS.
• ^ : > -
•
I
y'V>.-,
FIGURE . PAHERNS OF POLYIMIDE OBTAINED DIRECTLY BY HEATING THE PAL PATTERNS.
"
It
^:>
500 -
P
0)
400 -
D.
E
0)
h-
300 -
300
350
400
450
Final Bake—Temperature Cc)
'%./
Temperature
scan:
5*C/min in N2
10
V)
cn
O
20
• Dotted line is an ordinary
Polyimide.
JZ
30
40
100
1
1
1
200
300
400
Temperature
FIGURE
J I
1
500
600
700
800
("C )
THERMAL GRAVIMETRIC ANALYSIS OF THE POLYIMIDE PRODUCED FROM EAL AFTER HEATING
AT 150*C FOR 1 HOUR IN N2 FLOW.
V^
'O,./
TABLE 1. ELECTRICAL AND MECHANICAL PROPERTIES OF THE POLYIMIDE PRODUCED FROM PAL.
PROPERTIES
ELECTRICAL
DIELECTRIC STRENGTH, KILOVOLTS PER MM
275
DIELECTRIC CONSTANT AT 1 KILOHERTZ
3.0
DIELECTRIC LOSS TANGENT AT 1 KILOHERTZ, PERCENT
0.22
VOLUME RESISTIVITY, 10^* OHM-CENTIMETER
0.6
MECHANICAL
TENSILE STRENGTH, KILOGRAM PER SQUARE MIL
377
TFNSILE MODULUS, KILOGRAM PER SQUARE MIL
12.8
ELONGATION, PERCENT
10
TYPICAL
PROCESSING C O N D i T i O N
FOR OB TA i N i NG 2.5 um TH I CK
P rocess
FILM
C o n d i t i on
( 1)
Prebake of
( 2)
Coat ing
Wafer
Coupler
1)
1)
200°C-10min
C o a t i n g of
P iC - C - 3
amount of coupler : 3 - 5 g / w a f e r
coating : 4000
(3)
Coating
PAL
rpm-30sec
2)
Baking: 350''C-30mln
in a i r
1)
Amount of
2)
C o a t i n g : 5 0 0 r p m - 1 0 sec.
or O ,
PAL : 5 - 6 g / w a f e r
+ 4 5 0 0 r p m — 3 0 sec
(4)
Prebake*
1)
7 0 ± 3 ° C - 3 O m i n , f I i m t h i c k n e s s : ca. 5.0 um
( 5)
Exposure
1)
Photomask : c o n v e n t i o n a l
2)
Pr i n t e r : contact
3)
Exposure:
*
Keep p r e b a k e t e m p e r a t u r e b e i o w 75°C.
UV
g l a s s mask
printer
100mJ/cm'
at
365nm
C o n d i t i on
P rocess
(6)
Development
1)
PAL - D e v e l o p e r
2)
Developing
t i me :
1 8 0 - 2 4 0 sec b y d i p p i n g
(7 )
(8)
R 1 n s i ng
Post
Bake
3)
Developing
1)
E t h a n o l : i 5 sec
2)
Drying
in
temperature :
method
23 -
2 5 °C
Nj
1)200''C-30min
in
air
+ >400°C-60min
inN,
Prebake
E
IA
10
O
c
u
Postbake
->
1
I
2
Spinner Speed
Fig.
I
1
4
(xlO*rpm)
C o a t i n g P r o p e r t y of PAL
Prebake : 7 0°C-3 0 m l n
Postbake : 2 0 0 ° C - 3 0 m l n + 4 0 0"C-3 Omin
"N
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