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Materials Science and Engineering B100 (2003) 40 /46 www.elsevier.


Synthesis and characterization of tris-(8-hydroxyquinoline)aluminum

Hairong Li, Fujia Zhang *,1, Yanyong Wang, Daishun Zheng
School of Physical Science and Technology, Institute of Microelectronics, Lanzhou University, Lanzhou, Gansu 730000, Peoples Republic of China Received 24 May 2002; received in revised form 24 December 2002; accepted 10 February 2003

Abstract A comprehensive understanding of the characteristics of the organic electroluminescent (EL) material tris-(8-hydroxyquinoline)aluminum (Alq3) is meaningful for organic light-emitting devices (OLEDs). Thin films of Alq3 are among the most efficient EL molecular films known to date. Alq3 sample was synthesized and purified. The purity of Alq3 is up to 98.5%. The electronic structure and interaction in Alq3 molecule have been studied. The results of a joint experimental investigation based on a combination of Xray diffraction (XRD) spectra, hydrogen nuclear magnetic resonance (HNMR) spectra, infrared absorption (IRA) spectra, mass spectra (MS), X-ray emission (XRE) spectra and fluorescence spectra of Alq3 have been obtained. The analysis on HNMR spectra of Alq3 demonstrated that the coordinate interaction between Al3  and O ion is more intensive than that between Al3  and N ion. The Al /O bond is covalent bond in Alq3 molecule. Alq3 has two types of geometrical isomers, namely mer isomer and fac isomer. IRA spectra of Alq3 indicate a very intensive chelation of aromatic ring. From the MS spectra the ratio of charge to mass of Alq3 was obtained. Fluorescence data confirmed the existence of a fluorescent species formed between Al ion and 8-hydroxyquinolinol. # 2003 Elsevier Science B.V. All rights reserved.
Keywords: Organic compound; Chemical synthesis; X-ray diffraction; Nuclear magnetic resonance (NMR)

1. Introduction Efficient electroluminescence (EL) from an organic light-emitting device (OLED) was reported by Tang and VanSlyke [1,2] using tris-(8-hydroxyquinoline)aluminum (Alq3). Since those reports, the interest in Alq3 and other metal /chelate systems to produce EL in different spectra regions for display applications has considerably increased [3 /7]. Thin films of Alq3 are among the most widely used EL materials in OLEDs and have led to the point that products are entering the market place. The chemical structure of the Alq3 molecule is shown in Fig. 1. Alq3 is a metal chelate composed of one metal aluminum ion (Al3) and three 8-hydroxyquinoline (HQ) molecule. In Alq3 molecule, the electron structure of Al3 is 1s22s22p6, a metal ion structure similar to inert gas atom, so Alq3 has good stability in dry atmosphere. Alq3 is a received electron
* Corresponding author. Tel.: /86-931-891-3252; fax: /86-931891-3554. E-mail address: (F. Zhang). 1 E-mail: Tel.: /86-931-861-7511; fax: /86-931-891-1100; e-mail:

carrier transporting/photoemitter material. The metals, which have low work function have been chosen as cathode in order to enhance the injection efficiency of electron in the investigation and fabrication of EL devices. The analysis of possible chemical reactions between Alq3 and several atomic alkali and alkaline earth metals (Li, Al, K, Mg and Ca) and the injection characteristics at the Alq3/cathode interface have been of considerable interested by Shen et al. Recently [8,9], both from theoretical and experimental perspectives. Choong et al. have investigated the luminescence photoluminescence quenching phenomenon of Alq3 by using metal deposition [10]. Electronic structure of Alq3/ LiF/Al interface for organic electroluminescent (EL) device was studied by Mori et al. [11]. However, there remains a lack of systematic data relating to the metal chelate. A strong need still exists to deepen our knowledge of Alq3. In this article, we report systematically the synthesis, purification and the fundamental characteristics of Alq3 by the combination of X-ray diffraction (XRD) spectra, hydrogen nuclear magnetic resonance (HNMR) spectra, infrared absorption (IRA) spectra, mass spectra (MS), X-ray emission (XRE) spectra and fluorescence spectra analyses of Alq3 based on the

0921-5107/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0921-5107(03)00067-9

H. Li et al. / Materials Science and Engineering B100 (2003) 40 /46


Fig. 1. The chemical structure of Alq3 molecule.

surface and interface analysis of Alq3 and indium-tinoxide (ITO) [12] we have reported. These results are meant to be a reference for the monitoring of chemical processed that Alq3 may undergo during fabrication or degradation of light-emitting devices and for the understanding of the effects of ligand or metal substitution.

2. Experimental The fundamental principle of the synthesis of Alq3 is to combine HQ anion with Al3 in its aqueous solution. Alq3 is precipitated under the optimum condition by adjusting pH value of solution. The aqueous solution of aluminum nitrate or aluminum sulfate was chosen as Al3 ion. Sodium hydroxide (NaOH) was used to adjust the pH value of solution. The degree of chemical reaction depends on the acidity and alkalinity of reactive materials. The pH value of Alq3 when it is precipitated out completely ranged from 3 to 5. The chemical reaction during the synthesis of Alq3 is: C9 H7 NO  Al3  OH 0 C27 H18 AlN3 O3 H2 O (1) The concrete processes of synthesis are shown as follows: solution A was prepared by stirring 6.97 g HQ powder into 100 ml absolute ethanol and heating it up properly. Solution B was prepared by dissolving 15 g 9H2O /Aluminum nitrate into 200 ml deionized water and mixing completely. Dissolving 5.3 g NaOH into 60 ml deionized water to prepare solution C. Add solution A into B with full stirring until it dissolved absolutely and wait for about 15 min. The pH value of the mixed solution is 4. The floccule of Alq3 is precipitated by adding solution C dropwise into the mixed solution. The pH was adjusted to give a final value of 5. At last, we carried out the vacuum adsorptive percolation process after 24 h. The Alq3 filter cake was rinsed with deionized water. After repeating the process eight to ten times, transferred it into the vacuum chamber to dry at 150 8C. The prasinous Alq3 was obtained. It is important for the fabrication of EL devices to purify Alq3 and test the purity of it. But it is inevitable to bring impurities in during the synthesis of Alq3 due to the limitation of experimental conditions and purities of primary materials. Two methods of purification have been used in our experiments. Alq3 has a trend that it

would be sublimed under low-pressure. Therefore, we used vacuum sublimation process for first purification with a base pressure of 10 3 Pa. The vessel containing Alq3 sample was transferred into vacuum chamber with a big cleaned glass dish hanging over it. A baffle is between Alq3 and glass dish. Open the baffle when Alq3 was heated to about 230 8C in vacuum chamber. Alq3 was sublimed and adhered to the glass dish. Close the baffle when the temperature up to 270 8C. Then cooled it down to room temperature to get Alq3 powder from the glass dish. Vacuum sublimation process can only separate the impurities which their sublimation point is 20 8C higher or lower than that of Alq3. But it is not an effective method for materials which their sublimation point similar to that of Alq3. Thus column and thinlayer chromatography was used to further purify Alq3. Alq3 sample was injected into vaporizer of chromatograph rapidly and quantitatively, then was flowed into column by carrier gas after flash-vaporization. Each composition in Alq3 flowed out of column in turn due to their different dissolubility and absorbability, namely different distribution coefficient. So the impurities were separated. Because optimum effect can only achieved when sample was vaporized instantly, it is ought to be mindful to inject sample very quickly. The analysis of liquid chromatograph of Alq3 after purification shows that the purity of sample up to 98.5%. The color of Alq3 we got is bright yellow green.

3. Results and discussion 3.1. Purity test The purity of Alq3 either before and after purification was tested using a Varian Vista-5060 liquid chromatograph. Table 1 is the percentage concentration of each composition in Alq3. The purity of Alq3 has been enhanced greatly whereas the species and concentration of impurities have been decreased after it was purified. It is difficult to identify these impurities by using liquid chromatograph only. But some conjectures can be presented: there are two probabilities may introduce the impurities. One is attributed to that the slight amount of HQ ion would force the formation of more
Table 1 The percentage concentration of Alq3 and impurities in the sample Alq3 (100%) Before purification 81.15 Impurities (100%)

After vacuum sublimation process 91.50 After column chromatography 98.50 purification

1.45, 1.19, 1.63, 10.55, 4.13 0.37, 0.62, 0.65, 6.85 0.25, 1.25


H. Li et al. / Materials Science and Engineering B100 (2003) 40 /46

complex by chemical reaction. The formation of the complex ion was also followed by titrating solution, which contained NaOH. Another probability is that some inorganic matters were perhaps produced such as aluminum hydroxide. Of course we can not exclude the possibility that bring impurities in during the synthesis of Alq3 due to the limitation of experimental conditions and purities of primary materials. 3.2. The X-ray diffraction (XRD) spectra of Alq3 The XRD measurement was carried out using a CuKa radiation source (l /1.5405) in a Rigaku D/max2400 XRD spectrometer. The X-ray powder diffraction spectra of Alq3 formed at room temperature is shown in Fig. 2. The dominant peaks at 2u /9.090, 10.340, 13.540, 15.532, 18.360, 21.120, 22.520 and 24.022 are obvious. Their interplanar distance d calculated are 9.75, 8.57, 6.70, 5.72, 4.82, 4.16, 3.67 and 3.72, respectively. The allowable error decreased with the decreasing of d . The main values of d we got are basically within the allowable limits comparing with the standard data [13] and reveal that the chemical compound we got is really Alq3. No crystallographic structural information for the organic material Alq3 is available from the standard XRD data [13]. It is probably because single crystals of Alq3, which are essential for the structure determination, have not been obtained in the pure form because solvents are easily included in the crystals grown from solution [14,15]. 3.3. The hydrogen nuclear magnetic resonance(HNMR) spectra of Alq3 In order to study the local molecular structure of this chelate and interaction between Al3 and the ligand in Alq3 molecule, the investigation of HNMR of Alq3 and HQ were performed by using the AM-400 nuclear magnetic resonance spectrometer with a test frequency 400 MHz at room temperature. The solvent is deuterium chloroform solution (CDCl3). The HNMR spectra and the chemical structure of HQ molecule are shown in Fig.

3(a). The HNMR spectra of Alq3 is shown in Fig. 3(b). Although the H atoms in HQ molecule do not participate in coordinate reaction during forming Alq3, their inducibility contribute to monitoring the electronic environment at coordination bonds. The interaction between proton at aromatic rings and ligand also affect the HNMR of Alq3 to certain extent. From the variation of chemical shift Dd of H after coordinate reaction, the binding characteristics of metal /ligand and the informations of local molecular structure of this chelate were obtained. There are four environments of H atoms in HQ molecule, namely a, b, c and d, as shown in Fig. 3(a). The chemical shifts of H atoms at b, c, d atomic sites are all move downfield after coordinate reaction. It can be ascribed to the existence of Al3. Because the attractive power of Al3 made the density of electron cloud around H atomic nucleus of HQ ligands be decreased. Hence the shielding effect to external magnetic field be decreased. In addition, the variations of chemical shift also confirmed that Al3 have been participated the coordinate reaction. The variation of chemical shift at d atomic site (Dd /0.05 ppm) is smaller than that at c atomic site (Dd /0.09 ppm). It reveals that the effect on c atomic site is larger than that on d atomic site due to the existence of Al3. In other words, the coordinate effect between Al3 and O ion is more intensive than that between Al3 and N ion. The peak corresponding to the H nucleus at c atomic site should disappear if we assume that Al3 had replaced the H ions of hydroxy in HQ molecule. However, the appearance of the peak suggested that Al3 hasnot replaced H ion and the Al /O bond is covalence bond not ionic bond. There are still H  around O ion. As for the small peaks at high field band (d /3.344, 1.269, 1.249 ppm) are characteristic peaks of /OH, /O /CH2, /CH3 group. We consider that C2H5OH molecules may existed in compound. Another factor is noteworthy. Because the adjacent chelate molecules are close, the interaction between the definite magnetic field around H nucleus of a ligand and H ions of adjacent ligands leads to shielding or de-shielding effect which are related to geometrical structure of the

Fig. 2. The XRD spectra of Alq3.

H. Li et al. / Materials Science and Engineering B100 (2003) 40 /46


Fig. 3. (a) The HNMR spectra and chemical structure of HQ; (b) the HNMR spectra of Alq3.

chelate. Since there are six coordination bonds around Al3, O and N ions are all have strong binding force with Al3. So there are two types of stable octahedral isomers [7] which are illustrated in Fig. 4(a): meridional and (b): facial isomers. It is reasonable that the triple period is caused by 3-fold screw axis. Since the fac isomer has 3-fold symmetry, it cannot create triple period on stacking, and mer isomer is the unique candidate to form a such triple period ordering forming screw axis The fac isomer is instable at liquid or powder state. The meridional isomer is most. Thus, the special geometrical structure, meridional isomer, of Alq3 at powder state also affect its HNMR spectra.

3.4. The infrared absorption(IRA) spectra of Alq3 The IRA spectra of Alq3 shown in Fig. 5 was collected using Nicolet-1705x infrared spectrophotometer. The powder specimen is compacted into pellet with KBr. The broad characteristic peak at 3417 cm1 corresponding to OH  stretching vibration confirmed that the Al /O are coordinate not ionic bond. It is in good agreement with the HNMR results. The peak centered at 3055 cm 1 is attributed to the stretching vibration of C /H

Fig. 4. Geometrical isomers of Alq3 (a) meridional; (b) facial.

Fig. 5. The IRA spectra of Alq3.


H. Li et al. / Materials Science and Engineering B100 (2003) 40 /46

 , after at m /e /315 is the splintery ionic peak of Alq2 losing a neutral group of HQ from Alq3. We prospect if a further cleavage occurred, a peaks of Alq  after losing  a ligand from Alq2 should locate at m /e /171. However, the peak was not observed. The result is ascribed to the unique ionic state of Al. Each losing of ligand will change the metal /oxidation state of Al. The ionic state of Alq is difficult to exist.

bond in aromatic ring. Another vibrational mode at 1670 and 1604 cm 1 is assigned to the skeleton stretching vibration of /C /C / bond in aromatic ring. The prominent peaks which is the characteristic of the absorption vibration of the aromatic ring skeleton at 1588, 1550, 1467 and 1400 cm 1 suggested that the conjugate action of aromatic rings in molecule is very strong and all electron orbit of quinolinic rings are pbonding hybridizations. The peaks at 1390 and 1328 cm 1 is attribute to the stretching vibration of /C /N bond. The vibrational absorption peaks of /C /O at 1279 and 1251 cm1 are weaker and narrower than the homologous peaks of HQ (comparing with standard Sadtler IR spectral set). The disagreement between IRA spectra of Alq3 and HQ is excellent for indicating that there is a strong coordinate action which affect O bonding heavily between Al3 and O ions. The characteristic peaks of quinolinic rings from 600 to 800 cm 1 labeled the existence of quinolinc rings. Intensity of peaks at 460, 416 and 710 cm 1 were decreased, increased and disappeared, respectively, due to the coupling effect on vibrational modes between Al3 and ligands. However, the atomic coupling effect is not very strong because of the long bond distance. So that the Al /N vibrational mode can be regarded approximately as the vibration between Al3 and whole HQ molecule. The peaks corresponding to Al /N stretching vibration should locate in low frequency range around 200 cm 1 which is out of the measuring range of spectrophotometer if the big mass, long bond distance and low coupling coefficient of the molecule were considered. 3.5. The mass spectra (MS) of Alq3 The experiment carried out by using 2AB-HS massspectrometer. Since the location of characteristic peaks of ground oil, propenyl hydrate, are (92n/1), the MS of Alq3 after erasing the characteristic peak of ground oil is shown in Fig. 6. The peak at m /e /460.1 corresponds to  the molecular ion state Alq3 after capturing a H atomic. Therefore, the m /e of Alq3 is 459.1. The peak

3.6. The X-ray emission (XRE) spectra of Alq3 The XRE spectra of Alq3 is shown in Fig. 7. The electronic transition from specific orbit to fill vacant sites at inner orbit gives rise to XRE with specific wavelength. If electron originated from valence band, the corresponding fine structure of XRE spectra could reflect all kinds of orbit energy levels. The relative intensity of these peaks also reflects the bonding degree of different atomic orbits in specific molecular orbit. XRE spectra are often be used to investigate the binding characteristics in specific orbit. According to the selection rule of atomic orbit: DL /9/1, vacant sites in s orbit can detect the binding state of p orbital. At the same time, the vacant sites in p orbital can accept the transited electron from s, d orbital or molecular orbital with s, d orbital characteristics. The XRE data of Alq3 and Al are summarized in Table 2. Ka1,2 peaks of Alq3 were generated by the electronic transition from 2p to 1s orbit and affected by the ionization energy of 2p orbit. It is found that the Ka1,2 peaks have shifted comparing to Al due to the perturbation the ligand gives to 2p electron of Al. The perturbation is related to coordination intensity. The shift of Kb of Alq3 mainly resulted from the chemical environment variation around Al atomic. It also relates to binding intensity and coordination number. The intensity of Kb is lower than that of Ka (see Fig. 7). The wave length of Kb is shorter than that of Ka. Because the energy of M shell is higher than L shell, the energy decrease is large when exciting Kb, hence the wave length of Kb is short. However, the probability of transition from M to K shell is smaller than that from L

Fig. 6. The MS of Alq3.

Fig. 7. The XRE spectra of Alq3.

H. Li et al. / Materials Science and Engineering B100 (2003) 40 /46 Table 2 The XRE data of Alq3 and Al Peak site Al Alq3 Ka1 (eV) 1486.7 1487.0 Ka2 (ev) 1479.9 1481.5 Kb (eV) 1560.1 1556.6
? (eV) Kb


/ 1537.5

to K shell. Thus intensity of the Kb is weaker than Ka. The peak of Kb shifted to lower energy (about 3.5 eV) whereas the peak of Ka1,2 shifted to higher energy (0.3 and 1.6 eV) comparing to Al. The reason is that the formation of chemical bond has stronger influence on outer than inner shell. The electron in 2p orbit is inner electron with relative weak influence from ligand. When forming Alq3 molecular orbit, the decrease of the orbit energy made the outer electron attached to the molecular orbit tightly. So the energy decrease of Kb is larger than that of Ka when electron jumped to ground state exciting Kb. The over dense electronic cloudy between Al and ligand leaded to a decrease of charge shielding effect to 2p electron. It also resulted in the shifting of Ka towards higher energy region. Surprisingly, a weak adjoint peak at 1537.5 eV was observed from Fig. 7. We ascribed it to the formation of the hybridization orbit among O2s, O2p, N2s, N2p and Al3p orbits. The formed hybridization orbit has 3p orbit characteristics and contributed to Kb. Another point noteworthy is that there is a complex off-field electronic system (p-electronic system) in HQ molecule formed double-coordination-base chelate with Al. Al /O and Al /N are all s-bonds. If the ligands distributed symmetrically around Al, the N /Al /O should in one straight line, the s-bond should be co-formed by N2p, Al2p and Al3p, Kb. But the heterogeneous atoms N and O themselves, which have broken the symmetry of HQ molecule leads to complex fine structure of Kb. 3.7. The uorescence spectra of Alq3 Alq3 has excellent photoluminescence property. It emits bright fluorescence under ultraviolet radiation. The normalized fluorescence spectra of Alq3, Gaq3 and Inq3 with excited wave 400 nm are shown in Fig. 8. The peaks of Alq3 is at 510 nm (green range). The other metal /chelates, Gaq3 and Inq3, have the identical shape of spectra with Alq3. Their peaks have about 5 nm redshift comparing with Alq3. It confirmed the existence of a fluorescent species formed between metal cation and 8hydroxyquinolinol. It is not metal cation producing fluorescence. The chelated metal cations have an effect on system p-electronic cloudy and lone-pair electron of N. The effect depends upon ionic polarization force which have close relation to ionic radius, valency state and covalent characteristic. The more the ionic radius of chelated metal cations are, the lower valency state is.

Fig. 8. Normalized uorescence spectra of Alq3.

Thus the cations have weak polarization force and strong covalent characteristic. Since the ionic radius of Ga and In are larger than that of Al, their polarization force are weaker than that of Alq3. Thus the peaks of Gaq3 and Inq3 are red-shifted.

4. Conclusion In summary, the organic EL material Alq3 with high purity have been synthesized and purified. The analysis of IRA spectra explicated the bonding chacteristics of Alq3 and labeled the existence of quinolinc rings. The HNMR results demonstrated the interaction between metal ions and ligand in Alq3 molecule and the molecular geometrical isomers, namely mer isomer and fac isomer. The Al /O bond is covalent bond. Each H atom of Alq3 molecule has different belongingness. Electronic state of Alq3 is also discussed. From the MS the m /e ( /459.1) of Alq3 was obtained. The peak of Alq was not observed. Fluorescence data confirmed the existence of a fluorescent species formed between Al ion and 8-hydroxyquinolinol. It is not metal cation producing fluorescence.

Acknowledgements The authors would like to acknowledge Professor S.Y. Li and Dr Yong Qing for their fruitful discussions and useful suggestions. This work was partially supported by The State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. This work was supported by the National Science Fund of China (No. 60276026).

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