Sie sind auf Seite 1von 7

J Mater Sci: Mater Electron (2014) 25:1033–1039 DOI 10.1007/s10854-013-1683-3

Conductivity enhancement of PEDOT:PSS thin film using roll to plate technique and its characterization as a Schottky diode

Muhammad Zubair Navaneethan Duraisamy Kyung Hyun Choi Myung Teak Hyun

Received: 2 October 2013 / Accepted: 14 December 2013 / Published online: 27 December 2013 Springer Science+Business Media New York 2013

Abstract The conductivity of poly(3,4-ethylene dioxy- thiophene):poly(styrene sulfonate) was improved by pressing the PEDOT:PSS thin film using roll to plate sys- tem. PEDOT:PSS thin film was deposited on polyethylene terephthalate using electrohydrodynamics atomization technique. The physico-chemical properties of the pressed thin film at different loads were compared with an un- pressed sample. The electrical properties show that the film conductivity has been increased by four times. An opti- mized pressing load was found to have good conductivity and transmittance of the thin film. A hybrid device (PE- DOT:PSS/F8BT/ZnO/Ag) was fabricated using layer by layer method with PEDOT:PSS as anode. The IV charac- terization showed that the device with pressed PEDOT:PSS showed higher current densities. The results give a prom- ising future of PEDOT:PSS in electronics device applica- tions using printed electronics techniques.

1 Introduction

Since the dawn of conductive polymer [13], huge research growth has been achieved in conductive polymer field. The conductive polymers are used in many applications like optoelectronics [4, 5], sensors [68], batteries [9], super capacitors [10, 11], and superconductors [12, 13]. Conductive polymer materials have advantages of low cost, lightweight,

M. Zubair N. Duraisamy K. H. Choi (& ) Department of Mechatronics Engineering, Jeju National University, Jeju 690-756, Korea e-mail: amm@jejunu.ac.kr

M. T. Hyun Department of Mechanical Engineering, Jeju National University, Jeju 690-756, Korea

and large area coverage by vacuum free fabrication tech- niques [14]. These advantages allow conductive polymer materials to replace many metals and inorganic materials. In transparent electrodes, indium tin oxide (ITO) exhibits good transparency and high conductivity [15, 16] but has its shortfall as well. ITO has poor mechanical flexibility [17, 18], releases indium and oxygen in organic layer [19], has poor transparency for blue region [20] and is a scarce earth metal which makes it expensive [21]. The comparable alternative transparent electrodes are conducting polymers, carbon nanotubes and metal nanowires. The carbon nanotubes have short life [2224] and metal nanowires fail under current flow [25, 26] which make the environmentally stable conducting polymers ahead of its competitors. PEDOT:PSS [poly(3,4-ethylene dioxythiophene):poly (styrene sulfonate)] [27, 28] is a conductive polymer which is commercially available and dispersible in water. With latest non-vacuum techniques, PEDOT:PSS is easily pro- cessable into thin films from aqueous solution and has high strength, flexibility, excellent thermal, mechanical, and environmental stability. PEDOT:PSS prevents the electro- static discharges during film rewinding, reduces dust buildup after processing and has high transparency in the visible range [2932]. Many researcher have studied the conductivity enhancement of PEDOT:PSS [2940]. The conductivity was improved by heating, ultraviolet (UV) treatment, addition of solvents, adding nanowires and nanoparticles. Tsai et al. [29] improved conductivity by heating the solution of PEDOT before deposition. The conductivity was enhanced by adding and treating organic solvents like ethylene glycol (EG), 2-nitroethanol, methyl sulfoxide, 1-methyl-2-pyrrolidinone, poly(ethylene glycol) or dimethyl sulphoxide [3037]. Conductivity of PE- DOT:PSS improvement by carbon nanotubes doping was reported by Park et al. [38]. Lin and Su [40] and

123

1034

J Mater Sci: Mater Electron (2014) 25:1033–1039

1034 J Mater Sci: Mater Electron (2014) 25:1033–1039 Fig. 1 The electrohydrodynamics atomization deposition technique

Fig. 1 The electrohydrodynamics atomization deposition technique

Table 1 The parameter used in deposition of PEDOT:PSS ink on PET substrate by electrohydrodynamics atomization technique

Parameter

Value

Ink

PEDOT:PSS

Substrate

PET

Standoff distance

18 mm

Capillary inner diameter

410 lm

Flow rate

1,000 ll h -1

Voltage

5.7 kV

Sintering temperature

110 C

Sintering time

30 min

temperature 110 C Sintering time 30 min Fig. 2 Roll to plate system where ( 1

Fig. 2 Roll to plate system where (1) control panel touch screen, (2) printing module, (3) base frame module, (4) doctor blade module, (5) pattern module and (6) substrate module

Semaltianos et al. [39] used ZnO nanoparticles to improve the conductivity of PEDOT:PSS. Mechanical characteristic of PEDOT:PSS were discussed by Lang et al. [41]. In this paper the conductivity of PEDOT:PSS was enhanced by pressing the thin film using a roll to plate

123

by pressing the thin film using a roll to plate 123 Fig. 3 The thin film

Fig. 3 The thin film pressing technique-using roll to plate system

The thin film pressing technique-using roll to plate system Fig. 4 Hybrid Diode Device a structure

Fig. 4 Hybrid Diode Device a structure of hybrid diode and b energy level diagram

system. This is a very easy method used to increase the conductivity of the polymer. A thin film of PEDOT:PSS was deposited by electrohydrodynamics atomization (EHDA) process. The operating envelop of PEDOT:PSS ink was found with different applied voltage and flow rate parameter. The thin film was pressed by using a roll to plate system for printed electronics using different pressing loads. The surface of thin film was examined for its quality by using a field emission scanning electron microscope (FE-SEM). The conductivity and optical transmittance of the samples under different loads with respect to the un- pressed samples were studied. An optimal pressing load was determined for good conductivity and transparence. A hybrid device (PEDOT:PSS/F8BT/ZnO/Ag) was made and its electrical characterization was performed to show the higher conductivity of pressed PEDOT:PSS thin layer.

2 Materials and methods

PEDOT:PSS (Orgacon) was purchased from Agfa Materi- als Japan Ltd, Japan. The polyethylene terephthalate (PET)

J Mater Sci: Mater Electron (2014) 25:1033–1039

1035

substrate was washed by acetone, ethanol and DI-water in ultra-sonicator for 15 min. Followed by UV treatment in UV cleaner for 5 min. Finally, the substrate was treated by oxygen plasma to make the hydrophilic surface in low- pressure plasma (FEMTO Science Model Cute). EHDA is a simple, cost effective process, which can define the coating width while operating at room temper- ature and pressure conditions. The EHDA setup is shown in Fig. 1 (25 C, 50 % humidity). A metallic capillary of internal diameter 410 lm was attached to a nozzle adapter (NanoNC), which is con- nected to syringe (Hamilton, Model 1001 GASTIGHT syringe) using Teflon tubing. A syringe pump (Harward Apparatus, PHD 2000 infusion) was used to hold the syringe and maintain the flow rate. The voltage was applied to the nozzle adopters by high voltage DC power source (Hewlett Packard 54602B) which amplify the sin- gle produced by function generator (Hewlett Packard 33120A). A metal plate, connected to ground, was placed under the capillary. A high-resolution CCD camera (Motion Pro X) was used to observe the EHDA phe- nomena. A light source (Moritex MLET-A080W1LRD) was used for illumination. NI motion control board (NI PXI 7340) was used for the stage motion control. The PEDOT:PSS thin films were deposited on PET substrate by using parameters given in Table 1.

The prepared PEDOT:PSS thin film was pressed by roll to plate system (Printed Electro-Mechanical Systems Model PMT-102) with different load conditions. A roll to plate system was a semi-automated system used for gravure offset

printing. Roll to plate system is shown in Fig. 2. Controlled pressure was applied on the thin film as shown in the Fig. 3. Three samples were pressed under load conditions of 3, 5 and 7 kg F. Where 1 kg F was approximately equal to 9.80665 N. A Schottky diode with hybrid structure (PEDOT:PSS/ F8BT/ZnO/Ag) was layer by layer fabricated. The elec- trohydrodynamic atomization of zinc oxide (ZnO) and poly

[9,9-dioctylfluorenyl-2,7-diyl]-co-1,4-benzo-(2,1,3)-thiadi-

azole (F8BT) were discussed in our previous work [42, 43]. PEDOT:PSS was used as the anode of the device. Silver cathode was printed by silver nanoparticles ink using electrohydrodynamic printing technique as explained in our previous work [44]. The device structure and energy levels were shown in Fig. 4.

3 Results and discussion

3.1 EHDA process

In the EHDA process, the flow rate was kept at 1,000 ll h -1 . The distance from the tip of nozzle to the substrate, known as

distance from the tip of nozzle to the substrate, known as Fig. 5 Field emission scanning

Fig. 5 Field emission scanning microscope images of samples of PEDOT:PSS thin film on PET substrate in low magnification a un-pressed, b pressed at 29.4 N, c pressed at 49 N, d pressed at 68.6 N

123

1036

J Mater Sci: Mater Electron (2014) 25:1033–1039

1036 J Mater Sci: Mater Electron (2014) 25:1033–1039 Fig. 6 Field emission scanning microscope images of

Fig. 6 Field emission scanning microscope images of samples of PEDOT:PSS thin film on PET substrate in high magnification a un-pressed, b pressed at 29.4 N, c pressed at 49 N, d pressed at 68.6 N

at 29.4 N, c pressed at 49 N, d pressed at 68.6 N Fig. 7 The

Fig. 7 The I–V curves of un-pressed, pressed at 29.4, 49 and 68.6 N load PEDOT:PSS thin

standoff distance, was kept at 18 mm. By increasing voltage, different modes of atomization were observed which was dripping, micro-dripping, unstable cone-jet, stable cone-jet and multi-jet. EHDA process had been clearly explained in our previous work [4247].

123

clearly explained in our previous work [ 42 – 47 ]. 123 Fig. 8 The conductivity

Fig. 8 The conductivity and thickness of PEDOT:PSS thin film under different pressing loads

3.2 Surface analysis

The surface morphology of deposited thin films was exam- ined with field emission scanning electron microscope (FE- SEM) analysis. The polymer thin films were compressed as

J Mater Sci: Mater Electron (2014) 25:1033–1039

1037

J Mater Sci: Mater Electron (2014) 25:1033–1039 1037 Fig. 9 The hybrid device (PEDOT:PSS/F8BT/ZnO/Ag) current den-

Fig. 9 The hybrid device (PEDOT:PSS/F8BT/ZnO/Ag) current den- sities of under various load conditions were shown

den- sities of under various load conditions were shown Fig. 10 The optical transmittance of PEDOT:PSS

Fig. 10 The optical transmittance of PEDOT:PSS thin film on PET substrate of un-pressed, pressed at 29.4, 49 and 68.4 N load measured by UV/VIS/NIR spectrophotometer

shown by FE-SEM images in Figs. 5 and 6. In the conjugated polymers, the intermolecular electronic interactions are weak as the polymer structure is not in order. In conventional semiconductors, the charge transport is by band transport but in conjugated polymers, the charge transport between the chains is dominated by hopping conductivity [4850]. This compression result in closed packing of PEDOT:PSS structure, which resulted in lowering the localization length and lowering the effective energy barrier for hopping of charge carries between the PEDOT/PSS grains hence enhancing the conductivity of PEDOT:PSS thin film.

hence enhancing the conductivity of PEDOT:PSS thin film. Fig. 11 The conductivity and transmittance of PEDOT:PSS

Fig. 11 The conductivity and transmittance of PEDOT:PSS thin film shown with respect to the pressing load

3.3 Thickness

The thickness of thin film by EHDA depends on the standoff distance, flow rate, speed of substrate and time of spray. The thickness of the thin films was measured by non-destructive, thin film thickness measurement system (K-MAC Model ST4000-DLX). Working principle of K-MAC was the constructive and deconstructive interfer- ence in the spectrum of white light incident on the surface of thin film. Ten different points were used to calculate the average thickness of the thin films.

3.4 Conductivity

The electrical properties of deposited film were observed using semiconductor device analyzer (B1500A, Agilent, USA). The current voltage (IV) characterization of the

thin films samples were shown in Fig. 7. These graphs show good ohmic behavior with linear lines and increase of conductivity. The resistivity of the thin films was found by the equation:

q ¼

pt

V

ln 2

I

ð 1 Þ

where q is resistivity, t is thin film thickness, V is voltage, I is current. The respective conductivity of thin films was calculated. The conductivity and thickness of thin layer was compared at different pressed load that is presented in Fig. 8. The compression of thin film is also evident by the thin film thickness. As the thickness of thin film decreased, by applying pressing load, the film conductivity increased due to the enhanced molecular interaction.

123

1038

J Mater Sci: Mater Electron (2014) 25:1033–1039

3.5 Schottky diode characteristics

The Schottky diode fabricated by spraying F8BT and ZnO on PEDOT:PSS thin film. Here, PEDOT:PSS acts as anode and silver as cathode. In this device, ZnO acts as an elec- tron injection layer and also act as a hole blocking layer while F8BT is the active layer. The PEDOT:PSS layer is the only hole providing anode layer. The un-pressed PE- DOT:PSS layer with the lower conductivity restrained the current density of the device. The pressed samples show higher current densities as compared to the un-pressed samples as shown in Fig. 9.

3.6 Transmittance

The optical properties of thin film are equally important as the electrical properties. The UV/VIS/NIR spectropho- tometer (Shimadzu UV-3150) was used to analyze the optical properties of the samples. The optical properties of the un-pressed and pressed thin film samples at 29.4, 49 and 68.6 N loads were shown on Fig. 10. The transmit- tance of PEDOT:PSS thin layer decreased by increasing the pressed load. The close packing of inner contact of polymer structure of thin layer by compressing resulted in reducing the transmittance of light in visible region. The relation of conductivity and transmittance at different loads was presented in Fig. 11. Here the conductivity and transmittance have an inversely proportional relation, which gives a tradeoff between conductivity, and trans- mittance by pressing at different loads.

3.7 Optimized parameters

A pressing load of 49 N was chosen as the optimum load as

at this pressing load, the conductivity of thin film was 110.4 S cm -1 and transmittance at wavelength of 550 nm was around 73.86 % as shown in Fig. 11. This optimized pressing load the conductivity increased was four times

more than un-pressed sample and had a good transmittance

at wavelength of 550 nm was around 73.86 % in the visible

region. Hence the pressed PEDOT:PSS thin layer deposited by EHDA has better electrical properties and good optical properties without damaging the thin film.

4 Conclusion

The conductivity of PEDOT:PSS thin film was increased by four times using easy technique of pressing the thin layer by roll to plate system. The electrical, thickness and

optical properties of thin film proved the increase in con- ductivity while slight reduction in the transmittance of light

as the pressing load was increased. A pressing load of 49 N

123

was found to be optimal for increase in conductivity by four times while maintaining a good transmittance around 73.86 % at wavelength of 550 nm in the visible region. A hybrid structure of a Schottky diode (PEDOT:PSS/F8BT/ ZnO/Ag) was fabricated which showed the high current densities for the pressed PEDOT:PSS layer.

Acknowledgments This research was supported by the Technology Innovation Program (No. 10041596, Development of core technology for TFT free active matrix addressing color electronic paper with day and night usage) funded by the Ministry of Knowledge Economy (MKE, Korea) and the Global Leading Technology Program of the Office of Strategic R&D Planning (OSP) funded by the Ministry of Knowledge Economy, Republic of Korea (10042477).

References

1.

H.

Derivatives, J. Louis, A.G. Macdiarmid, J. Chem. Soc. Chem.

Commun. 16, 578 (1977)

2.

C.

Chiang, C. Fincher, Y. Park, A. Heeger, H. Shirakawa, E.

Louis, S. Gau, A. MacDiarmid, Phys. Rev. Lett. 39, 1098 (1977)

3.

W.J. Feast, J. Tsibouklis, K.L. Pouwer, L. Groenendaal, E.W. Meijer, Polymer (Guildf). 37, 5017 (1996)

4.

R.H. Friend, R.W. Gymer, A.B. Holmes, J.H. Burroughes, R.N.Marks, C. Taliani, D.D.C. Bradley, M. Lo, W.R. Salaneck, D.A. Dos Santos, J.L. Bre, Nature 397, 121 (1999)

5.

S.

Gu¨nes, H. Neugebauer, N.S. Sariciftci, Chem. Rev. 107, 1324

 

(2007)

6.

D.T. McQuade, A.E. Pullen, T.M. Swager, Chem. Rev. 100, 2537

 

(2000)

7.

J. Janata, M. Josowicz, Nat. Mater. 2, 19 (2003)

8.

K. Arshak, V. Velusamy, O. Korostynska, K. Oliwa-Stasiak, C.

Adley, IEEE Sens. J. 9, 1942 (2009)

9.

T.

Suga, H. Ohshiro, S. Sugita, K. Oyaizu, H. Nishide, Adv.

Mater. 21, 1627 (2009)

10.

M. Mastragostino, C. Arbizzani, F. Soavi, J. Power Sources 97–98, 812 (2001)

11.

M.

Mastragostino, C. Arbizzani, F. Soavi, Solid State Ionics 148,

493 (2002)

 

ˆ

12.

A.

Pron, P. Rannou, A . Synthe, Prog. Polym. Sci. 27, 135 (2002)

13.

H.

Hayden, S. Park, V. Zhirnov, R. Cavin, P.A. Kohl, J. Nano-

particle Res. 12, 2335 (2010)

14.

B.

Chen, T. Cui, Y. Liu, K. Varahramyan, Solid State Electron.

47, 841 (2003)

15.

D.

Raoufi, A. Kiasatpour, H.R. Fallah, A.S.H. Rozatian, Appl.

Surf. Sci. 253, 9085 (2007)

16.

H. Schmidt, H. Flu¨gge, T. Winkler, T. Bu¨low, T. Riedl, W. Kowalsky, Appl. Phys. Lett. 94, 243302 (2009)

17.

T.

Aernouts, P. Vanlaeke, W. Geens, J. Poortmans, P. Heremans,

S.

Borghs, R. Mertens, R. Andriessen, L. Leenders, Thin Solid

Films 451–452, 22 (2004)

18.

J.L. Koenig, P.L. Sutton, B.J. Cui, A. Wang, N.L. Edleman, J. Ni,

P.

Lee, N.R. Armstrong, T.J. Marks, Adv. Mater. 13, 1476 (2001)

19.

M.P. de Jong, L.J. van Ijzendoorn, M.J.A. de Voigt, Appl. Phys.

Lett. 77, 2255 (2000)

20.

S.-I. Na, S.-S. Kim, J. Jo, D.-Y. Kim, Adv. Mater. 20, 4061

 

(2008)

21.

M.

Garter, J. Scofield, R. Birkhahn, A.J. Steckl, Appl. Phys. Lett.

74, 182 (1999)

22.

Y.

Ohno, S. Maruyama, T. Mizutani, in Carbon Nanotubes, ed.

by J. M. Marulanda (InTech, 2010), p. 109

23.

S.

Reich, M. Dworzak, A. Hoffmann, C. Thomsen, M. Strano,

Phys. Rev. B 71, 033402 (2005)

J Mater Sci: Mater Electron (2014) 25:1033–1039

1039

24.

A. Hagen, M. Steiner, M. Raschke, C. Lienau, T. Hertel, H. Qian,

38.

J.

Park, A. Lee, Y. Yim, E. Han, Synth. Met. 161, 523 (2011)

A. Meixner, A. Hartschuh, Phys. Rev. Lett. 95, 197401 (2005)

39.

N.G. Semaltianos, S. Logothetidis, N. Hastas, W. Perrie, S.

25.

H.H. Khaligh, I.A. Goldthorpe, Nanoscale Res. Lett. 8, 235 (2013)

Romani, R.J. Potter, G. Dearden, K.G. Watkins, P. French, M.

26.

E.M. Goldys, K. Drozdowicz-Tomsia, F. Xie, T. Shtoyko, E.

Sharp, Chem. Phys. Lett. 484, 283 (2010)

Matveeva, I. Gryczynski, Z. Gryczynski, J. Am. Chem. Soc. 129,

40.

Y.-J. Lin, Y.-C. Su, J. Appl. Phys. 111, 073712 (2012)

12117 (2007)

41.

U. Lang, N. Naujoks, J. Dual, Synth. Met. 159, 473 (2009)

27.

F.

Jonas, B. Ag, Z.B. Zentrale, Synth. Met. 43, 831 (1991)

42.

M. Mustafa, H.C. Kim, Y. Doh, K.H. Choi, Polym. Eng. Sci.

28.

B.G. Heywang, F. Jonas, Adv. Mater. 4, 116 (1992)

(2013). doi:10.1002/pen.23608

29.

K.-H. Tsai, S.-C. Shiu, C.-F. Lin, in Improving the Conductivity of Hole Injection Layer by Heating PEDOT:PSS, ed. by Z.H.

43.

K.H. Choi, S. Khan, H.W. Dang, Y.H. Doh, S.J. Hong, J. Appl. Phys. 49, 05EC08 (2010)

Kafafi, P.A. Lane (Proc. of SPIE, 2008), p. 70521B

44.

K. Rahman, A. Khan, N.M. Nam, K.H. Choi, D.-S. Kim, Int.

30.

Y.-M. Chin, J.-C. Lin, Y.-J. Lin, K.-C. Wu, Sol. Energy Mater.

J.

Precis. Eng. Manuf. 12, 663 (2011)

Sol. Cells 94, 2154 (2010)

45.

N.M. Muhammad, S. Sundharam, H.-W. Dang, A. Lee, B.-H.

31.

J.Y. Kim, J.H. Jung, D.E. Lee, J. Joo, Synth. Met. 126, 311 (2002)

Ryu, K.-H. Choi, Curr. Appl. Phys. 11, S68 (2011)

32.

S.K. Jo¨nsson, J. Birgerson, X. Crispin, G. Greczynski, W. Osi- kowicz, A. Denier van der Gon, W. Salaneck, M. Fahlman,

46.

N.M. Muhammad, A.M. Naeem, N. Duraisamy, D.-S. Kim, K.-H. Choi, Thin Solid Films 520, 1751 (2012)

Synth. Met. 139, 1 (2003)

47.

N. Duraisamy, N.M. Muhammad, A. Ali, J. Jo, K.-H. Choi, N.

33.

J.

Gasiorowski, R. Menon, K. Hingerl, M. Dachev, N.S. Sari-

Malik, Mater. Lett. 83, 80 (2012)

ciftci, Thin Solid Films 536, 211 (2013)

48.

H. Ba¨ssler, A. Ko¨hler, B. Heinz, K. Anna, Top Curr. Chem. 312,

34.

S. Ashizawa, R. Horikawa, H. Okuzaki, Synth. Met. 153, 5 (2005)

1 (2012)

35.

J. Ouyang, Q. Xu, C.-W. Chu, Y. Yang, G. Li, J. Shinar, Polymer (Guildf). 45, 8443 (2004)

49.

X. Crispin, S. Marciniak, W. Osikowicz, G. Zotti, A.W.D. van der. Gon, F. Louwet, M. Fahlman, L. Groenendaal, F.D.E.

36.

T.

Wang, Y. Qi, J. Xu, X. Hu, P. Chen, Appl. Surf. Sci. 250, 188

Schryver, W.R. Salaneck, J. Polym. Sci. Part B Polym. Phys. 41,

 

(2005)

2561 (2003)

37.

O.P. Dimitriev, D.A. Grinko, Y.V. Noskov, N.A. Ogurtsov, A.A. Pud, Synth. Met. 159, 2237 (2009)

50.

H.-S. Park, S.-J. Ko, J.-S. Park, J.Y. Kim, H.-K. Song, Sci. Rep. 3, 2454 (2013)

123