1. 차세대 그래핀 기체/수증기 차단성 필름 개발 및 응용
Graphene barrier film development & application
2014. 11. 06
SANGBO corp.
Lee, Kyu
International Carbon Festival

2. 2
Contents
1. Sangbo Corp.
2. Traditional Barrier film
3. High-barrier film
4. Graphene barrier film
5. Technical Issues for high barrier film
6. Flexible OLED display as test device

3. Founded Products
Head Office Employee
Listed Sale
SANGBO corp.
3
Media/Industrial Product Line
Building/Car Window Film
Coating Product Line New Materials Product Line
Display Optical Film
CNT Film/Graphene
DSSC(Dye-Sensitized Solar Cell)
Media Film(Video/CD/DVD)
Industrial(PE/PP Products)

4. Water vapor
• Protection against drying up
• Protection of hygroscopic products
Chemical
• Protection against volatilization
• Chemical resistance
Aroma
• Loss of aroma
• Assuming a different smell
Gas (Oxygen, CO2 etc.)
• Prevention oxidation, Microbiologic spoilage
• Change of protective gas type
4
Protect
Against
Traditional barrier film - Applications

5. Traditional barrier film – WVTR or OTR requirement & market size
자료: Displaybank, Smithers Pira 2012, Fredonia(World Insulation 2011),
Solar & Energy 2011; 상보컨소시엄 분석
5
Market size
단위 : 억원

6. High barrier film – Barrier properties & application
Material OTR (cc/m2/day) WVTR (g/m2/day)
15 nm Al/PET 0.2 ~ 2.9 0.18
SiOx / PET 0.007 ~ 0.03
ORMOCER/PET 0.07
OLED requirement 10-3 ~ 10-5 10-6
자료: IDTechEx “Barrier Films for Flexibile Electronics 2013-2023”

7. 7
High barrier film – What does mean barrier values?
Soccer Field
110 x 75 m2 = 8,250 m2
1x10-6
1x10-4
1x10-2
1
10
100
Raw Film
Food
Packaging
Photovoltaics
OLED
Displays
& Lighting
1 μg per day
0.365 mg per year
3 mg per year
10 g per day
3.65 kg per year
1.8 L
X 2
30 T per year
10 mg per day
3.65 g per year

8. 8
High barrier film – OLED
<Dark spot formation>
<Brightness degradation>t1
Without barrier film
자료: Konica Minolta

9. High barrier film – Organic & Inorganic materials
고분자 필름 종류
OTR
[cc∙25 ㎛
/m2/day]
WVTR
[g∙25 ㎛
/m2/day]
Polyvinyl alcohol 0.05 1,000.00
Ethylene vinyl alcohol
copolymer
0.30 40.00
Polyacrylonitrile 15.00 18.00
Polyamide 6 18.00 40.00
Polyester (biaxially streched) 45.00 5.00
Polyvinyl choloride 120.00 50.00
Polyester (amorphous) 400.00 25.00
Polyethylene (high density) 1,800.00 0.60
Polypropylene 2,500.00 1.70
Polycarbonate 3,600.00 40.00
Polystyrene 6,500.00 30.00
Polyethylene (low density) 7,000.00 2.50
Polytetrafluoroethylene 7,500.00 1.00
Polybutadiene 35,000.00 65.00
Poly-4-methyl pentene 60,000.00 55.00
*Printing technology for flexible substrates, TRC R&D Library & InterLingua (2006)
Organic material Inorganic material
• Defect-free ceramic thin layer (100 nm)
: Theoretical result : > 10-6 g/m2/day
→ 기판의 표면 거칠기 / 증착 공정 시 미세
입자 생성 및 핀홀 발생으로 차단 효과 반감
Organic/inorganic hybrid
• 유무기층 적층으로 기판 평탄화 및 핀홀 보완해
10-6 g/m2/day 급 달성

10.  Decorrelation of defects (inorganic layers)
Tortuous path of the permeant
<Example of Barix® (by Vitex)>
Pros : Vitex have demonstrated a WVTR estimated to be equivalent to
2x10-6g/m2/day at ambient conditions using the Ca test
Cons : High cost
High barrier film – Vitex barrier film
10
(Proc. Soc. Info. Display Symp., Digest Tech. Papers, 34, 550 (2003))

11. 11
D. D. L. Chung, J MATER SCI, 37 (2002) 1475-1489
In-plane structure of graphene
Tortuous path↑
Gas He H2O H2 CO2 O2
Kinetic diameter (Å) 2.6 2.65 2.89 3.3 3.46
Graphene Graphene nanoplates/Polyner matrix
Graphene barrier film

12. 12
PV*용/진공단열재 외피재용
• 그래핀 습식공정
→ 평탄화 코팅층 적용
• OTR : 10-2
• WVTR : 10-1~10-2 (PV 용)
~ 10-4 (진공단열재피)
Display (LCD/OLED)
• 그래핀 건식/습식공정
→ 동시 적용
• OTR, WVTR : 10-6
• 빛 투과도 > 80%
Food packaging
• 보유기술활용 및 성능개선실험
• 10-1 (One layer)
→ 연구개발
• OTR, WVTR : 10-1~10-2
(Multi layer)
1
2
3
OTR, WVTR Applications
Food packaging
PV용 (DSSC)
LCD
진공단열재
외피재용
OLED
10-1
10-2
10-3
10-4
10-5
10-6
Graphene barrier film – Research target

13. 13
Technical Issues for High barrier film
Multi-Layer
Design
Intrinsic Barrier Property
-Material Characteristics
-Structure of Barrier Layer
-Apply labyrinth effects
Substrate Adaptability
-Surface treatment
-Under coating
-Various options of coating method
Defect Reduction
-Avoid crack generation
-Reduce Pin-holes
-Surface modification

14. 14
CVD
Graphene
Synthesis
&Transfer
Polymer
/GNP
Dispersion
&Coating
Deposition
of
Inorganic
Graphene
Mass
Production
Technical Issues for high barrier Film – Intrinsic Barrier Property

15. 15
Technical Issues for high barrier film – Intrinsic Barrier Property
Graphene/Polymer Dispersion Wet coating
Organic/Inorganic Barrier film
Base
film
Base
film
Sputtering

16. PVA 13wt.% PVA 10wt.%
PVA 10wt.% +
5wt.%
PVA 10wt.% +
3wt.%
PVA 3wt.%
PVA 13wt.% +
PSQ
0.7 nm 0.55 nm 0.52 nm 0.53 nm 0.49 nm 0.25 nm
PET
Hard coating
PET
4 nm
4nm 0.2nm
* GE
Technical Issues for high barrier film – Substrate Adaptability
 Surface Roughness

17. Structure WVTR [g/m2/day] V.T. (%) Etc.
1.42 x 10-2 84.5 Peel off
3.2 x 10-3 -
Adhesion
Improvement
Technical Issues for high barrier film – Substrate Adaptability
 Adhesion
Organic(Gr./Polymer)
Inorganic
PET
Adhesion
Improvement
90/1005/100

18. Structure WVTR [g/m2/day]
1.94 x 10-2
3.2 x 10-3
Technical Issues for high barrier film – Defect Reduction
Inorganic
PET
Organic(Gr./Polymer)
Inorganic
PET
SiOx /Graphene-Polymer
1.59 x 10-2 3.32 x 10-2
2.1 times
Avoid crack generationReduce Pin-holes
→ Bending 2.5R / 10K
PET
Inorganic
Organic
Pin hole ↓ & Tortuous path ↑

19. 19
0h 360h
Ref. Konica Minolta SangBo
OLED cell test
85℃ / 85% with Barrier film23℃ / 50% without Barrier film
<Dark spot formation>
<Brightness degradation>
t1
0h 24h

20. 감사합니다
20