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 OR
RO
introducing alkyl or alkoxy side chains. Figure 1 shows the structure of a
commercially available phenyl alkoxyphenyl PPV copolymer. The compound is
soluble in aromatic hydrocarbons, cyclic ethers and certain ketons.The quality
m
n of the film coating process (and thus also the resulting polymer-LED) strongly
OM e depends on the polymerization and the resulting molecular weight
data/molecular weight distribution. The latter parameters can be monitored
R= *

Conditions
Figure 1
Structure of phenyl alkoxyphenyl PPV copolymer Sample preparation
Samples were dissolved in stablized THF
and filtered (concentration 0.1 %)
Absorbance [mAU] Column
1200 3 × PLGel mixed C, 7.5 × 300 mm, 5 µm
Poly (p-phenyl vinylene) (Agilent p/n 79911GP-MXC)
Polymer standards
0
Polystyrene EasyCal vial standards
(Agilent p/n 5064-8281)
nRIU
15000 Flow rate
Solvent 1 ml/min
ingredients Column compartment temperature
Additives, oligomers
20° C
-2500
Injection volume
0 5 10 15 20 25 30
Time [min] 100 µl
Figure 2
Overlay of chromatograms obtained simultaneously by diode-
array and refractive index detection setting/evaluation
easily and precisely by GPC with Agilent Technologies PLgel columns and Equipment
tetrahydrofuran as eluent. Figure 2 shows an overlay of the diode array and
refractive index detector signals of a phenyl alkoxyphenyl PPV copolymer Agilent 1100 Series
analysis. The chromatograms and the GPC report obtained with the GPC-SEC system
ChemStation GPC data analysis software (figure 3) show the high quality consisting of
resulting from: • vacuum degasser for
• broad molecular weight distribution ranging from about 103 to 7×106 Dalton efficient degassing of the
• large polydispersity D of about 3.7 mobile phase
• very high molecular weight averages, e.g. Mw is larger than 800000 Dalton • Isocratic pump with large
• low concentration of additives and other compounds (figure 2)
solvent cabinet
• the purity of the polymer peak as proven by the overlay of UV-visible
• Autosampler with single
spectra acquired at various retention times (figure 4)
valve design
• Thermostatted column
compartment for precise
Method
Sample :
Calibration file : D:\ApplNotes\3PLMIXC2\3PLmixCEasiDADPoly3Jan20.CAL
column temperatures
Integration from:
MHK - A (Cal.):
12.081 ml
1.000E+0
Integration to :
MHK - K (Cal.):
22.858 ml
0.000E+0 ml/g
information
• Refractive index detector
Eluent : THF +BHT Flowrate : 1.000 ml/min
Concentration : 0.000 g/l Inject volume : 100.000 ul
Detector 1 : DAD A, Sig=260,10 Ref=off Delay volume : 0.000 ml
Detector 2 : RID A, Refractive Index Signal Delay volume : 0.197 ml
Operator : Heinz G. Acquisition interval : 0.400 sec

with automatic recycle

0.8

Molar mass valve

• ChemStation Plus with GPC-
0.6

distribution
0.4 SEC data analysis software
W(log M)
0.2

References
0.0
HP GPC-Addon Rev. A.01.03
4 5 6 7
10 10 10 10 g/mol

Molar mass

1.
Molecular
dad1A rid1A

Mn :
Mw :
Mz :
2.1652e5
8.1317e5
1.7186e6
2.3055e5
8.4313e5
1.7654e6
g/mol
g/mol
g/mol
Nu Yu, H. Becker, Covion
Mv :
D :
[n]:
Vp :
8.1317e5
3.7557e0
0.000000
1.5434e1
8.4313e5
3.6571e0
0.000000
1.5394e1
g/mol

ml/g
ml
weight data Technology Bulletin,
http://www.covion.com/techsum.
Mp : 7.5494e5 7.7939e5 g/mol
A : 4.4348e3 6.3271e4 ml*V
10% 1.0190e5 1.0937e5 g/mol
30% 2.8114e5 2.9857e5 g/mol
50% 5.2638e5 5.5312e5 g/mol
70%
90%
9.2617e5
1.9051e6
9.6022e5
1.9571e6
g/mol
g/mol html
2.
Path : D:\APPLNO~1\3PLMIXC2\SY-02.D
Date : Wednesday 08/30/00 08:22:43 Sign :
H. Becker, H. Spreitzer, W.
Kreuder, E. Kluge, H. Schenh, I.
Parker, Y. Cao, Adv. Mater., 12(1),
Figure 3 42(2000)
Single page GPC report including method parameters, molar mass
Kevin Treacher is research chemist at
distribution and molecular weight data
Covion Organic Semiconductors
GmbH, Frankfurt/Main, Germany
Norm Heinz Goetz is an application chemist
at Agilent Technologies, Waldbronn,
Germany
1500
For more information on our products
and services, visit our worldwide
Figure 4
website at
Proof of PPV peak http://www.agilent.com/chem
0 purity by overlay of
300 350 400 450 500 550 seven spectra © Copyright 2000 Agilent Technologies
Wavelength [nm] acquired at different Released 10/2000
retention times Publication Number 5988-0116EN