CHAPTER I

Introduction

A. Significance of the Study

Substrate-supported polymeric thin films and multilayers have received great attention in

electronics particularly as part of the device miniaturization trend and the search for more cost-

effective device manufacturing. Various organic electronic devices that are already in

commercial production call for more innovative fabrication of films on inexpensive, large-area

substrates.

Chemical preparation and the fabrication technique generally govern by the physical and

electrical properties of the film. Chemical preparation may follow from standard procedures that

detail 1) the monomer and the polymerization method, 2) the solvent or dispersion medium, and

3) the solution concentration of the polymer (Forrest, 2004, Collins, 2004). The fabrication

technique is determined by 1) the physical and chemical properties of the polymer, 2) film

requirements and application, and 3) the substrate on which the film will be mounted or

deposited (Cho, 2007; Skotheim, Elsenbaumer, and Reynolds, 1998).

Various film fabrication techniques have been developed since the market penetration of

organic electronics,. Film fabrication techniques vary in intricacy and applicability. The simplest

methods take advantage of the solution-processability of most conductive polymers. Dip coating

and spin coating, for example, involve the application of a liquid solution of a polymer in a

volatile solvent.

A relatively more practical method of depositing polymer solutions into substrates, with

great potential for efficient and low-cost large-scale production, is printing [ CITATION Mak08 \l

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1033 ]. Among the printing methods being optimized and already in industrial use are the

following: UV lithography, nanoimprinting lithography (NIL), rotogravure printing

(GRAVURE), flexographic printing (FLEXO) and roll-to-roll nanoimprinting lithography

(rrNIL) and inkjet printing (de Gans et al., 2004, Hakola, 2005). Most of these methods have

been adapted from commercial label manufacturing methods such as that for the mass production

of newspapers. Moreover, compared with other fabrication techniques such as epitaxy and

dimensions proved to be more controllable with printing. Printing allows for the direct patterning

of wires and even devices (see Figure 1), thereby reducing the necessity for additional

photolithographic and etching processes.

Figure 1: Inkjet-printed electronic components [ CITATION Hak05 \l 1033 ].

Inkjet printing is of particular interest in this study. This method can be done with a

commercially available desktop inkjet printer as demonstrated by Sturm et al. (2000). The

polymer solution can be replaced into the ink cartridges and the solution can be adjusted in order

to produce homogeneous, pinhole-free films. The proposed substrate is inkjet transparency film

that will be surface-modified to promote polymer film adhesion.

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 Polyaniline (PAni) is one of the most examined conjugated polymers [ CITATION Dav04 \l

1033 ]. With appropriate dopants, it can acquire metallic conductivity and is stable at room and

elevated temperatures. It is also relatively easy to synthesize and compatible with a number of

solvents in its salt form. Moreover, it is readily available.

The researcher intends to study the surface structure and mechanical characteristics of

inkjet-printed PAni films. The importance of these film properties in organic electronics will be

elaborated in the literature review. The results of this study may prove significant in the

following respects:

1. The introduction of an alternative method for film deposition;

2. The printer (deposition device) can be modified to allow the printing of materials other

than polymers such as metals, metal oxides, and ceramics;

3. And, with refinement and better environment control, the method may enable the low-

cost fabrication of directly patterned organic devices.

In addition, since the Materials Physics Research Cluster of the Physics Division

specializes in organic materials and devices such as chemical and biological sensors that

generally require the fabrication of thin films, this study may open new design concepts and

research areas.

B. Objectives

The study intends to produce polyaniline films by inkjet printing and to examine their

morphological and mechanical properties. Its specific objectives are the following:

1. To restructure a desktop inkjet printer for film fabrication;

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 2. To formulate a polyaniline solution suitable for inkjet printing by optimizing the

following solution properties:

a. Solvent,

b. Polymer concentration, and

c. Viscosity;

3. To deposit polyaniline films by inkjet printing the formulated solution on inkjet

transparencies;

4. To analyze the following morphological characteristics of the films through Atomic

Force Microscopy (AFM) and Scanning Electron Microscopy (SEM):

a. Average thickness,

b. Surface regularity, and

c. Surface features;

5. To analyze the following mechanical properties of the films by conducting stress tests:

a. Elasticity (ability to revert to the original shape after the application of stress),

and

b. Tensile strength (the amount of stress required to break or tear the film along its

width or length); and

6. To compare the films produced by inkjet printing with films (of the same material)

produced by dip-coating method.

C. Date and Place of Study

The study will be conducted starting on April 2010 until October 2010 in the Materials

Physics Research Laboratory of the Physics Division at the University of the Philippines Los

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Baños (UPLB). Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM)

characterization procedures will be done at SigmaTech Muntinlupa.

D. Review of Literature

Enormous research is currently being expended on the development of printed organic

displays, solar cells, and electronic circuitries. Lifetimes and efficacy impose a challenge on the

quality of the printed polymer layers. Thus, the polymer preparation, printing method, and the

substrate should be optimized. The literature on polymer inkjet printing, which the researcher has

acquired so far, is condensed below.

1. Polyaniline

The most conductive polyaniline state is the emeraldine salt. Its conductivity is affected by

environmental elements such as temperature, humidity and consequently, the water content of

the polymer (Abell and others, 1997, Wallace and others, 2003). The degree of protonation or

doping, however, is the most significant determinant of polyaniline conductivity (Wallace and

others, 2003). The emeraldine salt can achieve metallic conductivity.

The mechanical properties of polyaniline when made into films are largely dependent on

film formation factors namely: temperature, pressure, and polymer molecular weight.

The ambient temperature at the formation of the film determines the organization of the

molecules of polyaniline in the resulting film. In general, the higher is the degree of molecular

organization, the higher is the conductivity of the bulk material.

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 The molecular weight, which is proportional to the number of monomeric units in a polymer

chain, should be relatively high. It has been found that a molecular weight of 130 000 g/mole is

sufficient for fiber and film production (Laughlin and Monkman, 1997).

Shen and others (2005) studied the growth of polyaniline films at high pressure (450 MPa). It

was found that films tend to form faster, were relatively thicker, and have higher electrical

conductivity and surface smoothness compared to films produced at atmospheric pressure.

2. Inkjet Printing Technology in Polymer Film Fabrication

Hakola (2005) identified several advantages in using inkjet printing in the mass

fabrication of printable electronics (not limited to organic devices) over conventional printing

methods. One advantage is that circuit designs can be edited in the same way that ordinary soft

images are edited. That is, printout proportions (relative sizes) and dimensions (length, width,

thickness, etc.) can be adjusted through the computer that controls the printer. Another advantage

is that inkjet printers can be attuned to accommodate any type of substrate, whether flexible or

rigid, rough or smooth, and whether glass, plastic, or textile. It is comparably more efficient in

handling materials (inks) since circuits can be directly printed on the substrate, thus, eliminating

the need for photolithographic etching to produce the electrical tracks between electronic

components. And finally, these specialized printers can be easily integrated into operational

production systems in the printing industry to date.

The inkjet printing apparatus for laboratory research usually consists of polymer-refilled

disposable cartridges (integrated design) attached to a custom-made inkjet driver connected to a

pulse generator and a computer (see Figure 2). The substrates are mounted on an XY-motion

table which moves the samples while the printer head or driver remains stationary. The pulse

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generator controls each nozzle in the driver as well as the drop formation and dot spacing. Print

heads are usually improvised by using disposable cartridges with the addition of external ink

reservoirs. The apparatus is essentially an enlargement of the desktop inkjet printer.

Printer companies such as Epson and Hewlett-Packard have already invested in the

production of inkjet printers devoted to organic electronic devices. The Autodrop Platform by

Microdrop Germany and the Nano-Plotter by GeSiM are examples of specialized inkjets. Inkjet

printing of polymer electronic devices such as organic light-emitting displays uses already

existing printing machinery and production lines.

Figure 2: The general setup of an improvised inkjet printing apparatus (Sawney, 2006)

Sturm and others (2000) have demonstrated Inkjet printing functional organic devices using

desktop printers. A Cannon PJ-1080A piezoelectric inkjet printer was used. The printer has

nozzles 65 μm in diameter with a resolution of 640 dots per line. It has four ink cartridges and

four nozzles enabling the simultaneous ejection of four different colors. The single modification

done was the replacement of pigment inks in the cartridges with polymer solution. For

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convenience, a piezoelectric desktop inkjet printer, such as the one shown in Figure 3, with an

integrated ink cartridge system will be used in the study.

Figure 3: A Hewlett-Packard color inkjet printer

Among the advantages of inkjet printing over other wet organic casting techniques is that it

is not limited by the substrate. Recently, there has been great interest in flexible electronics, that

is, organic devices mounted on flexible substrates. A variety of flexible substrates have already

been studied and utilized commercially including transparent and opaque plastics, textiles and

metallic foils. The call for a range of substrates largely comes from the production of organic

light-emitting devices.

In this study, inkjet transparency will be used as the substrate. Inkjet transparency films are

usually made from polyester or cellulose acetate. The Gustaffson and others (1992) had

fabricated organic light-emitting devices by spin-coating an aqueous solution of water-soluble

conducting transparent polyaniline on to transparency together with a xylene solution.

Makela (2008) has demonstrated the feasibility of mass-producing polyaniline films by

various printing methods except inkjet printing. Sturm and others (2000) successfully produced

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organic films, excluding polyaniline, using a commercially available desktop inkjet printer. And

Gustaffson and others (1992) used conventional wet casting techniques to deposit polyaniline on

transparency. This study will be a superimposition of the above studies.

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