“Photoneece ”” DL-1000 - toray.jp · 1 Positive-Tone Photosensitive Polyimide for Insulation Layer in OLED/PLED “PhotoneeceTM”” DL-1000 Toray Industries, Inc. Comparison

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PositivePositive--Tone Photosensitive PolyimideTone Photosensitive Polyimidefor Insulation Layer in OLED/PLEDfor Insulation Layer in OLED/PLED

PhotoneecePhotoneeceTMTM DLDL--10001000

Toray Industries, Inc.

Comparison between DL-1000 and Novolak-resist / Acryl-resist

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Spacer Structures in OLED

*Spacer means a generic name of insulating layer, bank layer and wall.

Insulation LayerInsulation Layer

Insulation Layer shape requirementsRound edge shapeLow tapered angle (20-40)Thickness 1um

AnodeRib layer (Negative photoresist)

CathodeEmitting layer

AnodePlanarization layer

TFT

Glass Glass

Emitting layer

Cathode

3

DL-1000 vs. Other Materials

DL-1000 is the best material for an insulation layer in OLED/PLED

0

1

2

3

4

5

Patterning performance

Electrical performance

Thermal stability(Outgas)

Adhesion to substratesPixel shrinkage

Low tapered angle

Solution stability

DL-1000 Acryl Novolak PR

4

Material solution for Pixel Shrinkage

Initial

72hr

80/Dry

Torays polyimide Acrylic resin Novolak resin

Pixel shrinkage 0% 47% 64%

5

1. Developability with alkaline solution (2.38% TMAH)

2. High resolution: 1um line/space @1m thickness

3. Low temperature cure (230/30min in air)

4. Controllable side wall angle

5. Stable electrical and chemical properties

6. Excellent thermal stability (Lower outgas)

7. Good adhesion to various substrates

8. Good UV-O3 & O2-plasma resistance

9. Good solution stability

10. Compatible with existing display process tools

1. Developability with alkaline solution (2.38% TMAH)

2. High resolution: 1um line/space @1m thickness

3. Low temperature cure (230/30min in air)

4. Controllable side wall angle

5. Stable electrical and chemical properties

6. Excellent thermal stability (Lower outgas)

7. Good adhesion to various substrates

8. Good UV-O3 & O2-plasma resistance

9. Good solution stability

10. Compatible with existing display process tools

Features of DL-1000

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Family of PhotoneeceTM DL-1000

OLED(Low molecular EL)

PLED(Polymer EL)

DL-1000

Features

Target thickness 1-2 m 1-2 m 1-2 m 2-4 m

Tapered angle 35-45 degree 35-45 degree 20-30 degree 45-60 degree

Standard grade

30, 44 mPa s 40 mPa s 40 mPa s

Target coaterSpin

SlitSpinSpin Spin Spin

Photosensitivity Excellent Good Excellent Good

Good

SL-1900 SL-3000 SL-1100-4

Wide developing process margin Low tapered angle

High Tapered Angle

Viscosity

Process margin(developing)

40-50 mPa s

Excellent Good Good

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OLED PLED

DL-1000 SL-1900 SL-3000 SL-1100-4

Features Standard grade Wide developmarginLow Tapaered

AngleHigh Tapered

Angle

Thickness 12 m 1-2 m 1-2 m 2-4 m

Viscosity 30, 44 mPa s 40 mPa s 40 mPa s 50, 160 mPa s

Coater Spin, Slit&Spin Spin Spin Spin, Slit&Spin

Prebaking Hotplate 1202min 1203min

Exposure Broad Band (at I-line) 70mJ/cm2 60mJ/cm2 50mJ/cm2 150mJ/cm2

Reagent TMAH 2.38% TMAH 2.38%

Time 30s 60s 60s 45s

Oven 23030min (in air)23030min

(in air)

Hotplate 16015min23015min 16015min23015min

Residual thickness ratioat unexposured part

77% 90% 88% 94%

Properties Tapered Angle 35-45 35-45 20-30 45-60

Curing

DevelopmentCondition

Application

Details of DL-1000 Family

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10um L&S (x20k)

Cross Sectional Views

For OLED For PLED

10um L&S (x3k)

10um L&S (x20k) 10um L&S (x20k)

Thickness: 1umRound shapeLow tapered angle

(20-40)

Thickness: 2umHigh tapered angle

(45-60)

25 35 50

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Dielectric Breakdown Strength (Thermal Stability)Holding at 85

0

50

100

150

200

250

300

350

400

0 5 10 15 20

Days (at 85)

Die

lectr

ic S

trengt

h (kV

/m

m)

DL-1000

Acryl

Novolak

Cure: 230 for 30min (in air)Holding: 85 (in air)Measurement: JIS C 2110

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Dielectric Breakdown Strength (Light Stability)

Cure: 230 for 30 min (in air) Irradiation: Xe Longlife Fademeter (Suga)

irradiance(300-400nm) 37W/m2, illuminance(400-700nm) 7,300lxMeasurement: JIS C 2110

0

50

100

150

200

250

300

350

400

0 5 10 15 20

Irradiation Time (day)

Die

lectr

ic S

trengt

h (

kV/m

m)

DL-1000

Acryl

Novolak

Under irradiation

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Thermal Stability (Outgas): TGA Analysis

50

60

70

80

90

100

110

0 100 200 300 400 500

Temperature ()

Norm

aliz

ed w

eig

ht

(%)

DL-1000

Acryl

Novolak

Cure: 230 for 30min (in air)Measurement: TGA analysis (r.t.->400, in N2)

Heating from r.t. to 400 after 230 cure

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Holding at 120 after 230 cure

Cure: 230 for 30min (in air)Annealing: at curing temp(230) for 10min in the TG-MS apparatusMeasurement: at 120 for 4 hr

Outgas Components of DL-1000: TG-MS

0

2

4

6

8

10

0 50 100 150 200 250 300

Time (min)

Am

ount

of ga

s evolu

tion (w

tppm

)

m/z 18

m/z 42

m/z 44

m/z 54

m/z 94

m/z 99

total gas

at 120

No OutgasNo Outgas

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0

500

1000

1500

2000

2500

3000

0 50 100 150 200

Temperature (C)

Vola

tile

H2O

wei

ght

(ppm

)

DL-1000 Acryl Novolak

Water Absorption in the Atmosphere

Curing condition: 230C for 30min (in air)Storage: 24 hr in the atmosphere (25C, 60%RH)Measurement: monitoring the weight loss by TGA analysis

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Film Properties of DL-1000

Cure: 230 for 30min (in air)

Tensile Strength 120 MPa

Elongation 10 %

Youngs Modulus 3 GPa

Coefficient of Thermal Expansion 36 ppm/K

Glass Transition Temperature (Tg) 200oC

Dielectric Constant (25) 3.1 /kHz

Volume Resistivity 4.0x1016 . cmElectrical Properties

Thermal Properties 5% Weight Loss Temperature 350oC

Surface Resistivity 1.0x1015

Dielectric Breakdown Strength 350 kV/mm

Mechanical Properties

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Chemical Resistance

Dipping Time (at r.t.)Organic Solvent

IPA 1.35 1.35 1.35PGME 1.35 1.35 1.35

EL (Ethyl lactate) 1.35 1.35 1.35GBL (-Butyrolactone) 1.35 1.35 1.35

Organic solvent

NMP (N-methyl-2-pyrrolidone) 1.35 1.35 1.35

PGMEA 1.35 1.35 1.35Toluene, Xylene 1.35 1.35 1.35

HCl (4wt%; pH=1.0) 1.35 1.35 1.35Inorganic acid

H2SO4(1wt%; pH=1.0) 1.35 1.35 1.35Organic acid CH3COOH (67wt%; pH=0.9) 1.35 1.35 1.35

0 min 5 min 10 min

Cured Film Thickness (m)*

*Cure condition: 230C for 30min in air

The thickness shows no change against the various chemicals.

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Adhesion to various substrates

DL-1000 Acryl Novolak-PR

ITO >500hr 50hr 100hr

Glass(corning 1737)

>500hr 100hr 50hr

SiO2 >500hr 200hr 50hr

* Until the above adhesive time, the crosscut film is retained on the substrates without peeling. **The longer the adhesive retention time is, the higher the adhesion to the substrates is.

Cure condition: 230 for 30min (in air)PCT (Pressure Cooker Test) condition: 121, 2.0x105Pa (2.0atm), 100%RHMeasurement : Crosscut the cured film in 1mmx1mmx100pieces on the substrates

Scotch tape peel test (JIS K 5600)

Tape-pull adhesion test with PCT treatment

Cured film sample

Scotch tape

Substrate

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UV-O3 Treatment Resistance

0

0.1

0.2

0.3

0.4

0.5

0.6

0 20 40 60

UV-O3 Time (min)

Thic

kness

Reduction (um

)

DL-1000

Acryl

Novolak

Cure condition: 230 for 30min (in air)UV-O3 treatment: O3 concentration 100+-50ppm

Gap to lamp 25mmIlluminance 15mW/cm2 (at 254nm)

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O2-plasma Treatment Resistance

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

0 5 10 15 20

O2-Plasma Time (min)

Thic

kness

Red

uct

ion (um

)

DL-1000

Acryl

Novolak

Cure condition: 230 for 30min (in air)O2-plasma Treatment: Power 300W

Degree of vacuum 0.4TorrSWR

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Patterning Process Condition for DL-1000

An example for patterning process

Thickness Measurement Apparatus: DNS LambdaSTM-602

1. Solution viscosity 44 mPas (25)

2. Substrate ITO; 100mmx100mmx0.7mm

3. Spin coating 500rpm/10sec + 1200rpm/30sec

4. Edge back rinse OK73thinner (PGME/PGMEA)

5. Prebaking 120/120sec (Hot plate) [Thickness 1.52 um]

*Measure surface temp. at the top of a glass substrate

6. Exposure 70mJ/cm2 (Broad band, ghi mixed line)

or 200mJ/cm2 (I-line stepper)

7. Development (Dipping) 30sec (2.38TMAH) and 30sec (H2O Rinse)

[Thickness 1.34 um]

8. Curing 1) Oven: 230/30min (in air)

2) Hot Plate: 160/15min + 230/15min [Thickness 1.03 um]

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1

2

3

49

650mm

550mm

Coating Thickness Uniformity of DL-1000 (30mPas)

Viscosity: 30cPSPIN: 1300rpm for 8sec, slit&spin (19.2g)Vacuum dry: Slow vacuum for 5sec Main vacuum 40MPa (0.3Torr) for 63secEdge Rinse: OK73thinner (PGMEA/PGME)

MAX value 1.6838 umMIN value 1.6205 umMEAN value 1.6442 umRange 0.0633 um (1.92%)

MAX value 1.6838 umMIN value 1.6205 umMEAN value 1.6442 umRange 0.0633 um (1.92%)

Using a DNSs Coating System

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Solution Viscosity in the Shelf Life

0

10

20

30

40

50

0 10 20 30

Storage days (at 23)

Vis

cosi

ty (m

Pa s

)

No Change

Holding at 23

No Change

22

0

1

2

3

4

5

0 20 40 60 80Storage days (at 23)

Def

ect D

ensi

ty (p

artic

les/

cm2)

Measurement apparatus: Hitachi LD-5000 (particle size > 0.27um)

Holding at 23

No particle

Particles in the Shelf Life

No particle

Spacer Structures in OLEDDL-1000 vs. Other MaterialsMaterial solution for Pixel ShrinkageFeatures of DL-1000Family of PhotoneeceTM DL-1000Details of DL-1000 FamilyCross Sectional ViewsDielectric Breakdown Strength (Thermal Stability)Dielectric Breakdown Strength (Light Stability)Thermal Stability (Outgas): TGA AnalysisOutgas Components of DL-1000: TG-MSWater Absorption in the AtmosphereFilm Properties of DL-1000Chemical ResistanceAdhesion to various substratesUV-O3 Treatment ResistanceO2-plasma Treatment ResistancePatterning Process Condition for DL-1000Coating Thickness Uniformity of DL-1000 (30mPas)Solution Viscosity in the Shelf LifeParticles in the Shelf Life