Positive Tone Photosensitive

Polyimide Coatings

TM
“Photoneece ”
PW-series
Toray Industries, Inc.

1
 PW-series introduction

Why is PI necessary for “Semiconductor

semiconductor’s package? Package Structure”

Why is POSI PI the most adjustable

“Semiconductor Process”
to semiconductor’s process?

Why is PW-series the best solution of

“Solution examples”
your problems?

2
 Semiconductor Package Structure
1.TSOP or QFP Mold compound
The reason why PI is necessary is
Polyimide ---to protect filler attack
---to increase package’s reliability
Lead flame (buffer effectiveness)

2.FBGA(stacked type) Mold compound The reason why PI is necessary is

---to protect filler attack
Polyimide ---to increase package’s reliability
Solder bump (buffer effectiveness)
---to protect upper IC attack

3.Bare chip (Bump structure) Gold bump The reason why PI is necessary is
Polyimide ---to protect IC substrate(PI acts
like encapsulation)
---to increase adhesion to ACF

4.Wafer Level Package(WLP) Gold Bump The reason why PI is necessary is

---to protect IC substrate(PI acts
Redistributed
like encapsulation
line(metal)
---to increase adhesion to ACF
Polyimide ---to distribute line
3
 Semiconductor Process
Non-photosensitive PI photosensitive PI The number of process
is fewer than non-PSPI.
Al passivation
Si
PI coating
Photoresist coating PI coating
photoresist

Photoresist coating

exposure exposure

Photoresist developing PI developing

NEGA PSPI
exposure --organic solvent
--low resolution
Photoresist &PI developing
Passivation dry-etching PI curing
POSI PSPI
--alkaline solvent
Photoresist stripping Passivation dry-etching --high resolution
Photoresist stripping
The most adjustable!

PI curing

exposure 2 times exposure 1 time 4

 The reason why PW-series is the most suitable for all applications
Solution examples is that PW-series has following features solving your problems.

The features of PW-series Solution

High chemical resistance

High adhesion strength Useful for Bump & WLP
Good taper shape

Low residual stress Useful for 12” wafer

Useful for advanced memory & logic

High resolution (Advanced memory= fuse box size is about 5um,
Advanced Logic= left pattern width is 7um)

Low price Useful for every device using “NEGA”

Is there any problems about above matters with you?

We can provide solutions by recommending PW-series.
5
1. Marketing Data

6
 Customer’s Requirement Trends for PI
Package Density
Ⅲ Semiconductor and package downsizing
【Requirements】 Ⅳ CSP(WLP) and bump application
Higher resolution 【Requirements】
Higher adhesion to passivation layer Excellent chemical resistance
High adhesion to various materials
Availability for multi layer(High Tg)
TCP

PBGA STACKED BGA

FCBGA
QFP
WLP

FBGA
BARE CHIP
TSOP （BUMP IC）

6inch 8inch 12inch Wafer Size

4inch

Ⅱ Cost reduction of process and materials Ⅴ 12inch wafer application

Ⅰ Higher package reliability 【Requirements】 【Requirements】
【Requirements】 Availability for aqueous development(TMAH 2.38%) Good photo-speed
High electric and thermal resistance Low temperature curing process/Good photo-speed Low residual stress and CTE
High adhesive strength Long storage life
High resistance for dry etching process(1 mask process) 7
 PI’s Technical Trend

Non Photosensitive PI (negative tone) Have vanished

To stop hydrazine process

Non Photosensitive PI (positive tone) Decreasing…

To be fine resolution
To reduce process

But it has many problems such as…
needs organic development
needs HMDS for increasing adhesion
has less film & liquid properties
has out gas included
etc…
Solution of the problems
Photosensitive PI (negative tone) Decreasing…
To reduce cost(process & Photosensitive PI
materials)
To be high resolution (positive tone)
To prevent deposit on side-wall
To lower out gas It’s becoming standard!
To increase adhesion to MC and
passivation layer
To be environmental friendly

1980 1990 2000

8

Features of PW-series
Customer’s requirement
Ⅰ High package reliability
High electric and thermal resistance
High adhesion strength
Ⅱ Cost reduction of process and materials
Availability for aqueous development
Low temperature curing process
Good photo speed
Long storage life
High resistance for dry etching process
Ⅲ Semiconductor and package downsizing
High resolution
High adhesion strength to passivation layer
Ⅳ CSP and bump application
Excellent chemical resistance
High adhesion strength to various materials
Availability for multi layer
Ⅴ 12 inch application
Good photo speed
Low residual stress and CTE
We can show you more detailed information
in the following “Technical Data”
PW-series is(has)…
Satisfying IC’s requirement (Pure PI film)
Excellent adhesion strength to MC and Si,SiN,TEOS etc.
Available for TMAH 2.38%
Available for curing under 280℃
The best photo speed in positive tone PSPI
Stable at room temperature
Excellent resistance for 1 mask process
The highest resolution(3um at 8um thickness)
Excellent adhesive strength of even 5um line pattern to SiN
The highest chemical resistance in all PSPI
Excellent adhesion strength to many metals(Cu,Al,Ni,Cr,Ti,Au,etc)
High Tg and stability during curing process
The best photo speed in positivetone PSPI
less than 40MPa and 36ppm/℃
9
 The best solution example①
If you face following problems…
For non photosensitive customers:
Poor viscous stability or solution stability
Low resolution(around 30um□)
Numerous process
For negativetone photosensitive customers:
Expensive material cost
Low resolution(about 10um□)
Deposit on side-wall
Out gas
Weak adhesion to MC and passivation layer
Organic development
For PBO customers:
High CTE & residual stress
Low chemical resistance
Poor adhesion to passivaition layer
Less storage stability
Narrow cure process latitude
From PI customer’s view
Then we can provide you with solutions such as…
Excellent viscous stability
Far higher resolution(3um□)
Photoresist process reduction
Moderate PI price and availability for aqueous development
Higher resolution(3um□)
Far less out gas included and good taper shape
Far less out gas included
Excellent adhesion to that(not to need HMDS)
Availability for aqueous development
The lowest CTE & residual stress in all PSPI
Excellent chemical resistance(no crack during chemical process)
Excellent adhesion to passivation layer(even if 5um line is OK)
Excellent storage stability(no particle after R.T.storage)
Wider cure process window(available for curing in air)
10
 The best solution example② From IC manufacturer’s view

For buffer coatings application PI is/will be required for following things

<Memory> Pad PI layer
Si substrate
Fuse box
(The present) (The future)
A few pads A few pads
Fuse box 10×20um Fuse box 5×20um Higher resolution(3-5um□)
TSOP CSP

Higher chemical resistance for CSP & bump.

<Logic> Pad

Higher adhesive strength to passivaiton layer.

Left pattern
(The present) (The future) Higher chemical resistance for HF solution
A lot of pads A lot of pads during wet etching before dry etching.
Left pattern width 10um Left pattern width 5um
QFP CSP

For CSP & bump application CSP & bump is very promising package.
It can realize package shrinkage,improvement
PW-series emphasize this field
Au bump of electric properties, and cost reduction.
Under bump metal
Redestribution route

Higher adhesion strength to various metals.

Higher chemical resistance for various etchant,
flux, cleaner, solvent etc.
11
 The best solution example② From IC manufacturer’s view

DRAM Higher resolution

Conventional properties
Flash Electric property
Thermal property
Adhesion to MC & SIN
SRAM etc…

Device MRAM Low temperature curig

trend
Logic(Graphic,LCDdriver,ChipSet,MPU,etc) Higher Adhesion to SiN
High chemical resistance(HF)

Conventional properties+
System LSI Low temperature curing
Higher Adhesion to SiN
High chemical resistance

TSOP Conventional properties

Protective property for
Package fiiler in MC

trend Bump ,WLP High chemical resistance

(flux + cleaner,etchant,solvent)

In the future, you’ll need requirement.

PW-series is only PI which can satisfy these demands.

12
 PW-series basic properties
PW-1000 PW-1200 PW-1500 PW-2100
Type Standard Thick Film High Chemical High Photo-
Applicable Resistance Sensitivity
visc osity mPa.s 1,500 1,500 1,500 1,500
total solid c on te n t wt% 38 40 40 40
liqu id prope rty -16℃ mon th 9 9 9 9
life time 4℃ mon th 6 6 6 6
room temp. month 1 1 1 1
th ickn ess um 3-7 3-10 3-7 3-7
te n sile stre n gth Mpa(3 2 0 ℃) 130 150 150 150
250℃ c u re % - 20 20 20
320℃ c u re % 30 20 20 20
elogation 350℃ c u re % 20 20 10 20
380℃ c u re % 10 20 10 20
400℃ c u re % 10 20 10 20
you n g's modu lu s Gpa(3 2 0 ℃) 3.0 3.9 3.8 3.8
CTE ppm/ ℃ 36 36 36 36
250℃ c u re MPa - 26 35 30
re sidu al stre ss
320℃ c u re MPa 28 36 38 36
film prope rty
5 % we igh t loss te mp. ℃( 3 2 0 ℃) 480 475 435 475
250℃ c u re ℃ - 230 250 235
film property
320℃ c u re ℃ 270 305 320 310
Tg(TMA) 350℃ c u re ℃ 270 305 380 310
380℃ c u re ℃ 270 305 400 315
400℃ c u re ℃ 270 305 430 320
die lec tric c on stant - 2.9 2.9 2.9 2.9
volu me re sistan c e Ωc m2 >10^16 >10^16 >10^16 >10^16
su rfac e re sistan c e Ωcm >10^16 >10^16 >10-16 >10-16
bre akdown voltage kV/ mm >420 >420 >420 >420
wate r absorption % 0.6 0.6 0.6 0.6

13
 PW-series basic properties
PW-1000 PW-1200 PW-1500 PW-2100
c oat with ou t HMDS spin spin spin spin
prebake ℃/ min 120/3 120/3 120/3 115/3
3u m mJ/ cm2 175 150 150 10 0
exposu re 5u m mJ/ cm2 400 300 300 15 0
proc ess performanc e
7u m mJ/ cm2 650 550 550 25 0
PEB Not required Not required Not required Not required
de ve lop se c 20-120 20-120 20-120 20-120
c ure ℃/ min 320-380 250-380 250-380 250-380
NMP rt/ 15 min no change no change no change no change
GBL rt/ 15 min no change no change no change no change
solve nt EL rt/ 15 min no change no change no change no change
ac eton e rt/ 15 min crack no change no change no change
PGMEA rt/ 15 min no change no change no change no change
DMSO/ mono- 50% thickness decrease 10% thickness decrease 10% thickness decrease 10% thickness decrease
re sist strippe r 9 0℃/3 0min
c he mic al re sistanc e eth anolamin e
2 5% NaOH 4 0℃/1 0min no change no change no change no change
alkakine
10 %KOH 4 0℃/1 0min no change no change no change no change
H2 SO4/ H2O2 4 0℃/1 0min no change no change no change no change
etc h an t
1% HF ｒｔ/ 5min no change no change no change no change
flux De ltalux5 33 2 90 ℃/ 30 sec crack no change no change no change
c lean er Pine - arfa 40 ℃/ 30 min no change no change no change no change

14
2. Technical Data

15
 Adhesion to Substrate (Si and SiN)

Final Curing Temperature

Oxygen ３２０℃ ３５０℃ ４００℃

（ｐｐｍ） PCT treatment time（Ｈｒ．）

0 50 100 0 50 100 0 50 100

1 ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ

100 ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ

250 ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ

10000 ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ ＯＫ

Cure ：Koyo-Thermo Systems CLH-21CD

PCT :121 C, 2 atm 16
 Adhesion to Metals(Cu,Ti,Cr)

Metals is made by spattering process after each treatment.

Test method:Peeling test after 0hr,100hr at 150℃ (peeling pcs/total pcs)

Adhesion
treatment Ｃｕ Ti Ｃｒ
0hr 100hr 0hr 100hr 0hr 100hr
no treatment 0/100 0/100 0/100 90/100 0/100 0/100
O2 (Plasma) 0/100 0/100 0/100 30/100 0/100 0/100
CF4(RIE) 0/100 0/100 0/100 0/100 0/100 0/100
AR(Spatter) 0/100 0/100 0/100 0/100 0/100 0/100

17
 Residual Stress

40
Non photosensitive P I (35MPa)
35
Residual Stress（MPa）

30
Cooling
25
PW-1000
20
15
10 Heating
5
0
0 50 100 150 200 250 300 350
Temperature（℃）

18
 Gas Analysis (During cure process)
Positive Type Polyimide Negative Type Polyimide
PW-1000
BG-2430
Heating Condition ：RT→(3.5℃/min)→170℃×30min→(3.5℃/min)→320℃×60min→(3.5℃/min)→500℃

Mass Amount (%) Heating Condition ：RT→(3.5℃/min)→170℃×30min→(3.5℃/min)→350℃×60min→(3.5℃/min)→500℃

Chemical group
m/z
a
RT～170℃×30min 170℃～320℃×60min 320℃～500℃ Mass Amount（％）
Chemical Group
a
m/z RT～160℃×30min 160℃～350℃×60min 350℃～500℃
18 H2O （ImidizationSensitizer） 0.65 1.21 1.80

28 N2, etc （Sensitizer） 2.03 1.06 0.07 18 H2O (Imidization） 4.32 1.49 1.01

32 Organic gas （Imidization） 0.68 2.64 0.37 44 CO 2(Sensitizer） 6.49 1.91 0.93
86(<-42) r-Butylolactone （Solvent） 1.20 1.95 0.14 99 NMP （Solvent剤） 5.57 0.09 0.00
44 CO 2 （Sensitizer） 0.25 0.25 0.33
86(<-42) r-Butylolactone （Solvent） 4.18 2.00 0.88
118(<-45) Ethyl lactate （Solvent） 0.77 1.05 0.02
28 Organic gas (Sensitizer) 3.05 0.64 1.27
64 Organic gas （Sensitizer） 0.00 0.02 0.51
132(<-45) PGMEA and Organic gas 0.22 0.19 0.08
104(<-85) Orgaic gas (Polymer） 0.00 0.00 0.00
157(<-58) Organic gas (Sensitizzer) 3.82 2.93 0.03
94 Organic gas （Sensitizer） 0.00 0.00 0.20
130(<-87) Organic gas (Sensitizer) 0.13 0.08 0.05
99 Organic gas （Sensitizer） 0.00 0.94 0.11
86 Solvent, Organic gas 0.75 0.34 0.13
108 Organic gas （Sensitizer） 0.00 0.00 0.18
100 Organic gas (Sensitizer) 0.75 0.00 0.02
116 Organic gas （Sensitizer） 0.00 0.00 0.04
Total Amount（％） 29.29 9.67 4.40

Total amount／ｗｔ％ 5.58 9.12 3.77

19
 Patterning Process of PW-1000

Spincoat 700rpm for 10sec and 3000rpm for 30sec

120 C×3min (Hot plate) (Thickness:5.1 μm)
o
Prebaking
Exposure 175 mJ/cm2 (g-line, i-line stepper)
3ｕｍ Development 45 sec. ×2 Paddle development (Thickness:4.2 μm)
(2.38% TMAH solution)
o o
Curing 170 C for 30min+320 C for 60min (N2)
(Thickness:3.1 μm)

Spincoat 700rpm for 10sec and 2100rpm for 30sec

115 C×3min (Hot plate) (Thickness:8.1 μm)
o
Prebaking
Exposure 325 mJ/cm2 (g-line, i-line stepper)
Development 45 sec. ×2 Paddle development (Thickness:6.9 μm)
5ｕｍ (2.38% TMAH solution)
o o
Curing 170 C for 30min+320 C for 60min (N2)
(Thickness:5.0 μm)

20
 Spincoat 700rpm for 10sec and 1600rpm for 30sec
115 C×3min (Hot plate) (Thickness:11.6 μm)
o
Prebaking
Exposure 450 mJ/cm2 (g-line, i-line stepper)
7ｕｍ Development 60 sec.×2 Paddle development (Thickness:10.0 μm)
(2.38% TMAH solution)
o o
Curing 170 C for 30min+320 C for 60min (N2)
(Thickness:7.0 μm)

21
 Example Patterning Recipe using TEL Mark-7

for 5 μm Thickness after Curing(Manual Coating)

Coating Recipe(manual coating)
１． Polyimide coating (Mark 7) Dispense
STEP Time Rotate Accell.
C/S (sec) (rpm) (rpm/sec)
↓ 1 10.0 200 1000 PI Dispense
COL 23℃ X 60 s 2 5.0 0 1000 0
↓ 3 10.0 700 2000 0
COAT 4 30.0 2100 1000 0
↓ 5 2.0 0 1000 0
Pre-Bake (HP) 115℃ X 180 s
↓
COL 23℃ X 60 s Development Recipe
↓
C/S STEP Time Rotate Accell. Dispense
(sec) (rpm) (rpm/sec)
1 1.0 1000 10000 0
2 3.0 1000 10000 17
２．Exposure 3 1.0 500 10000 17
I-line Stepper （GCA 8000 DSW WAFER STEPPER） 4 1.0 100 10000 17
Exposure Dose 325 mJ/cm2) 5 4.0 30 10000 17
focus 0μm 6 36.0 0 10000 5
7 3.0 1000 10000 17
３．Development (Mark 7) 8 1.0 500 10000 17
C/S 9 1.0 100 10000 17
↓ 10 4.0 30 10000 17
DEV 11 31.0 0 10000 5
↓ 12 5.0 0 10000 5
C/S 13 5.0 500 10000 349
14 5.0 2000 10000 349
４．Curing 15 10.0 3000 10000 0
Appratus：INH-21CD (Koyo Thermosystem)
Heating：r.t. → 170℃×30 min → 320℃×60 min → r.t. (slope 3.5℃/min) Developer（TMAH 2.38%）Flow rate：0.6 L/min
Oxygen concentration：<500 ppm（Nitrogen gas purge） Rinser（water）Flow rate：1.2 L/min
Back rinse（water）Flow rate：150 mL/min
Exhaust：60 Pa
Nozzle：Stream Nozzle 22
for 5 μm Thickness after Curing(Auto Dispense)
Coater recipe(Auto)
STEP Time Rotation Accel Dispence Arm1 Arm2
１． Polyimide coating (Mark 7) 1 1.0 0 100 0 1 center W home
C/S 2 2.0 0 100 0 1 center NW home Dispence No.
3 9.0 50 100 1 1 center NW home 1：PI dispence
↓ 4 6.0 50 100 1 1 center NW home 5：back rince（OK73）
COL 23℃ X 60 s 5 5.0 0 10000 0 1 center NW home 6：edge rince（OK73）
↓ 6 10.0 1100 10000 0 1 home NW home
COAT 7 30.0 1530 10000 0 1 home NW home
8 5.0 1530 10000 0 1 home NW in1
↓ 9 1.0 1000 10000 6 1 home NW in1 Film thickness is controled in step 7,8.
Pre-Bake (HP) 115℃ X 180 s 10 30.0 1000 10000 56 1 home NW in2
↓ 11 1.0 1000 10000 56 1 home NW in1
COL 23℃ X 60 s 12 25.0 1000 10000 56 1 home NW in2 Edge rince flow rate：10ml/min
13 5.0 1000 10000 6 1 home NW in2 Back rince flow rate：70ml/min
↓ 14 1.0 1000 10000 0 1 home NW home
C/S 15 2.0 500 10000 0 1 home NW home

Development Recipe

２．Exposure STEP Time Rotate Accell. Dispense

I-line Stepper （GCA 8000 DSW WAFER STEPPER） (sec) (rpm) (rpm/sec)
Exposure Dose 325 mJ/cm2) 1 1.0 1000 10000 0
focus 0μm 2 3.0 1000 10000 17
3 1.0 500 10000 17
３．Development (Mark 7) 4 1.0 100 10000 17
C/S 5 4.0 30 10000 17
↓ 6 36.0 0 10000 5
DEV 7 3.0 1000 10000 17
↓ 8 1.0 500 10000 17
C/S 9 1.0 100 10000 17
10 4.0 30 10000 17
４．Curing 11 31.0 0 10000 5
Appratus：INH-21CD (Koyo Thermosystem) 12 5.0 0 10000 5
Heating：r.t. → 170℃×30 min → 320℃×60 min → r.t. (slope 3.5℃/min) 13 5.0 500 10000 349
Oxygen concentration：<500 ppm（Nitrogen gas purge） 14 5.0 2000 10000 349
15 10.0 3000 10000 0
Developer（TMAH 2.38%）Flow rate：0.6 L/min
Rinser（water）Flow rate：1.2 L/min
Back rinse（water）Flow rate：150 mL/min
Exhaust：60 Pa
Nozzle：Stream Nozzle 23
 Coated Film Stability
after coating
Keeping days 0 3 7
Thickness 11.52μｍ 11.52μｍ 11.52μｍ

Thickness after
10.06μｍ 10.05μｍ 10.02μｍ
developing
Sensitivity 425mJ/cm2 425mJ/cm2 425mJ/cm2

after exposure
Keeping days 0 3 7
Thickness 11.52μｍ 11.52μｍ 11.52μｍ
Thickness after
10.06μｍ 10.04μｍ 9.96μｍ
developing
Sensitivity 425mJ/cm2 425mJ/cm2 425mJ/cm2
Prebaking Condition ：１１０℃×4min (TEL Mark-7)
Development Condition：２．３８％ＴＭＡＨ solution 120sec(total time)b
Sensitivity ：5μm resolution @7μm thickness
24
 Film Thickness Uniformity
Thickness Range Sigma Wafer Thickness
Wafer No. （μｍ） （Å） （Å） No1 （μｍ）
1 7.8043 1040 264
1 7.8208
2 7.8000 713 233
3 7.7900 828 292
2 7.7708
4 7.8031 848 316 3 7.7991 ８
5 7.7936 772 259 4 7.7857
6 7.7702 546 224 5 7.7883
7 7.8055 573 201 6 7.8319 7 1
8 7.8558 711 254 7 7.8597
9 7.8385 863 314 8 7.8149
10 7.7771 513 220
9 7.7892
11 7.7686 606 226 13
12 7.7380 1121 408 10 7.8052
13 7.9036 936 311 11 7.8066
14 7.8005 1153 373 12 7.7557
15 7.7960 835 329 13 7.8280
16 7.8075 1081 354 Mean（μｍ） 7.8043
17 7.8102 1264 491
18 7.8467 1243 445
Range（Å） 1040
19 7.8712 1553 546 σ（Å） 264
20 7.8622 1142 388
21 7.7697 657 234
22 7.8696 676 290 Coater : Tokyo Electron Mark-7
23 7.8050 539 200
24 7.8281 980 329
25 7.8784 168 64
Mean 7.8162
25
 Critical Dimension after Development
Ｖ４－②　 Mask Size 5μｍ
12
Aperture Size ( m)

10 Process Condition
8 Top
Pre-baking 120℃×3min (proximity)
6 Bottom
(Thickness 7.90μm)
4
Exposure tool i-line stepper
2
Development 120sec. Paddle (2.38%TMAH solution)
0
(Thickness 6.67μm)
150 200 250 300 350
Exposure Dose (mJ/cm2)

Mask Size 20μｍ

Mask Size 10μｍ
26
16

Aperture Size ( m)
Aperture Size ( m)

24
14
22
12
20
10
18 Top
8 Top 16 Bottom
6 Bottom 14
4
150 200 250 300 350
150 200 250 300 350
Exposure Dose (mJ/cm2)
Exposure Dose (mJ/cm2)

26
 Mask Linearity after Development

Ｖ４－②　Bottom Size Ｖ４－②　Top Size

30 30
Aperture Size ( m)

Aperture Size ( m)
25 25
20 20μm Mask 20 20μm Mask
15 15
10 10μm Mask 10 10μm Mask
5 5μm Mask 5 5μm Mask
0 0
150 200 250 300 350 150 200 250 300 350
Exposure Dose (mJ/cm2) Exposure Dose (mJ/cm2)

27
 Critical Dimension after Curing
Ｖ４－②キュア　Mask Size 5μｍ
12
Aperture Size ( m)

10 Curing Condition
8 Apparatus INH-21CD (Koyo Thermosystem)
6 Heating 140℃×60min+320℃×60min
4 Ｔｏｐ (slope: 3.4℃/min)
2 Ｂｏｔｔｏｍ Oxygen under 300ppm (Nitrogen gas purge)
0
(Thickness 5.12μm)
150 200 250 300 350 400
Exposure Dose (mJ/cm2)

Ｖ４－②　Mask Size 10μｍ Ｖ４－②　Mask Size 20μｍ

16 26

Aperture Size ( m)
Aperture Size ( m)

14 24
12 22
10 20
8 Ｔｏｐ 18 Ｔｏｐ
6 Ｂｏｔｔｏｍ 16 Ｂｏｔｔｏｍ
4 14
150 200 250 300 350 400 150 200 250 300 350 400
Exposure Dose (mJ/cm2) Exposure Dose (mJ/cm2)

28
 Mask Linearity after Curing

Bottom　Size Top Size

30 30
Aperture Size ( m)

Aperture Size ( m)
25 25
20 20μm Mask 20 20μm Mask
15 15
10 10μm Mask 10 10μm Mask
5 5μm Mask 5 5μm Mask
0 0
150 200 250 300 350 400 150 200 250 300 350 400
Exposure Dose (mJ/cm2) Exposure Dose (mJ/cm2)

29
 DOF and Mask linearity
DOF of PW-1000（５μｍ） DOF of PW-1000（２０μｍ）

Actual Size（μｍ）
Actual Size（μｍ）

6 21
5 20
4
3
2 19
1 18
0
-5 0 5 -5 0 5
Focus（μｍ）
Focus（μｍ）

DOF of PW-1000（１０μｍ） Mask Linearity of PW-1000

11

Actual Size(μｍ）
Actual Size（μ

60

10 40
ｍ）

9 20

0
8
0 20 40 60
-5 0 5 Mask Size (μｍ）
Focus（μｍ）

30
 Storage Stability
Viscosity Exposure Dose
2000 1400
1200

mPa・ｓ 1500
1000
800

msec
1500cp 600
1000
400
200
500 0
0 5 10 15 20 25 30 0 5 10 15
Storage days (at 23℃) Storage days (at 23℃)

Viscosity Exposure Dose

4000 1400
1200

3000
1000
mPa・ｓ

800

msec
3000cp 600
2000
400
200
1000 0
0 5 10 15 20 25 30 0 5 10 15
Storage days (at 23℃) Storage days (at 23℃)
31
Relationship between Reaction rate and Curing Temperature

100
reaction rate(%)
80
60
40
20
0
0 200 400 600
cure temperature
32
Supplement

33
 Basic Principle of Photosensitivity
O
Polymer N2
Sensitizer COOH

OH OH
Photo Reaction
X SO2 SO2
X
OR OR
R R
Naphtoquinone diazido Indene carbonic acid
Soluble in Alkaline Insoluble in Alkaline Soluble in Alkaline

【exposure】

【Alkaline Developer】

Positive tone pattern Hardly Soluble Easily Soluble

34
Comparison of Negative-tone and Positive-tone Polyimide Structure
１． Negative tone Photosensitive Polyimide/Ester type
O O
O O Heat
H
N N N N
H
*ROOC COOR* n
R*NR2+H2O O O n

Polyamic acid ester O Polyimide

O
R*: CH2CH2O

２． Toray Positive tone Photosensitive Polyimide

O O CH3
H2 O O
H
NH Si O C N H
N N
CH3 x y H
*ROOC COOR*
*ROOC COOR*
n m
Polyamic acid ester

R*: CH3 O
CH3 O
Heat H2
Si O H
C N N N
CH3 x y
O O
R*

Si-unit 35
 Assumed Model Adhesion between PI and EMC

１． Negative tone Photosensitive Polyimide/Ester type

Si unit additives Polymer

Curing

Epoxy Molding Indirect bonding

Compound

２． Toray Positive tone Photosensitive Polyimide

Polymer
Si-unit

Curing

Epoxy Molding
Direct bonding
Compound 36
 Stability for Chemicals
１．Cured Film
Suflic acid
+ 40C for 1hr. No change
Hydrogen Peroxide

Fumed RT 1hr. No change

Nitric acid 50C 10min Completely Resolved

NMP, DMF, IPA, MEK etc. Inert

２．Uncured Film(As developed)

NMP GBL Cyclo-Pentanone Ethyl-lactate Acetone IPA

Easily soluble Easily soluble Easily soluble Soluble Insoluble Insoluble

Positive resist stripper, such as TOK-106, can be removed PW-1000 before curing easily.
37
 Plasma Etch Resistance of “PW-1000”
Ｏ２－ＲＩＥ etchin ＣＦ４－ＲＩＥ etching

3.50 1.00

Etching thickness（μｍ）
Etching thickness（μｍ）

3.00
0.80
2.50
OFPR-800 0.60 OFPR-800
2.00
PW-1000 PW-１０００
1.50 0.40 BG-2480
BG-2480
1.00
0.20
0.50
0.00 0.00
0 1 2 3 4 5 6 0 2 4 6
Treatment Treatment time (min.)

ＣＦ４－Ｏ２－ＲＩＥ etching

5.00 （１） RIE condition

Apparatus Reactive Ion Etching Model RIE-ION（samco）
Etching thickness（μｍ）

4.00 Gas ①O2: 50.2 SCCM

3.00 OFPR-800 ②CF4/O2: 25.1/25.3 SCCM
PW-1000 ③CF4: 50.0 SCCM
2.00 BG-2480 RF-Power RF-cont: 500 FWD: 278W REF: 1W
1.00 Time 1min, 3min, 5min
Pressure 0.60 Torr
0.00
0 1 2 3 4 5 6
Treatment time (min.) 38
Lithographic Performance on I-Line Exposure System
Characteristic Curve of "PW-1000”
(5 μm Thickness after Curing)

100%
Prebaking Temperature
Normalized Remaining

80%
115℃
60% 120℃
Film Thickness

125℃
40%
20%
0%
1 10 100 1000 10000

Exposure Dose(mJ/cm2)
Exposure: i-line Stepper (GCA DSW-8000:NA=0.42)
Thickness:7.8μm after Prebaking on Si
39
 Effect of Curing Condition (PW-1000)
Adhesion
Curing 5%Weight
（Si, Al, SiN） Elongation
Temp. Loss Temp.
after PCT 400 Hr

320 C OK 30 % 480 ℃

350 C OK 20 % 522 ℃

400 C OK 10 % 540 ℃

<Curing Condition>
・ Koyo-Thermo Systems CLH-21CD
・170 C×30min＋ X ℃×60min
40