2011. Feb.
“Photoneece” Low Temperature Curing Series
Toray Industries
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
About Toray “Photoneece”
“Photoneece” is photosensitive polyimide coatings which developed Toray by
awarded* original technologies. Currently, the “Photonecce” are widely used as a
buffer coating for semiconductor devices, micro-lens for image sensors, insulator for
OLED, interlayer-dielectrics for electronic components and so on.
Toray “Photoneece” is world leading photosensitive polyimide coatings for
semiconductor, display and electronic devices.
To maintain our current status, we are developing low residual stress type
photosensitive polyimide coatings.
*: Technical award from Chemical Society Japan (2009) by development of positive tone photosensitive polyimide
by partial esterification of polyimide precursor.
Technical award from Polymer Society Japan (1991) by development of ionic bonded type negative tone
photosensitive polyimide.
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Polyimide coatings for next generation
High speed connection → Bump connection (WL-CSP)
Stress Concentration
Solder
CTE：20ppm/℃
LSI chip
CTE：４ppm/℃
Polyimide
CTE：40ppm/℃
Low stress（Thick coat）
Underfill
CTE：70-150ppm/℃
Board
CTE：20ppm/℃
Smaller feature of LSI → Device structure, materials change
Low thermal
curing thick
coatings
Lower thermal budget
High K gate insulator
Porous Low K＋Cu wiring
Weak for heat treatment
Mechanically weak
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Low temperature cure for next generation buffer coating
Cure temp.：<200C（Low thermal budget）、Heat stability：>300C（Solder process）
Low temp. curable PSPI
Degradation temperature［℃］）
４００
Polyimide
Low temp （High temp. cure)
High temp.
（Solder process）
３００
×
２００
Soluble PI
・No imidization
＋
New cross-linker
working at 150C
Imidization conversion
（>300C）
Low temp.
Epoxy
Acrylic
１００
Low temp
0
１００
High temp
２００
Process temperature（℃）
Toray proprietary
３００
4００
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Low cure temperature polyimide design
<Requirements>
1. Less damage to device during PI cur---Less thermal budget
2. Applicable to super thin chip---Less stress to wafer
3. More protective film-------------Thicker film applicable(20-30um)
<Design concept>
Key concept for New polyimide: Low molecular weight polyimide change
into polyimide molecular weight by heat treatment. High molecular weight
polyimide contribute to realize tough film after post cure
Polyimide
150∼180C
Small Shrinkage
Macromolecule of Polyimide
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Negative Tone Type
Features of PN-Series
（１）Negative tone and Alkali Developable（2.38% TMAH）
（２）Low Shrinkage after Cure : about10%（Good Planarization, Low Stress)
（３）Wide Cure emperature Range (165-300 ℃)
（４）Good Mechanical Properties as well as conventional Polyimides
（５）Sufficient Chemical Resistance to Bumping Processes
（６）Good Thermal Stability >300℃ （∼200℃）
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Negative Tone Type
Patterning Process of PN-2000(1500cp)
Spincoat
Prebaking
Exposure
1500cP PEB
Development
Curing
700rpm for 10sec and 1500rpm for 30sec
100oC×3min (Hot plate) (Thickness:18.1 um)
400mJ/cm2 (800msec) (g, h, i-line)
100oC×1min (Hot plate)
40s × 2 Puddle development (Thickness:17.4 um) *2.38% TMAH solution
200oC for 60min (N2) (Thickness:15.0 um)
Spincoat
Prebaking
Exposure
1500cP PEB
Development
Curing
700rpm for 10sec and 2300rpm for 30sec
100oC×3min (Hot plate) (Thickness:12.3 um)
300mJ/cm2 (600msec) (g, h, i-line)
100oC×1min (Hot plate)
30s × 2 Puddle development (Thickness:11.7 um) *2.38% TMAH solution
200oC for 60min (N2) (Thickness:10.0 um)
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Negative Tone Type
Patterning profile of PN-2010
PB 100℃×3min Exposure dose 250mL/cm2 PEB 100℃×1min Development 30ｓ×2
F=-4um
F=-1um
F=0um
F=+1um
F=+4um
4umL&S
5umL&S
10umL&S
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Negative Tone Type
Film Properties of “Photoneece” PN-series
C u rin g c o n ditio n
T e n s ile s tre n gth
Elo n gatio n
Y o u n g 's Mo du lu s
Re s idu al s tre s s
5 % w e igh t lo s s te m p.
T g( T M A)
D ie le c tric c o n s tan t
Vo lu m e re s is tan c e
S u rf ac e re sis tan c e
W ate r abso rptio n
D e ve lo pe r
℃
3 50X1h
M Pa
122
%
25
Gpa
3 .9
M Pa
48
℃
434
℃
334
1 MH z
3 .2
Ω ・ c m 2 > 1 0 ^1 6
Ω ・ c m > 1 0 ^1 6
%
1 .4
PN - 2 0 0 0
2 8 0 X2 h 2 0 0 X 1 h
119
108
40
34
3 .3
3 .5
41
36
401
382
284
201
3 .1
3 .1
> 1 0 ^1 6 > 1 0 ^1 6
> 1 0 ^1 6 > 1 0 ^1 6
1 .4
1 .6
2.38% TMAH
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Positive Tone Type
Features of Positive Low Temp. “Photoneece”
（１）Low Temperature Curable（∼200℃）（Less Damage to Devices）
（２）Low Shrinkage after Cure : about10%（Good Planarization, Low Stress)
（３）Common 2.38％TMAH Developable
（４）Good Mechanical Properties as well as conventional Polyimides
（５）Sufficient Chemical Resistance to Bumping Processes
（６）Good Thermal Stability >300℃
（７）Fine Patterning Properties
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Positive Tone Type
Positive Tone Low Temp. “Photoneece”
We successfully developed “Positive tone Photo Definable Polyimide Coatings” by
combining ong history of polyimide designing technologies and our competitive photo
sensitive polymer technologies.
Type
Lithographic
Developer
Properties
Rinser
Cure Temperature
Tensile Strength
Mechanical
Elongation
Properties
Modulus
5% Weight Loss
Thermal
Temp.
Properties
Tg (DSC)
Positive tone
2.38% TMAH
DI water
200C
105MPa
10%
3.9GPa
331C
240C
5um 抜き
5um
line
10um 抜き
10um
line
20um 抜き
20um
line
5um
line
5um 抜き
10um 抜き
10um
line
20um
line
20um 抜き
As
Dev.
現像後
As
キュア
後
Cure
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Positive Tone Type
Patterning of Positive Low Temp. “Photoneece”
Conditions
Prebaking：120℃ 180sec
Prebaked film thickness = 6.2um
Exposure 5000J/m2 at i-line (Eth= 3500J/m2)
Development 40sec by 2.38% TMAH
Cure：200℃ 1h
Thickness after Development = 5.6um
Thickness after Cure = 5.1um, Shrinkage = 9%
3 um
5um
10um
20um
3 um L&S
5um L&S
10um L&S
20um L&S
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.
Toray Polyimide Coatings Line-up
Stress Buffer Coat
Thermal,. Electrical,
Mechanical prpeperties
Buffer Coat
EMC
Polyinmide Coatings
Non Photo
“Semicofine”
Photo
“Photoneece”
＜Soluble by exposure＞
Lead Frame
Non Photo type
“Semicofine”SP-series
SP-042：CTE 18ppm
SP-341：Elongation 100%
SP-453：Good adhesion
•Patterning by Photo-resist, Many steps
•Less Resolution（ca３０μｍ）
•Organic solvent develop→Expensive
Negative •Resolution limit is about 10μｍ
＜Insoluble by exposure＞
•Alkali developpable
Positive
•Resolution limit is about 3μｍ
Negative tone Poyimide
“Photoneece”UR,BG-series
BG-2430：CTE 25ppm
Alkali Developable
BG-8440：iline
Photosensitivity
Alkali dev.
Photosensitivity
Low Temp. Curable
Thick Film （＞20
μm）
（＞20μ
Positive tone Pokyimide
“Photoneece”PW-1000
Adhesion to Au
PW
-1900
PW-1900
Bumping、WL-CSP
Negative
Negative Low
Low Temp.
Temp.
““Photoneece”
Photoneece” PN
-series
PN-series
PN
-2000
PN-2000
Positive
Positive Low
Low Temp.
Temp.
New
New type
type
Chemical Resistance
High Tg
““Photoneece”
Photoneece”
PW
-1200、PW-1500
PW-1200、PW-1500
High Sens.
PW
-2000series
PW-2000series
High Sensitivity
Bumping , WL-CSP
PW
-3000series
PW-3000series
Toray proprietary
Copyright 2011Toray Industries, Inc. All Rights Reserved.