APPLIED PHYSICS LETTERS

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 uorene 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 prole, 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 LangmuirBlodgett lms,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.79 The other utilizes anisotropic photoreactions of poly vinyl cinnamate derivatives6,1012 and polyimides PIs 1315 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 claried. 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 lms 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 lms. PI lms were deposited by rst 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
a

FIG. 1. Chemical structures of PIs used.

of the PI lm was controlled at 50 nm. The PI lms 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 lm 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 lled into the cells in the isotropic state 120 C . Dichroic ratios of the LC cells were measured using one polarizer and a UVvisible spectrometer, Perkin Elmer Lambda 19. PI lm birefringences were measured using an instrument described previously.16 Infrared spectra of the PI lms 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: mnishi@lci.kent.edu b Electronic mail: johnwest@scorpio.kent.edu

PI-1 PI-2

0003-6951/98/72(19)/2403/3/$15.00 2403 1998 American Institute of Physics Downloaded 07 Sep 2011 to 129.137.195.31. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions

2404

Appl. Phys. Lett., Vol. 72, No. 19, 11 May 1998

Nishikawa, Taheri, and West

FIG. 2. Relationship between UV exposure time and dichroic ratios of LC cells on PI lms.

FIG. 4. UV absorption spectra of PI lms.

parallel to the UV polarization. Figure 2 shows the relationship between the polarized UV exposure time and dichroic ratios of LC cells. Dichroic ratios of LC cells initially increase logarithmically with UV dosage, and approach a constant value at higher dosage. Furthermore, PI-2 shows low sensitivity to UV exposure compared with that of PI-1. To elucidate the LC alignment mechanism, we conrmed the effective axis for LC alignment. Rubbed PI lms were exposed normally with polarized UV parallel and perpendicular to the rubbing axis for 040 min. Figure 3 shows the relationship between polarized UV irradiation time and dichroic ratios of LC cells. In both PIs, dichroic ratios of LC cells exposed with polarized UV parallel to the rubbing direction gradually decreased with UV irradiation time. On the other hand, those with polarized UV exposure perpendicular to the rubbing direction showed no change of their dichroic ratios. It is well known that the rubbing treatment of the PI surface results in the alignment of PI chains parallel to the rubbing direction.17 These results suggest that polarized UV absorbed parallel to the aligned PI main chains selectively causes the photochemical reaction of PI, and results in the decreases of the dichroic ratios of the LC cells. Changes in the UV absorption spectra of the PI lms

before and after polarized UV exposure were monitored. PI lms on quartz substrates were prepared after polarized UV exposure for 2 h at surface normal. Figure 4 shows UV absorption spectra of the PI lms before and after polarized UV exposure. After UV exposure, both PI lms showed decreases in the broad absorption around 250 nm, which can be attributed to * transitions of benzene rings in PI, and increases in the broad absorption above 290 nm. We have not yet determined the photochemical changes in the PI lms, but it is clear that the broad absorption above 290 nm is generated by the decomposition of PI, which corresponds to the broad absorption around 250 nm. These phenomena have been previously reported on PI material with different chemical structure.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, respectively. Dichroic UV absorbance was measured using a surface lm polarizer. In the case of rubbing Fig. 5 , PI-1 shows a positive dichroic spectrum, and PI-2 shows a negative dichroic spectrum. The behaviors using polarized UV exposure are opposite to those produced by rubbing Fig. 6 . Furthermore, it should be noted that the subtraction spectra of UV absorption spectra

FIG. 3. Relationship between polarized UV exposure time after rubbing and FIG. 5. Dichroic UV absorption spectra (A para A per) of rubbed PI lms dichroic ratios of LC cells. measured relative to the rubbing direction. Downloaded 07 Sep 2011 to 129.137.195.31. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions

Appl. Phys. Lett., Vol. 72, No. 19, 11 May 1998

Nishikawa, Taheri, and West

2405

we conclude that before UV exposure, PI chains in the lm are randomly aligned. PI chains parallel to the exposed UV polarization direction are selectively decomposed by UV exposure, and photoproducts after UV exposure are randomly relocated in the PI lms. The residual PI chains perpendicular to the exposed UV polarization, which show no photodecomposition, cause the anisotropic van der Waal forces to align the LC along its optical axis. Also, the interplay between the main chain and the side uorene unit leads PI-2 to have low sensitivity to polarized UV compared with that of PI-1 as shown in Fig. 2. The authors acknowledge Dr. L. C. Chien, Dr. T. Kosa, and Dr. X. D. Wang of Kent State University for material synthesis, birefringence measurement, and useful discussions. They also acknowledge Dr. N. Bessho and Dr. Y. Matsuki of JSR Co., Ltd. for their support in this research. Research was supported in part by NSF Science and Technology Center ALCOM, DMR 89-201747.

FIG. 6. Dichroic UV absorption spectra (A para A per) of UV exposed PI lms measured relative to the UV polarization.

above 290 nm show no dichroism Fig. 6 . The birefringence measurement of PI lms after linearly polarized UV exposure also showed that PI-1 had the optic axis perpendicular to the UV polarization, and PI-2 had the optic axis parallel. Changes in the PI lms before and after polarized UV exposure were also monitored using infrared absorption spectra. PI lms on silicon wafers were normally exposed to polarized UV for 2 h. In both PI lms, peak intensities at 1380 cm 1 attributed to the (imide CNC) decrease and those at 1720 cm 1 attributed to the (C 0) increase after UV exposure. These results suggest that imide rings in PIs were decomposed by UV exposure, and a new band with infrared absorption at around 1720 cm 1 was generated by the by-product after the decomposition of PI. We calculated the conformations of PI-1 and PI-2 using the molecular mechanics method Fig. 7 .18 The optical axis of PI-1 is aligned along the polymer backbone. On the other hand, the uorene unit in PI-2, which has a large birefringence, is aligned perpendicular to the axis of the main chain. Through the experiments and simulation in this letter,

FIG. 7. PI conformations calculated using the molecular mechanics method.

M. Nishikawa, T. Miyamoto, S. Kawamura, Y. Tsuda, and N. Bessho, Proceedings of the 12th International Display Research Conference, 819 1992 . 2 T. Sasaki, H. Fujii, and M. Nishikawa, Jpn. J. Appl. Phys., Part 2 31, L632 1992 . 3 H. Aoyama, Y. Yamazaki, N. Matsuura, H. Mada, and S. Kobayashi, Mol. Cryst. Liq. Cryst. 72, 127 1981 . 4 Y. Kawata, K. Takatoh, M. Hasegawa, and M. Sakamoto, Liq. Cryst. 16, 1027 1994 . 5 E. S. Lee, P. Vetter, T. Miyashita, T. Uchida, M. Kano, M. Abe, and K. Sugawara, Jpn. J. Appl. Phys., Part 2 32, L1436 1993 . 6 A. Dyadyusha, V. Kozenkov, T. Marusii, Y. Reznikov, V. Reshetnyak, and A. Khizhnyak, Ukr. Fiz. Zh. 36, 1059 1991 . 7 P. J. Shannon, W. M. Gibbons, and S. T. Sun, Nature London 368, 532 1994 . 8 Y. Iimura, J. Kusano, S. Kobayashi, Y. Aoyagi, and T. Sugano, Jpn. J. Appl. Phys., Part 2 32, L93 1993 . 9 K. Ichimura, Y. Hayashi, H. Akiyama, and T. Ikeda, Appl. Phys. Lett. 64, 449 1993 . 10 M. Schadt, K. Schmitt, V. Kozinkov, and V. Chigrinov, Jpn. J. Appl. Phys., Part 1 31, 2155 1992 . 11 Y. Iimura, T. Saitoh, S. Kobayashi, and T. Hashimoto, J. Photopolym. Sci. Technol. 8, 258 1995 . 12 N. Kawatsuki, H. Ono, H. Takatsuka, T. Yamamoto, and O. Sangen, Macromolecules 30, 6680 1997 . 13 M. Hasegawa and Y. Taira, J. Photopolym. Sci. Technol. 8, 703 1995 . 14 J. L. West, X. D. Wang, Y. Ji, and J. R. Kelly, SID Symp. Dig. 26, 703 1995 . 15 J.-H. Kim, Y. Shi, S. Kumar, and S.-D. Lee, Appl. Phys. Lett. 71, 3162 1997 . 16 D.-S. Seo, S. Kobayashi, M. Nishikawa, and Y. Yabe, Liq. Cryst. 19, 289 1995 . 17 M. Nishikawa, Y. Yokoyama, N. Bessho, D.-S. Seo, Y. Iimura, and S. Kobayashi, Jpn. J. Appl. Phys., Part 2 33, L810 1994 . 18 M. Nishikawa, N. Bessho, T. Natsui, Y. Ohta, N. Yoshida, D.-S. Seo, Y. Iimura, and S. Kobayashi, Mol. Cryst. Liq. Cryst. 275, 15 1996 .

Downloaded 07 Sep 2011 to 129.137.195.31. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions