4
Jpn. 2003, 72, 3041. m) J. W. Lynn, Q. Huang, C. W. Brown, V. L. Miller, M. L. Foo, R. E. Schaak, C. Y. Jones, E. A. Mackey, R. J. Cava, Phys. Rev. B 2003, 68, 214516. n) J. D. Jorgensen, M. Avdeev, D. G. Hinks, J. C. Burley, S. Short, Phys. Rev. B 2003, 68, 214 517. [6] C. Fouassier, G. Matejka, J.-M. Reau, P. Hagenmuller, J. Solid State Chem. 1973, 6, 532. [7] R. J. Balsys, R. L. Davis, Solid State Ionics 1996, 93, 279. [8] C. Delmas, C. Fouassier, P. Hagenmuller, Physica 1980, 99B, 81. [9] Y. Takahashi, Y. Gotoh, J. Akimoto, J. Solid State Chem. 2003, 172, 22. [10] J.-J. Braconnier, C. Delmas, C. Fouassier, P. Hagenmuller, Mater. Res. Bull. 1980, 15, 1797. [11] C. Delmas, J.-J. Braconnier, P. Hagenmuller, Mater. Res. Bull. 1982, 17, 117. [12] K. Takada, K. Fukuda, M. Osada, I. Nakai, F. Izumi, R. A. Dilanian, K. Kato, M. Takata, H. Sakurai, E. Takayama-Muromachi, T. Sasaki, J. Mater. Chem. 2004, 14, 1448. [13] S. Miyazaki, S. Kikkawa, M. Koizumi, Synth. Met. 1983, 6, 211. [14] J.-J. Braconnier, C. Delmas, C. Fouassier, P. Hagenmuller, Mater. Res. Bull. 1980, 15, 1797. [15] L. Zhu, K. Seff, D. H. Olson, B. J. Cohen, R. B. von Dreele, J. Phys. Chem. B 1999, 103, 10 365. [16] a) N. Strukan, M. Cindric, B.Kamenar, Acta Crystallogr. C 1999, 55, 291. b) M. S. Wickleder, Z. Anorg. Allg. Chem. 2001, 627, 1439. c) J. A. Kaduk, Acta Crystallogr. B, 2002, 58, 370. [17] I. D. Brown, D. Altermatt, Acta Crystallogr. B 1985, 41, 244. [18] M. Karppinen, S. Asako, T. Motohashi, H. Yamauchi, Chem. Mater. 2004, 16, 1693. [19] F. Izumi, T. Ikeda, Mater. Sci. Forum 2000, 321±324, 198. [20] F. Izumi, R. A. Dilanian, in Recent Research Developments in Physics, Vol. 3, Part II, Transworld Research, Kerala, India 2002, pp. 699±726. [21] H. M. Rietveld, J. Appl. Crystallogr. 1969, 2, 65. [22] F. Izumi, S. Kumazawa, T.Ikeda, W. Z.Hu, A. Yamamoto, K. Oika- wa, Mater. Sci. Forum 2001, 378, 59. Red, Green, and Blue Colors in Polymeric Electrochromics** By Gursel Sonmez,* Hayal B. Sonmez, Clifton K. F. Shen, and Fred Wudl Having three additive primary colors (red, green, and blue (RGB)) constitutes an important step forward for the use of conducting polymers in polymeric electrochromic devices (PECDs). Although many red- and blue-colored polymers in their neutral form have been reported, the first report of a green-colored conjugated polymer has only recently been dis- closed. [1,2] The main reason for this delay has been the diffi- culty in obtaining the absorptions required in the visible re- gion to reflect green light. Since the three components of color space are completed, all other colors can be obtained ac- cording to color-mixing theory [3] which states that if two color stimuli are mixed, the resulting color stimulus will lie some- where along a straight line connecting two points on the chro- maticity diagram. The position of the point depends on the ra- tio of the amounts of the two mixed colors. A ªfine-tuningº of color is possible by adjusting film thickness. Here we report three additive primary colors (RGB) based on conjugated polymers as well as other colors obtained from their mixtures. Studies on electrochromic devices began with inorganic compounds such as tungsten trioxide (WO 3 ) and iridium diox- ide (IrO 2 ). [4] Because of the different colors observed with these compounds while switching among their different redox states, [5,6] organic materials (viologens, metallophtalocyanines, and conducting polymers) have recently received much atten- tion for electrochromic applications. [7] Conducting polymers in particular have several advantages over inorganic com- pounds. These include outstanding coloration efficiency, fast switching ability, [8] multiple colors with the same material, [9] and fine-tuning of the bandgap (and the color) through chemi- cal-structure modification. [10,11] As shown here and elsewhere almost all colors can be obtained using different conducting polymers at various oxidation states. [12,13] However, it would also be possible to get all colors from only three polymers that reflect RGB colors by mixing them in appropriate propor- tions. We have recently discovered a conjugated polymer from the electrochemical polymerization of 2,3-di(thien-3-yl)-5,7- di(thien-2-yl)thieno[3,4-b]pyrazine (DDTP) (2) that reflects green light in the neutral state and is transmissive in the oxi- dized state. [1] Dioctyl substitution of DDTP produced a more soluble monomer, 5,7-bis-(3-octyl-thiophen-2-yl)-2,3-di-thio- phen-3-yl-thieno[3,4-b]pyrazine (2), as well as its polymer and gave the first soluble green electrochromic conjugated poly- mer in its neutral form. [2] A combination of green 2 with red poly(3-alkylthiophene) (1) and blue poly(3,4-ethylenedioxy- thiophene) (3) completes the RGB additive color-space. Polymers 1, 2, and 3 were electrochemically polymerized onto indium tin oxide (ITO)-coated glass slides according to the procedure explained previously, [1] giving very smooth and homogeneous polymer films. These polymer films on the ITO-coated glass slides were used for further characterization and color mixing. Figure 1 presents the structures and a com- bined spectroelectrochemistry of 1, 2, and 3 in their neutral states. Obviously, polymer 1 absorbs in the blue region of the electromagnetic spectrum's visible region with a maximum peak at 500 nm and reflects red light. Polymer 3 absorbs in the red region of visible region with a maximum at 615 nm and reflects blue light. Since polymer 2 has two chromophores coming from two different conjugations, [1] it has a blue and red absorption of the visible with maxima at 380 and 760 nm COMMUNICATIONS Adv. Mater. 2004, 16, No. 21, November 4 DOI: 10.1002/adma.200400546 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1905 ± [*] Prof. G. Sonmez, [+] Dr. H. B. Sonmez, Dr. C. K. F. Shen, Prof. F. Wudl Department of Chemistry and Biochemistry and Exotic Materials Institute University of California Los Angeles, CA 90095-1569 (USA) E-mail: [email protected] [+] Permanent address: Sabanci University, Faculty of Engineering and Natural Sciences, Orhanli 34956 Tuzla, Istanbul, Turkey. [**] We gratefully acknowledge financial support from the Air Force Of- fice of Scientific Research through F49620-00-1-0103 and the Army Research Office through MURI DAAD19-99-1-0316. Instrumentation for this research was partially funded by NSF grand DGE-0114443.

Red, Green, and Blue Colors in Polymeric Electrochromics

Embed Size (px)

Citation preview

Page 1: Red, Green, and Blue Colors in Polymeric Electrochromics

���� ����� ��� ����� �� � � �� � �� ��� �� �� � ���� � �� ��������� �� �� ���� �� �� !"��#� �� $� � �%� �� &� ��!#��� �� ���'�� ��� �� � � ����� ��� (�� )�*� � � +� ���� %� � �� &',��'�+� -� �� #%� � �� ������� � "��.� ��� �� � � ����� ��� (�� )�/�

0*1 �� ����%%���� -� ��.�2#�� �3�� ����� 4� ���� ������� �� ����� ���������� ����� �� )�(�

0/1 �� � ���%�%� �� �� +�'�%� ����� ����� ����� ����� ��� (/5�061 �� +����%� �� ����%%���� 4� ���� ������� ����� ����� ���� 6��051 $� 7�#�"�%"�� $� -�.�"� � &#���.�� �� ����� ����� ����� ����� ����

((�0��1 �3� ���!� ���� �� +����%� �� ����%%���� 4� ���� ������� ���� �

��� �!��� ����� �"� �/5/�0��1 �� +����%� �3� ���!� ���� 4� ���� ������� ���� � ��� �!��� �����

��� ��/�0�(1 8� 7�#�,�� 8� ��#�,�� �� 9%�,�� :� ;�#��� �� :<���� �� &� +��� �� �

8� 8�.�� �� 7�#�.�� �� �#����� �� 7�#�����3������!"�� 7� �%�#���� ���� � ����� ���� �#� ���6�

0��1 � ����<�#�� � 8�##���� �� 8��<���� ����� ���� ����� �� (���0��1 �3� ���!� ���� �� +����%� �� ����%%���� 4� ���� ������� ���� �

��� �!��� ����� �"� �/5/�0�)1 �� ="�� 8� �>>� +� �� 9�%� � �� � ��"� � �� �� '� +������ �� ���

����� � ����� �$�� �� �*)�0�*1 �� ;� .��#� � �� �� ,��!� ��8��� ��� %��� � �����& � � ����� ""�

(5�� ?� �� � �!#��,��� '� %�� &� %��&� ����� ����� ���� ���5�!� � &� 8�,�#� %��� � �����& � �� ����� "�� �/��

0�/1 :� +� ���� � +� &�.����..� %��� � �����& � � ���� #�� (���0�61 �� 8��@@� � � � &%�#�� 7� ��.�"�%"�� �� $����!"�� ����� ���� �

���� ��� �*5��0�51 �� :<���� 7� :#�,�� ���� � ���� (� !� ����� ���)��#� �56�0(�1 �� :<���� �� &� +��� �� � � ������ ���� �� *� �������� �� �����

���� �� 4��. ::� 7�� %����, ��%���!"� 8������ : ,�� ����� @@� *55A/(*�0(�1 �� �� ���.'��,� �� %���� � �����& � ����� �� *)�0((1 �� :<���� � 8���<���� 7� :#�,�� � =� ��� &� $�����.�� 8� 9�#�3

��� ���� � ���� (� !� ����� ���� )5�

�� � ������ �� ���� ������ ����������� �������� ������!!

�� +! �� �����,�B -��� �� �����,����.��� /� (� ����� � , ( �� 0!��

��'� � ."��� �,,�.�'� @������ !����% C��,� ���� � � , ?���C�-��� !� %.�.�.�% � ��@��.� . %.�@ >�����, >�� ."� �%� �>!� ,�!.� � @������% � @�������! ���!.��!"����! ,�'�!�%C4��+%�� &�."���" �� � ��,3 � , ?���3!�����, @������% �

."��� ��.��� >��� "�'� ?�� ��@��.�,� ."� >��%. ��@��. �> ����� 3!�����, !� 2���.�, @������ "�% � �� ��!� .�� ?�� ,�%3!��%�,�0��(1 7"� ��� ���%� >�� ."�% ,���� "�% ?�� ."� ,�>>�3!��.� � �?.�� � � ."� �?%��@.�� % ��D����, � ."� '�%�?�� ��3��� .� ��>��!. ���� ���".� � !� ."� ."��� !��@� � .% �>!���� %@�!� ��� !��@��.�,� ��� �."�� !����% !� ?� �?.�� �, �!3!��,� � .� !����3��E� � ."����0�1 �"�!" %.�.�% ."�. �> .�� !����%.����� ��� ��E�,� ."� ��%��.� � !���� %.�����% ���� ��� %���3�"��� ��� � � %.����". �� � !� �!.� � .�� @�� .% � ."� !"��3��.�!�.� ,������� 7"� @�%�.�� �> ."� @�� . ,�@� ,% � ."� ��3.�� �> ."� ���� .% �> ."� .�� ��E�, !����%� & F>� �3.� � �G �>!���� �% @�%%�?�� ?� �,2�%.� � >��� ."�!# �%%� ���� �� ��@��.."��� �,,�.�'� @������ !����% C�-�� ?�%�, � !� 2���.�,@������% �% ���� �% �."�� !����% �?.�� �, >��� ."��� ��E.���%� .�,��% � ���!.��!"����! ,�'�!�% ?��� ��." � ���� �!

!��@�� ,% %�!" �% .� �%.� .���E�,� C9�� � , ���,��� ,��E3�,� C:�9(��

0�1 ��!��%� �> ."� ,�>>��� . !����% �?%��'�, ��."."�%� !��@�� ,% �"��� %��.!"� � ��� � ."��� ,�>>��� . ��,�E%.�.�%�0)�*1 ���� �! ��.�����% C'������ %� ��.����@".���!�� � �%�� , !� ,�!.� � @������%� "�'� ��!� .�� ��!��'�, ��!" �..� 3.�� >�� ���!.��!"����! �@@��!�.�� %�0/1 �� ,�!.� � @������%� @��.�!���� "�'� %�'���� �,'� .���% �'�� � ���� �! !��3@�� ,%� 7"�%� � !��,� ��.%.� ,� � !�����.�� �>>�!�� !�� >�%.%��.!"� � �?���.��061 ���.�@�� !����% ��." ."� %��� ��.������051

� , >� �3.� � � �> ."� ?� ,��@ C� , ."� !����� ."����" !"���3!��3%.��!.��� ��,�>�!�.�� �0�����1 &% %"�� "��� � , ��%��"�������%. ��� !����% !� ?� �?.�� �, �%� � ,�>>��� . !� ,�!.� �@������% �. '�����% �E�,�.�� %.�.�%�0�(���1 ����'��� �. ����,��%� ?� @�%%�?�� .� ��. ��� !����% >��� � �� ."��� @������% ."�.��>��!. �-� !����% ?� ��E� � ."�� � �@@��@���.� @��@��3.�� %�� "�'� ��!� .�� ,�%!�'���, � !� 2���.�, @������ >���

."� ���!.��!"���!�� @�������<�.�� �> (��3,�C."�� 3�3���3)�/3,�C."�� 3(3���."�� �0���311@���<� � C++74� C�� ."�. ��>��!.%���� ���". � ."� ��.��� %.�.� � , �% .�� %��%%�'� � ."� �E�3,�<�, %.�.��0�1 +��!.�� %�?%.�.�.�� �> ++74 @��,�!�, � ����%���?�� �� ����� )�/3?�%3C�3�!.��3."��@"� 3(3���3(��3,�3."��3@"� 3�3��3."�� �0���3?1@���<� � C��� �% ���� �% �.% @������ � ,��'� ."� >��%. %���?�� ���� ���!.��!"����! !� 2���.�, @���3��� � �.% ��.��� >����0(1 & !��?� �.�� �> ���� � ��." ��,@���C�3��#��."��@"� �� C�� � , ?��� @���C���3�."��� �,��E�3."��@"� �� C�� !��@��.�% ."� �-� �,,�.�'� !����3%@�!��4������% �� �� � , � ���� ���!.��!"���!���� @�������<�,

� .� � ,��� .� �E�,� C:79�3!��.�, ���%% %��,�% �!!��,� � .�."� @��!�,��� �E@��� �, @��'���%���0�1 ��'� � '��� %���." � ,"����� ���% @������ >���%� 7"�%� @������ >���% � ."�:793!��.�, ���%% %��,�% ���� �%�, >�� >��."�� !"���!.���<�.�� � , !���� ��E� �� ������ � @��%� .% ."� %.��!.���% � , � !��3?� �, %@�!.�����!.��!"���%.�� �> �� �� � , � � ."��� ��.���%.�.�%� 9?'���%��� @������ � �?%��?% � ."� ?��� ����� �> ."����!.����� �.�! %@�!.���H% '�%�?�� ����� ��." � ��E����@��# �. )�� � � , ��>��!.% ��, ���".� 4������ � �?%��?% � ."� ��, ����� �> '�%�?�� ����� ��." � ��E���� �. *�) �� , ��>��!.% ?��� ���".� � !� @������ � "�% .�� !"����@"���%!��� � >��� .�� ,�>>��� . !� 2���.�� %�0�1 �. "�% � ?��� � ,��, �?%��@.�� �> ."� '�%�?�� ��." ��E��� �. �6� � , /*� �

��

��

��

������

���� ����� ����� �� ��� ��� ������ � ���� �������� ���������� ���� ��������� ������ �� � ��� ����� ��� !�� ����

A"#$ %��&� �� '� �(�")$ *�� �� +� '� �(�

*�� �� �� ,� '!� � %��&� ,� �-.�*�/��0� 0 �& �!��10�2 � . +��3!��10�2� . �4�0�3 5�0�����1 � 10�0-0�6 ����1�02 �& ����&�� ����1 � ����1� �� 7��78��897 :6'�;�����< 1� �(=1�� 3�- ����.-

")$ %��� � 0 �..��11< '�� 3� 6 ����1�02� ,�3-�02 �& � �� ���� � � .��0-��� '3�� 3�1� >�!� �� ?�789 @-(��� �10� -�� @-�A�2�

"##$ �� ���0�&-��2 �3A �B��.�� &� � 3��� 1-//��0 &�� 0!� ��� ,��3� >&�&�3� �& '3�� 0�&�3 C�1���3! 0!��-�! ,�79�����������? � . 0!� ��2C�1���3! >&&�3� 0!��-�! 56C� *��*�7�77����?�9� � 10�-� 0�0�� &�� 0!�1 ��1���3! B�1 /��0����2 &- .�. 2 �', ��� . *���������?�

Page 2: Red, Green, and Blue Colors in Polymeric Electrochromics

� , � '����� �. ))� �� :. �% ��@��.� . .� �.� ."�. ."�%� �?3%��@.�� ��E��� � , �� ��� ��� ��!�.�, �E�!.�� �. ."� ��'�3�� �."% �"�!" ��� ��D����, � ��,�� .� ��>��!. ���� C������>�� , � !� 2���.�, @������%�� :. %"���, ��%� ?� �.�, ."�. �!��?� �.�� �> ."� %@�!.�� �> ."�%� ."��� @������% !�'��% ."��"��� '�%�?�� ����� !��@��.��� ��."��. ��>��!.� � � � ���".������� ( @��%� .% !����% ."�. !� ?� �?.�� �, >��� �� �� � ,

� �% ���� �% � ��E.��� �> !����% ."�. !� ?� �?.�� �, >���@������% �� �� � , � � .�� �E�,�.�� %.�.�% C ��.��� � , �E�3,�<�,�� ��� !���� ��E� � �E@����� .%� @������ >���% ���� @�.3.�� �, � :793!��.�, ���%% %��,�%� >������, ?� >�!�3.�3>�!� � 3%��.�� � � D���.< I�3'�% !�'�..� !� .�� � � ��� �.�.��?�.������ ��� "�E�>�����@"�%@"�.� C���;4�*� � �!�3.� �.���� C&�;� �% ���!.����.�� : �,,�.�� � @��.� �� � , %��'������ ���!.��,�% ���� �%�, >�� !� .����� � ."� @�.� .���% .�!"� �� ."� �E�,�.�� %.�.�% �> @������%� ;��.��� @������% �� , � ��>��!. ��, � , ���� !����%� ��%@�!.�'���� 7"� ��E.����> ."�%� .�� !����% @��,�!�% � '��� ,��# ?��� !����C���� (&3:�� &% � ��% �E�,�<�,� �.% !���� !"� ��, >��� ���� .� .�� %��%%�'� ?��� � , C� ��E.��� �>� ."�% !���� ��." ��,@��,�!�, � ,�>>��� . .� � �> ?��� C��,,�%"3?��� � !����C���� (&3::��� 7"� �E�,�<�, %.�.� �> � ��'�% � %#�3?��� !�����"�!" ��'�% � ,��#3���� !���� �"� ��E�, ��." ��.��� �C���� (&3:::�� "� ."� �E�,�<�, %.�.�% �> � � , � ��� ��E�,�� ����A?��� !���� �% �?.�� �, C���� (&3:��� ��������� ,�>>��3

� . !����% !� ?� �?.�� �, >��� � !��?� �.�� �> � � , �� � ,� � , � C���%� (���� ��%@�!.�'����� :. �% ��@��.� . .� �.� ."�.���."���" ."� %��� @������% ���� �%�, � ������% (&A�� !����.� �% '��� ,�@� ,� � � ."� !���� �> �."�� @������ @��%� .�"� %.�,�� � � !����� �.% "�� ���� '��� ,�@� ,� � � �.% ����3�� �.�� � , �.% %����� ,� �%� :����� �.�� !"� ��% ."� "��?�!��%� �> ."� !���� �> ���".� ����� �% ."� @��,�!. �> ��'�3�� �."% ."�. ��� ��."�� �?%��?�, �� ��>��!.�, ?� ."� %��>�!� �>� �?2�!. ?�� � %.�� ��� ������ �.�,� 7"� "�� �@@���% .� ��.���!!��,� � .� � !����H% %����� ,� �% �% ."� ��.� � �% �>>�!.�, ?�."�%� ��'��� �."% � , ."� %.����� ��� !���� �!�.�, .� ."�!��.�E C."� @��. �> ."� ?��� ."�. � �?��% �% .� ,�%.� ���%" � �%"�,� >��� � �."����

��

��

��

�����

��

���� ���� ��������� ������ �� � ��� ����� ��� !�� ����������� ���� ���� ����� ����� �� ��� ��� ������ �

a)

b)

300 400 500 600 700 800 9000.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

P3MeTh PDDTP PEDOT

visible

Ab

sorb

ance

(a.

u.)

Wavelength (nm)

������ � �; '0�-30-�� �& 0!� /��2��1 -1�. &�� �..�0��� /����2 3����1� . ; 0!��� 3�� �. 1/�30�����30��3!��10�2 � 0!� �-0��� &��< �:%?5�@!;� � :%**@%;� � . � :%�*>@;�

I II III IV

I II III IV

I II III IV

������ � *�&&��� 0 3����1 �0�� �. B!� �; � � . �� +; � � . �� � .�; � � . � B��� �4�. �0 0!� �-0��� : ; � . �4�.�(�. :�; 10�0�1� ���< �: ; � . � : ;� ����< � : ; � . � :�;� �����< � :�; � . � : ;� ����< � :�; � . �:�;D +��< � : ; � . � : ;� +���< � : ; � . � :�;� +����< � :�; � . � : ;� +���< �:�; � . � :�;� ���< � : ; � . � : ;� ����< � :�; � . � : ;� �����< � : ; � . �:�;� ����< � :�; � . � :�;�

Page 3: Red, Green, and Blue Colors in Polymeric Electrochromics

: �,,�.�� .� ."� �� .�� �, �,'� .���% �> !� 2���.�,@������% �% ���!.��!"����!%� ."��� �% � �."�� '��� ��@��.� .@�� . �"�!" "�% �. ?�� � ,���� �, %� >��� �"�!" �% ."� ,�>>��3� . �E�,�.�� %.�.�% ."�. ��'� ,�>>��� . .� �% �> ."� %��� !������ %���.���% ,�>>��� . !����% >��� ."� %��� @������� &%%"�� � ������ ��� ."� �E�,�.�� %.�.�% �> � !� ,�!.� � @���3��� !� ��%��� ?� !� .�����, ?� � ���!.��!�� @�.� .��� �"�!"!"� ��% ."� �E�,�.�� %.�.� �> @������� ,�@� ,� � � ."�

�@@���, @�.� .���%� ��� �E��@��� 4�+97 C�� !� ?� %��.!"�,%.�@��%� >��� �.% >���� ��.���� ,��#3?��� %.�.� �. A��5 �� .� �.�� %@��� . %#�3?��� !���� � �.% >���� �E�,�<�, %.�.� �. J��� �C���� ���� 7"��� ��� �. ���%. (� %.�@% ."�. !� ��%��� ?� !� 3.�����, ?� !"� �� � ."� �@@���, @�.� .���� ��%��.� � � ,�>>��� .� .� %�.��% �> ."� %��� @������H% �?%��@.�� �. ."� %�����'��� �." � ."� '�%�?�� %@�!.���� ���� %������ ��%��.% ������@��.�, >�� ��� !� ,�!.� � @������% � !��,� � � � , �� � !���!" �> ."�%� %.�@% @��,�!�% ,�>>��� . !���� .� �%� � ,��� @���3

����! ���!.��!"����! ,�'�!�0��1 �%� � .�� ,�>>��� . !� ,�!.� �@������% !� @��,�!� �. ���%. ��� ,�>>��� . !����% C(� !����%>��� � � @������ .���% (� !����% >��� ."� �."���� : @�� !�3@��� ?�%�, � ."�% @��,�!.� �"� !� 2���.�, @������% ��."."� ."��� @������ !����% C�-�� ��� �%�, >�� !���� ��E� �� �.���%. �(�� ,�>>��� . !����% !� ?� �?.�� �, >��� ."��� ��E.����: !� !��%�� � ."� �,,�.�'� @������ !����3%@�!� ��% !��3

@��.�, ?� ."� ,�%!�'��� �> ."� >��%. ���� @�������! ���!.��3!"����!� ��E.���% �> � � .�� �> ."� ."��� �,,�.�'� @������!����% � '�����% �E�,�.�� ��'��% !� @��,�!� ."��%� ,% �>!����% ��%��.� � >��� @�%%�?�� .� �% �> ."�%� @������% ."�.!� ?� �?.�� �, �. ,�>>��� . �E�,�.�� ��'��%� ��� �> ."� !��3��% ."�. !� ?� �?.�� �, >��� � �� .�� ��,�E %.�.�% �> ."�%�."��� @������% C>���� �E�,�<�, � , >���� ��,�!�,� �% ���� �%."� ."��� �,,�.�'� @������ !����% ��� ��'� � ������ �?� ���3?� � � ."� �� � �,'� .���% �> !� ,�!.� � @������% .���."����." ��!� . ,�'���@�� .% � � #2�. @�� .� � .�!" ������%>�� �%"�% ."� @�%%�?���.� �> @�� .� � ."�� ��. C�. � %@�!�>�!��%���.�� � � .� >��E�?�� %�?%.��.�%�0��1 � ?����'� ."�. ."�!��@��.�� �> �,,�.�'� @������ !����3%@�!� .���."�� ��." ."�,�%!�'��� �> ."� >��%. ���� @�������! ���!.��!"����! "����,%� 4��+ ����

23�� �������

&�� !"���!��% ���� @��!"�%�, >��� &�,��!" �"���!��� 4��@��� �!��?� �.� C4�� C55�/K� � "�,���%�� ,�!"������."� � C+���� � ,�!�.� �.���� C&�;� ���� ,�%.����, �'�� !��!��� "�,��,� ?�>��� �%�����!.��@�������<�.�� ��% !�����, ��. ��." � �& ����L @�.� 3

.��%.�.� ��@���� � :793!��.�, ���%% %��,�% �% ���#� � ���!.��,�� �@��.� �� >��� �� ���� �% !�� .�� ���!.��,�� � , � %��'�� ���� �� ���� �&�L&�;9� C&�L&�J� �% ��>��� !�� 7"� ���!.����.� �%�, ��% ��� � �>.�.��?�.������ ��� "�E�>�����@"�%@"�.� C���;4�*� � +���&�;� �� ��E.��� �> &�; � , +��� 7"� ���!.��,�@�%�.�� ��% @��3>����, >��� � ���� � %���.�� �> ."� �� ���� � ."� ���!.����.� @�3.� .��,� ���!���� �. � %!� ��.� �> (� ��%A� �� @�.� .��%.�.�!���� �.)� ���?�'� ."� �E�,�.�� @�.� .��� �> �� ����� @�!.�����!.��!"���!�� ,�.� ���� ��!��,�, � � �����.. 4�!#��,

6�)� I�3'�% %@�!.��@"�.���.�� !� �!.�, .� � !��@�.��� & ."���3���!.��,� !��� �%%��?�� ��% �%�, �"��� ."� ���#� � ���!.��,� ��% � :793!��.�, ���%% %��,� C/ ��M)� ��M��* ��� �% � �� �L�� +��.�7�!" ������% : !��� ."� !�� .�� ���!.��,� ��% � @��.� �� ���� � , �&� ���� ��% �%�, �% @%��,�3��>��� !� ���!.��,�� 7"� @%��,�3��>��3� !� ��% !���?��.�, �E.�� ���� �%� � � ) �� %���.�� �> >����!� �C�!L�!J� � ."� ���!.����.� C2�L(C�!L�!

J� NJ����� � '��%�% &� ����� , J���6� � '��%�% &�L&�J � ��� � ���;4�*L&�;�� 7"� @�.� .���%��� ��@��.�, '��%�% &�L&�J� 4������ >���% >�� %@�!.�����!.��!"���%3.�� ���� @��@���, ?� @�.� .��,� ���! ,�@�%�.�� � :793!��.�,���%% %��,�%���� !����3��E� � �E@����� .% � ������ (� @������ >���% ���� >��%.

���!.��!"���!���� ,�@�%�.�, � :793!��.�, ���%% %��,�%� @�..�� �, ?�!���>�� ����'�� �> %��� @��.% �> @������%� 7"� � >�!�3.�3>�!� � %��3.�� �> .�� @�..�� �, @������3!��.�, :793%��,�% � � D���.< I�3'�%!�'�..� !� .�� � � � ��� � ���;4�* � &�; �% ���!.����.� ��% >��3����,� 4��.� �� � , %��'�� ����% ���� �%�, �% !�� .�� � , ��>��� !����!.��,�%� ��%@�!.�'���� .� !� .��� @�.� .���% >�� !"� �� � ."� �E�,�3.�� %.�.�% �> @������%�& ��2�>��� C�� �4�E &���� ,���.�� !����� ��% �%�, .� .�#� @"�.�3

���@"% �> ."� @������% �. "��" ��%���.�� �

��!��'�,O &@��� ��� (����� �� '��%�� O � � (�� (���

��

��

��

������

���� ����� ����� �� ��� ��� ������ � ����������� ���� ���� ��������� ������ �� � ��� ����� ��� !�� ����

400 600 800 1000 1200 1400 16000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8 visible

+1.0 V

+1.0 V-0.9 V

-0.9 V

Abs

orba

nce

(a.u

.)

Wavelength (nm)

-0.90 V -0.80 V -0.70 V -0.60 V -0.50 V -0.40 V -0.30 V -0.20 V -0.15 V -0.10 V -0.05 V +0.00 V +0.05 V +0.10 V +0.15 V +0.20 V +0.25 V +0.30 V +0.35 V +0.40 V +0.50 V +0.60 V +0.70 V +0.80 V +0.90 V +1.00 V

a)

b)

������ � �; '/�30�����30��3!��10�2 �& � �0 .�&&��� 0 �4�.�0�� 10�0�1B�0! � 1�0 /�30-��1 �& �����0�� � 0!� �-� 3���� �0 .�&&��� 0 �4�.�0�� ������1� ; *�&&��� 0 3����1 �0�� �. -1� � �40-��1 �& C�+ 3����1 � . 0!���0B� ��.�4 10�0�1�

Page 4: Red, Green, and Blue Colors in Polymeric Electrochromics

A0�1 -� � ��<� �� 8� �� "� � $� ��?� � �� �,�� %�&�4� ����� ���� 2��

���� #�� ��56�0(1 -� � ��<� �� �� � ��<� �� 8� �� "� � �� �%.� $� ��?� � �� �,��

��� ������!�� ���� � @��%%�0�1 �� +� 9'��"���� +� �� �� ��� 5�&�� ��� ���� � ����� ;�� $��#

�����0�1 � �� +��.���� .3 ��."� *���� ����� �� ��0)1 4� �� � �� #� �� � ���.����� +� �� ��%%�� %#�� 2���� ��� ����6

(!��������� ��� %����������� ���� �� "���� -���� � ����0*1 8� �� ��� 7� ���?#�� %� � ���� � ����� �� ���0/1 �� � ���.����� 2���� �������� %���� ����� ##� (5/��061 &� 8����� +� �� ��%"� �� �� ���'� .� �� 4����E� 8� &� &??��,�

� �� ��� ��,%� ����� ���� � ����� �$� 65*�051 -� � ��<� �� �� �� �� �,�� ����� ���� � ���� ��� )/��0��1 -� � ��<� :� !"�� ,��� � 4� !"�..�� ,� 8� =� �� � �� ���3

��,%� ��� ������!�� ����� ��� *�5�0��1 :� !"�� ,��� � �� ��!#�� � -� � ��<� 4� !"�..�� ,� 8� =� ��

+� �� ��%"� � �� ��� ��,%� ����� ���� � ����� �#7 ���6�0�(1 � &� �@@� -� &� �.<� �� � �� ��� ��,%� ����� ���� � ����� �$�

(����0��1 �� �� 7"��@%� � 4� !"�..�� ,� 8� =� �� � �� ��� ��,%� ����� ��8

�� � ����� ��� �)*��0��1 @�!��� �%%�� � F: #2�. 4�� .� � �> �� !.�� �� ��.�����%G� ���

�!��� ����� ��� 6�(�

"��#$%�&���'� � ������ "��������� ��������� (�& �$�������& )�� ��!!

�� +!����!�� (������ 9��: �� �� ��� ���� /� -� -��%�� �� % ��� �� *� �� ���/��,���0������ ;� �� -!�:� � , ����� � -� ( ����B

4"�%� %�@���.�� � @������ ?�� ,% �% %.�� ��� ,�@� ,� .�@� %�?%.��.� %��>�!� � �����0�1 �� ��!���� '���� � ."�% %��3>�!� � ����� �. �% @�%%�?�� .� � ,�!� @����,�! %.��!.���% � �@������ ?�� , >����0(1 %� !� � � !��@� � . �> ."� ?�� , ����@��>��� .����� �����.� ���� >��� ����� % �> "��"�� %��>�!�� ���� �> ."� ,�>>��� !� � %��>�!� � ���� ?�.��� ."� .������� % �% %�>>�!�� .�0�1 ��� ,% �> !� 2���.�, @������% "�'�?�� �%�, �E.� %�'��� � ."� >�?��!�.�� �> @������ ���".3���.3.� � ,�'�!�% C4��+ �� .��!.���� ��,�>�!�.�� % � ."� @���3

���% �%�,� �% ���� �% ,�>>��� . ?�� , !��@�%�.�� %� @��'�,����.�% .����,% �@.���<�, ,�'�!� �>>�!�� !��%� :. "�% ?�� ,��3� %.��.�, ."�. !� .����� � ."� ���@"����� �> ."� @"�%�3%�@�3��.�, %.��!.��� � %�,� ?�� , ,�'�!�% !� ?� �%�, .� � "� !��E!�.� ,�%%�!��.�� � , @"�.�,��,� @��>���� !��0�A*1 ���3�'��� �'� � ."� ?�%. ,�'�!�%� � �� � ����.�, ���� . �> ���".!� �%!�@� ."� ,�'�!� %� !� � �%.���.�, /�K �> ."� ���".�� ���.�, �% .��@@�, � ."� ��'����,� ��,� C���� ��� � , �%�� ������ ��%. ."����" �,�� ���%%�� �� ��3�?%��@.�� �0/1

�'���� �@@���!"�% �"�!" ��� ?�%�, �@� ."� � .��,�!.�� �>@����,�! !������.�� % %�!" �% %@� !��.� � � .�@ �> � !����3��.�, @"�.���%�%. �����061 �� ?� ��?�%%� � ."� ���%%�'� �����051

"�'� ?�� �%�, .� �E.��!. %�!!�%%>���� ."� @������3� �,���'����,� ��,�� ?�. ��� ���� � �,,�.�� �� ��."����@"�! .�!"3 �D��%� : ."�% !���� �!�.�� � �� ��@��. � ."� � !��%�� �>%��>3���� �<�,� .��3,��� %�� �� C(+� @"�.� �! %.��!.���% ��."

��

��

��

�����

��

���� ���� ��������� ������ �� � ��� ����� ��� !�� ���� �������� ���������� ���� ����� ����� �� ��� ��� ������ �

A"#$ %��&� C� �� ,��� .� *�� �� ���3��� � %��&� %� �� �� ���")$

*�� �� �� ����1� *�� E� *� 5�3�� (������ .�1! �����0��2� *�/��0� 0 �& %!21�316 ����1�02 �& ����.��5�.� ���2 C��.� ����.�� �+? ��� :6�;�����< �!&��=3���3�-A�� ,�3!�0� *�� �� @� '� �-3A5������� �����0��2 &�� %��2�� '2 0!�1�1� *�/��0� 0 �& �!��10�26 ����1�02 �& ����.���� 1&���. C��.� ����.�� �+� ��� :6�;

")$ %��1� 0 �..��11< ,�3-�02 �& '3�� 3����0�� ��6 ����1�02 �& '� ��/������B�� �� 0 C�.�� C��.� '��F8�?� '� ��/����

"##$ �� �3A �B��.�� 0!� �%'C� :�� ,�;� 0!� ����.�� �-��/�� @�-10� . C���0 ���.� �� ,����B1!�/ :�� ��;� ����.�� *�1/��2 @�3!� ����2 :��,�;� '0 E�! G1 ������� :%� �� �� ��;� ��� � . 0!� �1��3��B0� @�-10 :�� @� '� ��; &�� &� � 3��� 1-//��0�

C8H17C8H17

**

n

PFO

C8H17C8H17

*

nNN

S

F8BT

(a) (b)

(c)

(d)

������ � �; ���!0���11�� �.�1 �& � 02/�3�� /��2�� ��* 1!�B� � 0!�1-�&�3� ��11�� � . �@>H/��2�� B����-�.� �.�� ; ���!0���11�� �.�1 �& � /����.�3���2 /�00�� �. /��2�� �� . ��* 1!�B� � 0!�1-�&�3� ��11�� � . ��3�����. �@>H/��2�� B����-�.� �.��3; �� I �� � �,5 /!�1� ���� �& F��30� 2�0��3!����1��� � '�5 /�� 0�.� >��/��1� 0���0�. %�*>@<%'' B�0! 0!� '�5 3!��3�� 10�-30-��1!�B � 0!� � 1�0� @!� �4�1 1!�B � :3; .�&� � 0!� /����2 � � . ���1-��� 0 .���30�� 1� .; �!��3�� 10�-30-��1 �& ,J+@ � . %,>�