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VOLUME 72, NUMBER 19
11 MAY 1998
Mechanism of unidirectional liquid-crystal alignment on polyimides with linearly polarized ultraviolet light exposure
M. Nishikawa,a) B. Taheri, and J. L. Westb)
Liquid Crystal Institute, Kent State University, Kent, Ohio 44242
Received 9 February 1998; accepted for publication 5 March 1998 Unidirectional liquid-crystal LC alignment by a linearly polarized ultraviolet light UV exposure was examined using two types of polyimide PI . PI with a ﬂuorene unit incorporated in a side chain showed LC alignment perpendicular to those of conventional PIs, i.e., perpendicular to the rubbing direction and parallel to the exposure polarization of UV. The results of the dichroic ratio measurement of LC cells, UV absorption spectra, birefringence, infrared absorption spectra, and PI conformation calculations using molecular mechanics suggest that the photodecomposition of PI by UV exposure produces anisotropic van der Waals forces, which align LC along its optical axis. © 1998 American Institute of Physics. S0003-6951 98 00919-X
Liquid-crystal LC displays LCDs are widely used because of their low-power consumption, thin proﬁle, and full color capability. To fabricate LCDs, unidirectional LC alignment with a controlled pretilt angle is typically produced using surface rubbing techniques.1 However, rubbing may cause static charge, dust, or scratches, which lower the production yield of LCDs. Methods such as Langmuir–Blodgett ﬁlms,2 stretched polymers,3 microgrooves,4 stamped polymers,5 and linearly polarized ultraviolet light UV exposure of polymers,6 have been proposed, which produce unidirectional LC alignment without rubbing. Among them, LC alignment using linearly polarized UV exposure is a strong candidate for overcoming the above problems in addition to greatly simplifying production of multidomain displays. Two main types of material for LC alignment using a polarized UV exposure have been proposed. One is based on photoisomerization of azocompounds doped in polymers.7–9 The other utilizes anisotropic photoreactions of poly vinyl cinnamate derivatives6,10–12 and polyimides PIs 13–15 produced by linearly polarized UV exposure. Much effort has been devoted to develop photoreactive PIs which show high heat resistance compared with those of azocompounds and poly vinyl cinnamate derivatives. However, the mechanism of unidirectional LC alignment using PIs exposed to linearly polarized UV has yet to be clariﬁed. In this letter, we wish to explore the mechanism and characteristics of unidirectional LC alignment using UV exposed PIs. The PI materials used in these experiment are shown in Fig. 1. PI ﬁlms were prepared by heat curing of precursor polyamic acid solutions, which were synthesized from the reaction between tetracarboxylic dianhydride and diamines. LC cells were prepared to measure dichroic ratios of LCs aligned by linearly polarized UV-exposed PI ﬁlms. PI ﬁlms were deposited by ﬁrst spin coating dilute solutions of the respective polyamic acids on indium tin oxide glass substrates and then curing at 250 °C for an hour. The thickness
FIG. 1. Chemical structures of PIs used.
of the PI ﬁlm was controlled at 50 nm. The PI ﬁlms were exposed with linearly polarized UV incident normal to the surface. We used a 450 W xenon lamp Oriel, model 6266 as the UV source, and a surface ﬁlm polarizer Oriel, model 27320 whose effective range is between 230 and 770 nm. The intensity of UV after passing through the polarizer was about 6 mW/cm2. LC cells for dichroic ratio measurement were fabricated using two polarized UV-exposed substrates with parallel polarization axes. Dichroic LC, ZLI-2293 Merck and 0.5% M-618 Mitsuitoatsu, max 550 nm , was ﬁlled into the cells in the isotropic state 120 °C . Dichroic ratios of the LC cells were measured using one polarizer and a UV–visible spectrometer, Perkin Elmer Lambda 19. PI ﬁlm birefringences were measured using an instrument described previously.16 Infrared spectra of the PI ﬁlms were measured using an infrared spectrometer, Nicolet 550. The LC alignments produced by either rubbing or exposure to normally incident polarized UV are summarized in Table I. PI-1 shows LC alignment parallel to the rubbing direction and perpendicular to the UV polarization. This is consistent with results reported previously.13,14 PI-2, however, aligns LC perpendicular to the rubbing direction and
TABLE I. LC alignment on PIs. LC alignment direction PI Rubbing Parallel Perpendicular Polarized UV Perpendicular Parallel
On leave from Yokkaichi Research Laboratories, JSR Co., Yokkaichi, Mie, 510-0871, Japan. Electronic mail: firstname.lastname@example.org b Electronic mail: email@example.com
0003-6951/98/72(19)/2403/3/$15.00 2403 © 1998 American Institute of Physics Downloaded 07 Sep 2011 to 184.108.40.206. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
Lett. measured relative to the rubbing direction. On the other hand. To elucidate the LC alignment mechanism. Redistribution subject to AIP license or copyright. and results in the decreases of the dichroic ratios of the LC cells. 4. In the case of rubbing Fig.org/about/rights_and_permissions . and PI-2 shows a negative dichroic spectrum.31. and increases in the broad absorption above 290 nm. 72. 3. it should be noted that the subtraction spectra of UV absorption spectra FIG. FIG. respectively. those with polarized UV exposure perpendicular to the rubbing direction showed no change of their dichroic ratios.13 Figures 5 and 6 show the dichroic UV absorption spectra obtained by subtracting absorptions measured parallel (A para) and perpendicular (A per) to the rubbing direction and the exposed UV polarization. After UV exposure. We have not yet determined the photochemical changes in the PI ﬁlms. Dichroic UV absorption spectra (A para A per) of rubbed PI ﬁlms dichroic ratios of LC cells. No. Dichroic UV absorbance was measured using a surface ﬁlm polarizer.195.aip. 5 . which corresponds to the broad absorption around 250 nm. we conﬁrmed the effective axis for LC alignment. Figure 3 shows the relationship between polarized UV irradiation time and dichroic ratios of LC cells. 5.2404 Appl. UV absorption spectra of PI ﬁlms. see http://apl. The behaviors using polarized UV exposure are opposite to those produced by rubbing Fig. These phenomena have been previously reported on PI material with different chemical structure. 11 May 1998 Nishikawa. Changes in the UV absorption spectra of the PI ﬁlms before and after polarized UV exposure were monitored. 2. Figure 4 shows UV absorption spectra of the PI ﬁlms before and after polarized UV exposure. Phys. Figure 2 shows the relationship between the polarized UV exposure time and dichroic ratios of LC cells. and West FIG. 6 . Relationship between polarized UV exposure time after rubbing and FIG. Taheri. which can be attributed to – * transitions of benzene rings in PI. parallel to the UV polarization. 19.137. In both PIs. both PI ﬁlms showed decreases in the broad absorption around 250 nm.17 These results suggest that polarized UV absorbed parallel to the aligned PI main chains selectively causes the photochemical reaction of PI. and approach a constant value at higher dosage. Furthermore. Furthermore. PI ﬁlms on quartz substrates were prepared after polarized UV exposure for 2 h at surface normal. Vol. PI-1 shows a positive dichroic spectrum. It is well known that the rubbing treatment of the PI surface results in the alignment of PI chains parallel to the rubbing direction. PI-2 shows low sensitivity to UV exposure compared with that of PI-1. but it is clear that the broad absorption above 290 nm is generated by the decomposition of PI. Dichroic ratios of LC cells initially increase logarithmically with UV dosage. dichroic ratios of LC cells exposed with polarized UV parallel to the rubbing direction gradually decreased with UV irradiation time. Rubbed PI ﬁlms were exposed normally with polarized UV parallel and perpendicular to the rubbing axis for 0–40 min.. Relationship between UV exposure time and dichroic ratios of LC cells on PI ﬁlms. Downloaded 07 Sep 2011 to 129.
Ono. Kobayashi. L632 1992 . Kozinkov. PI conformations calculated using the molecular mechanics method. Kawamura. West. Seo. and O. 36.-H. Kobayashi.Appl. Abe. 3162 1997 . Sangen. 127 1981 . Fujii. N. Hasegawa and Y. the ﬂuorene unit in PI-2. C. Kawatsuki. Changes in the PI ﬁlms before and after polarized UV exposure were also monitored using infrared absorption spectra. Bessho and Dr.. The residual PI chains perpendicular to the exposed UV polarization. L. and J. W. Ji. J. Mol. D. Y. Phys. 15 1996 . Y. Cryst. Kusano. Phys. and V.. Marusii. Liq. and M. Nishikawa. Matsuura.-S. H. N. J. FIG. 71. Uchida. M. Cryst. Miyashita. X. Photopolym. Bessho. J. Hayashi. 2 T. D. Nishikawa. K. Sun. 13 M. T.-S. above 290 nm show no dichroism Fig. 8 Y. Saitoh. and T. S. Kano. L. and M. Wang of Kent State University for material synthesis. Miyamoto. Part 2 33. S. Lett. Y. is aligned perpendicular to the axis of the main chain. Chien. J.. and T.. Redistribution subject to AIP license or copyright. M. Y. which show no photodecomposition. 19. 2. D. Cryst. Ohta. PI chains parallel to the exposed UV polarization direction are selectively decomposed by UV exposure. The birefringence measurement of PI ﬁlms after linearly polarized UV exposure also showed that PI-1 had the optic axis perpendicular to the UV polarization. X. Yabe. J. M. Vol. Sasaki. Liq. Jpn. Mada. Y. Ichimura. 1 Downloaded 07 Sep 2011 to 129. Cryst. Phys. Aoyama. Schadt. 819 1992 . In both PI ﬁlms. 2155 1992 . T.. 703 1995 . 18 M. 12 N. Ukr. Iimura. 7. Shi. 19. Y. 275. Part 1 31. Y. Sugawara. Research was supported in part by NSF Science and Technology Center ALCOM. Taira. Jpn. Iimura. and Dr. Jpn. and PI-2 had the optic axis parallel. and S. Kozenkov. Phys. Through the experiments and simulation in this letter. Fiz. M. T. N. 5 E.. and photoproducts after UV exposure are randomly relocated in the PI ﬁlms. Yamazaki. No. 11 Y. Khizhnyak. 72. Kobayashi. Shannon. Ikeda. Yokoyama. 1059 1991 . Phys. Appl.-S. 16. These results suggest that imide rings in PIs were decomposed by UV exposure. Kumar. Kim. Part 2 32. Yoshida. V. We calculated the conformations of PI-1 and PI-2 using the molecular mechanics method Fig. The authors acknowledge Dr. 3 H. Schmitt. T. 17 M. Dyadyusha. Yamamoto. Bessho. Nishikawa.org/about/rights_and_permissions . 8. and West 2405 we conclude that before UV exposure. Jpn. Sakamoto. 14 J. Appl. J. 6680 1997 . 449 1993 . 64. Aoyagi. Iimura. P. H. 703 1995 . Kosa. S. peak intensities at 1380 cm 1 attributed to the (imide C–N–C) decrease and those at 1720 cm 1 attributed to the (C 0) increase after UV exposure. Liq. T. which has a large birefringence. Nature London 368. J. Appl. Sci. FIG. Kobayashi. Macromolecules 30. 26. Matsuki of JSR Co. Lee. and N. and S. Kobayashi. Part 2 32.-D. D. and A. Lett. S. Technol. 10 M. cause the anisotropic van der Waal forces to align the LC along its optical axis. Y.31. for their support in this research. J. H. Ltd. Cryst. 1027 1994 . 6. Kelly. Phys. and S. Phys. N. Y.aip. T. V. Reshetnyak. S. Appl. Gibbons. 11 May 1998 Nishikawa. Cryst. and Y. S. Sugano. Nishikawa. Nishikawa. L1436 1993 . M. 289 1995 . the interplay between the main chain and the side ﬂuorene unit leads PI-2 to have low sensitivity to polarized UV compared with that of PI-1 as shown in Fig. 16 D. see http://apl. Y. Lee. Lett. Appl. 15 J. Zh. Natsui. Seo. Tsuda. T. and useful discussions. Hashimoto. Kobayashi. T. M. 7 P. 72. and S. L810 1994 . Sci. 4 Y. Hasegawa. and S. 9 K. Bessho. Jpn. PI ﬁlms on silicon wafers were normally exposed to polarized UV for 2 h. H. Part 2 31. Takatoh. Kawata.18 The optical axis of PI-1 is aligned along the polymer backbone. T. V. and K. 7 . Appl.. Phys.137. Takatsuka. Mol. Dichroic UV absorption spectra (A para A per) of UV exposed PI ﬁlms measured relative to the UV polarization. SID Symp. Photopolym. N. 6 . K. 6 A. Liq. On the other hand. Vetter. Proceedings of the 12th International Display Research Conference. PI chains in the ﬁlm are randomly aligned. and a new band with infrared absorption at around 1720 cm 1 was generated by the by-product after the decomposition of PI. 8. Reznikov. and T. Iimura. They also acknowledge Dr. J. Y. L93 1993 . 258 1995 . Dig. Also. Akiyama. Chigrinov. H. Dr. R. Technol. Seo. birefringence measurement. Wang. DMR 89-201747. Taheri. 532 1994 .195. Appl. Y.
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