Characterization of light-emitting polymers

Kevin Treacher Heinz Goetz

Light-emitting polymer technology is set to open a complete new world of applications for a wide range of products, such as small (and eventually large) flat screen displays, warning signs, decorative lighting and illuminated advertising 1,2. The active layer of polymer-LEDs can be prepared by simple coating methods, such as spin coating. All colors are now available for these displays which can be made as thin as one millimeter. High brightness can be achieved at low power consumption and long life times of more than 30000 hours. Light emitting polymers are organic, conjugated, macromolecules of very high molecular weight. An important example are phenyl-substituted poly(p-phenylene vinylene) (PPV). To make them soluble and to process them into thin films they are modified, for example, by OR RO introducing alkyl or alkoxy side chains. Figure 1 shows the structure of a OR RO commercially available phenyl alkoxyphenyl PPV copolymer. The compound is soluble in aromatic hydrocarbons, cyclic ethers and certain ketons.The quality of the film coating process (and thus also the resulting polymer-LED) strongly depends on the polymerization and the resulting molecular weight OM e data/molecular weight distribution. The latter parameters can be monitored
m n

R=

Conditions
Figure 1 Structure of phenyl alkoxyphenyl PPV copolymer

Absorbance [mAU] 1200 Poly (p-phenyl vinylene) 0 nRIU 15000 Solvent ingredients -2500 0 5 10 Additives, oligomers 15 20 Time [min] 25 30

Sample preparation Samples were dissolved in stablized THF and filtered (concentration 0.1 %) Column 3 PLGel mixed C, 7.5 300 mm, 5 m (Agilent p/n 79911GP-MXC) Polymer standards Polystyrene EasyCal vial standards (Agilent p/n 5064-8281) Flow rate 1 ml/min Column compartment temperature 20 C Injection volume 100 l

Figure 2 Overlay of chromatograms obtained simultaneously by diodearray and refractive index detection setting/evaluation

easily and precisely by GPC with Agilent Technologies PLgel columns and tetrahydrofuran as eluent. Figure 2 shows an overlay of the diode array and refractive index detector signals of a phenyl alkoxyphenyl PPV copolymer analysis. The chromatograms and the GPC report obtained with the ChemStation GPC data analysis software (figure 3) show the high quality resulting from: broad molecular weight distribution ranging from about 103 to 7106 Dalton large polydispersity D of about 3.7 very high molecular weight averages, e.g. Mw is larger than 800000 Dalton low concentration of additives and other compounds (figure 2) the purity of the polymer peak as proven by the overlay of UV-visible spectra acquired at various retention times (figure 4)

Equipment
Agilent 1100 Series GPC-SEC system consisting of vacuum degasser for efficient degassing of the mobile phase Isocratic pump with large solvent cabinet Autosampler with single valve design Thermostatted column compartment for precise column temperatures Refractive index detector with automatic recycle valve ChemStation Plus with GPCSEC data analysis software

Sample : Calibration file : Integration from: MHK - A (Cal.): Eluent : Concentration : Detector 1 : Detector 2 : Operator :

D:\ApplNotes\3PLMIXC2\3PLmixCEasiDADPoly3Jan20.CAL 12.081 ml 1.000E+0 THF +BHT 0.000 g/l DAD A, Sig=260,10 Ref=off RID A, Refractive Index Signal Heinz G.

Integration to : MHK - K (Cal.): Flowrate : Inject volume : Delay volume : Delay volume : Acquisition interval :

22.858 ml 0.000E+0 ml/g 1.000 ml/min 100.000 ul 0.000 ml 0.197 ml 0.400 sec

Method information Molar mass distribution

0.8

0.6

0.4

W(log M)
0.2

References
HP GPC-Addon Rev. A.01.03

0.0 10 4 10 5 10 6 10

g/mol

Molar mass

dad1A Mn : Mw : Mz : Mv : D : [n]: Vp : Mp : A : 10% 30% 50% 70% 90% 2.1652e5 8.1317e5 1.7186e6 8.1317e5 3.7557e0 0.000000 1.5434e1 7.5494e5 4.4348e3 1.0190e5 2.8114e5 5.2638e5 9.2617e5 1.9051e6

rid1A 2.3055e5 8.4313e5 1.7654e6 8.4313e5 3.6571e0 0.000000 1.5394e1 7.7939e5 6.3271e4 1.0937e5 2.9857e5 5.5312e5 9.6022e5 1.9571e6 g/mol g/mol g/mol g/mol ml/g ml g/mol ml*V g/mol g/mol g/mol g/mol g/mol

Molecular weight data

Path : Date :

D:\APPLNO~1\3PLMIXC2\SY-02.D Wednesday 08/30/00 08:22:43

Sign :

Figure 3 Single page GPC report including method parameters, molar mass distribution and molecular weight data Norm 1500 Figure 4 Proof of PPV peak purity by overlay of seven spectra acquired at different retention times

1. Nu Yu, H. Becker, Covion Technology Bulletin, http://www.covion.com/techsum. html 2. H. Becker, H. Spreitzer, W. Kreuder, E. Kluge, H. Schenh, I. Parker, Y. Cao, Adv. Mater., 12(1), 42(2000)
Kevin Treacher is research chemist at Covion Organic Semiconductors GmbH, Frankfurt/Main, Germany Heinz Goetz is an application chemist at Agilent Technologies, Waldbronn, Germany For more information on our products and services, visit our worldwide website at http://www.agilent.com/chem
Copyright 2000 Agilent Technologies Released 10/2000 Publication Number 5988-0116EN

0 300 350 400 450 500 Wavelength [nm] 550