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268

Rylene and Related Diimides for Organic Electronics

Xiaowei Zhan,* Antonio Facchetti,* Stephen Barlow,* Tobin J. Marks,* Mark A. Ratner,* Michael R. Wasielewski,* and Seth R. Marder*
electrons to empty orbitals, respectively.[1] Organic HT and ET materials differ from Organic electron-transporting materials are essential for the fabrication of classical inorganic p- and n-type semiconorganic p-n junctions, photovoltaic cells, n-channel eld-effect transistors, ductors in that they are generally undoped, and complementary logic circuits. Rylene diimides are a robust, versatile class and so that very few charge carriers are typof polycyclic aromatic electron-transport materials with excellent thermal and ically present except under an applied eld, oxidative stability, high electron afnities, and, in many cases, high electron in which case carriers can be injected from mobilities; they are, therefore, promising candidates for a variety of organic electrodes, from other proximate organic materials, or are generated via photoexcielectronics applications. In this review, recent developments in the area of tation. Charge transport can be described high-electron-mobility diimides based on rylenes and related aromatic cores, as a series of successive electron-transfer particularly perylene- and naphthalene-diimide-based small molecules and reactions between neutral and charged polymers, for application in high-performance organic eld-effect transistors molecular or polymeric repeat units. In and photovoltaic cells are summarized and analyzed. the hopping transport regime this process involves essentially localized radical cations (HT) or anions (ET) and the corresponding neutral species, while the orbitals of a -conjugated 1. Introduction polymer chain can facilitate intrachain electron transfer in the Organic charge-transporting materials are -conjugated molesuperexchange or coherent tunneling regime.[2] The tendency cular or polymeric compounds in which charge carriers migrate of the holes (electrons) to migrate under the inuence of a eld under the inuence of an electric eld. These materials can can be described by the hole (electron) mobility, , of the matebe classied as hole- or electron-transport (HT or ET) material; this has units of velocity per unit eld and is, in general, rials according to whether the majority charge carriers, under dependent on both the electric eld and temperature. An addia given set of conditions, arise from removal of electrons from tional class of materials, ambipolar materials, have similar hole the manifold of lled molecular orbitals or from the addition of and electron mobilities and can act as either HT or ET materials, depending on the dominant injection processes occurring under the experimental conditions of interest. Prof. X. Zhan In general, development of high-performance (environmenBeijing National Laboratory for Molecular Sciences tally stable, high-mobility) organic ET materials has lagged Institute of Chemistry behind that of HT materials despite their importance for fabriChinese Academy of Sciences, Beijing 100190, China cating organic photovoltaic (OPV) cells and n-channel organic E-mail: xwzhan@iccas.ac.cn eld-effect transistors (OFETs), which are particularly valuable Prof. A. Facchetti, Prof. T. J. Marks, Prof. M. A. Ratner, as components of organic complementary logic circuits, which Prof. M. R. Wasielewski Department of Chemistry require both p- and n-channel transistors.[3,4] To achieve acceptMaterials Research Center, and Argonne-Northwestern Solar Energy able performance, ET materials must have: i) high electron Research Center afnity (ideally greater than 3 eV, but not exceeding 5 eV) to Northwestern University facilitate injection from contacting electrodes in OFETs or to facilEvanston, Illinois 60208-3113, USA E-mail: a-facchetti@northwestern.edu; t-marks@northwestern.edu; itate exciton separation in conjunction with typical HT materials ratner@northwestern.edu; m-wasielewski@northwestern.edu for OPV applications; ii) good intermolecular electronic orbital Prof. A. Facchetti overlap to facilitate high mobility; and iii) good air stability, idePolyera Corporation ally both as neutral and radical anion materials and, as discussed Skokie, Illinois 60077, USA in more detail below, under device operating conditions.[1] For Dr. S. Barlow, Prof. S. R. Marder general reviews on ET materials, see references [1,3] and [4]. School of Chemistry and Biochemistry The criteria for useful ET materials described above can often Center for Organic Photonics and Electronics Georgia Institute of Technology be met by appending strong electron-withdrawing substituents, Atlanta, Georgia 30332-0400, USA such as uoro, cyano, or acyl, to -conjugated cores such as E-mail: Stephen.barlow@chemistry.gatech.edu; acenes and oligothiophenes, which, in the absence of these subseth.marder@chemistry.gatech.edu stituents, exhibit HT properties. Other classes of ET materials, DOI: 10.1002/adma.201001402 such as the fullerenes, which have been widely studied for a

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variety of applications, have inherently moderate to high electron afnities in the absence of electron-withdrawing substituents. Another extensively studied materials class, which is the focus of this review, is that of rylene tetracarboxylic diimides. Rylenes are hydrocarbon families that can be regarded as naphthalene oligomers, with bonds between the 1 and 1 positions and between the 8 and 8 positions of adjacent naphthalene units, i.e., they are oligo(peri-naphthalene)s. The rylene tetracarboxylic diimides considered here all bear two six-membered dicarboxylic imide rings fused to the terminal naphthalene units; the three simplest rylene diimide systems, naphthalene1,8:4,5-tetracarboxylic diimide (2, NDIs), perylene-3,4:9,10-tetracarboxylic diimide (4, PDIs), and terrylene-3,4:11,12-tetracarboxylic diimide (5), are shown in Figure 1. Interest in rylene diimides and other aromatic diimides, such as those based on benzene and anthracene (1 and 3, respectively, Figure 3), stems from early observations of ET behavior and the ability to tune molecular electronic properties by well-established organic chemistry, through either variation of substituents on the imide nitrogen atoms or on the rylene skeleton. Rylene diimides can exhibit relatively high electron afnities, high electron mobilities, and excellent chemical, thermal, and photochemical stabilities. These molecules and their derivatives have been used not only as building blocks for electronic and optoelectronic devices such as organic light-emitting diodes,[5] dye lasers,[6] optical switches,[7] and photodetectors,[8] but also as electron acceptors for studying photoinduced energy- and electron-transfer processes.[9] Several accounts have summarized the synthesis and organization for various applications of PDI and NDI materials.[1014] In the present review, we focus on the most recent developments on high-mobility rylene-diimide-based small molecules and polymers for high-performance OFETs and OPVs (see Figure 2 for device structures and operation principles). The high electron afnities of rylene diimides makes them attractive candidates for ET materials in OFET and OPV devices; however, as will be seen in the following sections, challenges in achieving optimum ambient device operation remain.

Antonio Facchetti is a cofounder and the CTO of Polyera Corporation. He obtained a Ph.D in Chemical Sciences from the U. Milan (Italy) and carried out postdoctoral research at the University of California, Berkeley and at Northwestern University, where he is currently an Adjunct Professor. Dr. Facchetti has published about 200 research articles, 6 book chapters, and holds about 30 patents. He received the 2009 Italian Chemical Society Research Prize and the team IDTechEx Printed Electronics Europe 2010 Award. Xiaowei Zhan obtained a Ph.D. degree in chemistry from Zhejiang University in 1998. He was then a postdoctoral researcher at the Institute of Chemistry at the Chinese Academy of Sciences (ICCAS) from 19982000, and in 2000 he was promoted to associate professor at ICCAS. Dr. Zhan worked at the University of Arizona and Georgia Institute of Technology from 20022006 as research associate and research scientist. He has been a full professor at ICCAS since 2006. His research interests include the development of organic and polymeric materials for organic electronics and photonics. Tobin J. Marks is the Vladimir N. Ipatieff Professor of Chemistry and Professor of Materials Science and Engineering at Northwestern University. He received his B.S. from the University of Maryland (1966) and Ph.D. from MIT (1971), and came to Northwestern immediately thereafter. In 2006, he was awarded the National Medal of Science, the highest scientic honor bestowed by the United States Government. Marks is on the editorial boards of 9 major journals, consultant or advisor for 6 major corporations and start-ups, and has published 935 research articles and holds 93 U.S. patents.

2. Empirical Relationships Between Electronic Structure and Device Operation Under Ambient Conditions
Before discussing specic materials in detail, it is important to stress one generic issue that is important for all ET materials: their air stability. In most cases, air instability is not due to degradation of intrinsically chemically unstable neutral materials, but arises from the vulnerability of the corresponding radical anions to reaction with atmospheric H2O or O2, an issue rst discussed by de Leeuw et al.[15] This vulnerability of the charge carriers to trapping under ambient conditions, which can frequently be precluded to some degree by operation under inert conditions (e.g., vacuum or encapsulation),[16] can seriously impair ET. Given that the ultimate promise of organic semiconductors is in inexpensive, large-area, solution-processed, or printed electronics, compatible with high-throughput reel-toreel manufacture, developing air-stable materials is crucial to minimize costly vacuum- or inert-atmosphere-based fabrication steps and device encapsulation.[3,4]

Rational strategies for enhancing rylene ambient stability must prevent the trapping species from reaching the charge-transporting lm area and/or involve the design of molecules or polymers in which the mobile electrons are

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X Y O R N O R 1a CH2CH2C8F17 2a 2b 1b O C8H17 N O R 3a 3b 3c 3d C8H17 C8H17 CH2C3F7 CH2C3F7 X X CN H Br CN 2k CF3 X O C8H17 N O X 2l 2m X CN Br O O N C8H17 X O X= 6a O OC12H25 OC12H25 OC12H25 O 4q 4r O C7F15CH2 N O N CH2C7F15 CF3 X O N R O O R N O R H C8H17 4a 4b 4c CH3 CF3 CH2CH2C8F17 4d O N R O O R N O R C6H5 C8H17 C13H27 C18H37 OC12H25 OC12H25 OC12H25 4f CH2C3F7 4g 4h 4i 4j 4k 4l CH2C3F7 CH2C3F7 CH2C3F7 CH2C3F7 C6H5 O N R O O R N O Y X R X CN CN F F Cl Cl Br Br CN F Cl Cl Cl O X O Cl X NH O Cl Cl Cl Y H H H F Cl Cl Br H H H O N R O

2c CH2C7F15 2d O N C8H17 O 2e 2f 2g C6F5 2h CH2CH2C6F5 2i 2j C6H13 CF3 O C5H11 N O

4e

4m CH2C3F7 4n O N C5H11 O 4o 4p CH2C3F7 C8H17 C6F6 Cl O X O

5a X

(H2C)3O

Figure 1. Chemical structures of some rylene diimide small molecules.

kinetically or thermodynamically resistant to trapping. It is generally believed that H2O and O2 can be excluded either by utilizing crystalline materials with sufciently dense molecular packing to resist penetration by these species or by appropriately encapsulating the devices in inert atmosphere, although, as noted above, additional encapsulation steps should ideally be avoided. Thermodynamic stability is a complex issue. A solution phase electrochemical reduction potential more positive than 0.66 V vs the saturated calomel electrode (SCE) is generally thought necessary to stabilize the charge carriers in ET materials with respect to H2O reduction.[17] This means that the lowest unoccupied molecular orbital (LUMO)[18] of this molecule should lie at an energy below approximately 3.7 eV with respect to vacuum. Several materials satisfy this requirement, including the perylene and naphthalene diimide cores. However, molecular materials in which negatively charged carriers are not thermodynamically susceptible to O2 oxidation would require a far more daunting reduction potential of greater than +0.57 V (vs SCE), and thus, LUMO energies less than 4.9 eV. Materials with such large electron afnities are rare; moreover, suitable partner HT materials for use in applications such as OPV cells would require very low-lying highest occupied molecular orbitals (HOMOs), possibly raising additional stability issues due to the susceptibility of the holes to reduction by water. However, an overpotential to the charge carrier + O2 reaction could, in principle, prevent ambient trapping in materials where the LUMO energies are considerably less negative.

Recent experimental and theoretical studies empirically identied this energetic threshold at approximately 4.0 to 4.3 eV (Figure 3), which scales to an overpotential versus O2 reduction of approximately 0.9 to 0.6 V and is applicable to several rylene diimide and other families of OFET materials.[16,1922] In the following sections, we will see that ambient operational stability for rylene and other aromatic diimide ET materials, particularly in FET devices, can be achieved by following two design strategies: 1) the introduction of (per)uorinated substituents at the imide N,N positions to create close-packed solid-state atmospheric barriers and 2) the introduction of highly electronwithdrawing substituents such as cyano (CN) and F on the aromatic core, thereby lowering substantially the LUMO energies.

3. Rylene and Other Aromatic Diimide Small Molecules for OFET Devices
3.1. Phenylene, Naphthalene, and Anthracene Diimides In this section we review small molecules based on the simplest rylene diimide system, naphthalene-1,8:4,5tetracarboxylic diimide (Figure 1, 3). In addition, we consider diimides based on other small aromatic cores, benzene-1,2:4,5tetracarboxylic diimide (pyromellitic diimide, 1) and anthracene-2,3:6,7-tetracarboxylic diimide (3), both of which differ

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attained in NDIs by varying N,N substitution, Shukla et al. reported that compared to linear Id , V d Metal cathode n-hexyl chains, cyclohexyl substituents assist I Source Drain Donor-Acceptor Blend in directing intermolecular stacking, Semiconductor affording a dramatic increase in mobility ITO anode Vg Dielectric from 0.70 (2j) to a reported 6.2 cm2 V1 s1 (2i) in vacuum.[29] Gate Compared to work on NDIs, there have LUMO hv been very few reports on pyromellitic diime ides and anthracene-2,3:6,7-tetracarboxylic e --diimides. Katz et al. reported the only + h LUMO example of OFETs based on a pyromellitic diimide:[23]1a (Figure 1) exhibits a mobility of HOMO 0.054 cm2 V1 s1 in air, an order-of-magnitude HOMO ITO Donor Rylene Metal lower than the NDI analogue with the same Contact Rylene diimide diimide N,N substituents (2f),[27] however compound 1b exhibits a mobility approaching Figure 2. Structures and operation principles of an OFET and OPV cell based on rylene diim2 1 1 2 1 1 ides. a) OFET material components (top) and energetics of electron injection from the FET 0.1 cm V s in vacuum and 0.4 cm V s source contact into the rylene lowest unoccupied molecular orbital (LUMO). In an FET, the in the air. Marks et al. reported the only examcurrent ow between source and drain electrodes (Id) on application of a drain-source bias (Vd) ples of OFETs based on anthracene-2,3:6,7is modulated by the bias applied between gate and source electrodes (Vg). When Vg = 0 V, Id tetracarboxylic diimides.[31] Devices based on is minimal and the device is in the off state. When Vg 0 V is applied (VSG > 0 V for n-type 3b exhibit a mobility of 0.02 cm2 V1 s1 in transistors) the device turns on and charge carriers are accumulated at the semiconductor vacuum, 10 times lower than its NDI counterdielectric interface, resulting in a gate-controlled Id. Principal FET gures-of-merit include eldpart with the same substituents (2b). However, effect mobility (), current on-to-off ratio (Ion:Ioff ), threshold voltage (Vth) dening, respectively, the average charge carrier drift velocity, drainsource current ratio between on and off OFETs based on 3b do not operate in air due states, and the gate voltage at which the injected carriers are mobile. b) OPV cell material com- to the relatively low electron afnity. Introducponents (top) and energetics of the light absorption and charge-collection processes involving tion of cyano groups at the 9,10 positions of a rylene diimide as the acceptor material. In an OPV device, the light passing through the trans- the anthracene ring signicantly increases the parent contact (typically indium tin oxide, ITO) is absorbed in the active layer to form excitons electron afnity and, therefore, improves air (hole-electron pairs), which dissociate into free charges at the interface between the donor and stability; devices based on 3a exhibit a mobility the acceptor layer. Holes and electrons ow in the donor and acceptor (rylene diimide) regions, 2 1 1 respectively, and are collected at the electrodes, resulting in the generation of electrical power. of 0.02 cm V s in air, which is somewhat Principal gures-of-merit include the power conversion efciency (PCE), short-circuit current lower than that found for an NDI analogue (Jsc), and the open-circuit voltage (Voc), ll factor (FF), dening, respectively, the ratio between having the same substituents (2l).[32] the output device electrical energy versus the input solar energy, the device current when no The optical properties and crystal structures reverse bias is applied, and the device voltage when no current ows through the cell, and the of these diimides provide interesting insights ratio between maximum power of the device and Jsc Voc, respectively. into their comparative electronic structures, solid-state packing, and potential for applications. As expected, the optical absorbtion maximum shifts to from the other diimides considered here in that the cores are longer wavelengths upon proceeding from benzene (e.g., for not strictly rylenes and in that they contain ve-membered 1a max 310 nm) to naphthalene (e.g., for 2l max 350 nm, imide rings.[2331] The earliest attempt to fabricate OFETs from naphthalene dimides (NDIs; Figure 1) yielded a mobility of 104 cm2 V1 s1 for compound 2a.[24] Later, Katz et al. demonstrated that the performance and air stability of the OFETs -3.2 could be greatly improved by varying the NDI N,N substituNC -3.4 F ents. Replacing hydrogen with an n-octyl group at the N,N NC O C H positions of 2a led to a 103 times enhancement in mobility C H CH S O N O -3.6 S C F O NC to 0.16 cm2 V1 s1 measured in vacuum for 2b,[25] although NC S almost no FET activity was measurable in air. It was found that NC CN -3.8 S S S CH the n-CH2C7F15N,N substituents in 2c signicantly improve O N O S O CH O N O CH O N O device air stability, with mobilities of 0.050.1 cm2 V1 s1 measCH O N O -4.0 F O S CN NC ured in air.[25,26] Replacing the methyl substituents on the N,N CF C H 5 benzyl groups of 2d with CF3 groups in 2e leads to 10 times O N O O O O N O -4.2 CH C H NC O N O CN enhancement of the mobility in air,[25] while elongating CF3 to NC CH CN C H O O -4.4 n-CH2CH2C8F17 further enhances the mobility from 0.12 (2e) to C H C H 0.57 cm2 V1 s1 (2f)[27]. Strikingly, inserting an ethylene bridge CN NC -4.6 between the nitrogen atoms and the peruorophenyl substituAmbient Sensitive Ambient Stable ents of 2g to give 2h (Figure 1) leads to a crystalline, rather than 6 an amorphous, material and boosts the mobility from <10 to Figure 3. LUMO energy vs ambient stability correlation for OFETs based on several organic ET materials. 0.31 cm2 V1 s1.[28] In another example of morphology control

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Field-Effect Transistor

Photovoltaic Cell

energy [eV]

energy [eV]

LUMO Energy (eV)

12

25

12 25

8 17

6 13

8 17

8 17

8 17

8 17

6 13

8 17

8 17

17

17

12

25

8 17

12 25

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Figure 4. Optical absorption of a core-cyanated naphthalene (a) and an optically transparent thin lm transistor (TFT) (b) based on compound 2l. Reproduced with permission.[30] Copyright 2007, American Chemical Society.

Figure 4) to anthacene (e.g., for 3a max 420 nm) diimides. Thus, the negligible optical absorption of these semiconductors through most of the visible region of the spectrum may enable their application in optically transparent devices. Katz and Marks have independently demonstrated transparent FETs based on 2h[28] and 2l,[30] which exhibit electron mobilities of 0.2 cm2 V1 s1 and 0.1 cm2 V1 s1, respectively (Figure 4). The crystal structure of at least one member each rylene family has been reported (Figure 5). The crystal structure of 1b exhibits a unique cofacial packing between the phenyl substituent ring and the -pyromellitic diimide core. The majority of crystal structures reported of NDI derivatives exhibit variations of the classic herringbone packing motif, characterized by edge-to-face interactions.[32] Indeed, in the case of a single triuoromethyl substituent at the 4 position of the benzyl group (2e), packing occurs in a herringbone fashion, whereas in the case with trifluoromethyl groups at the 3 and 5 positions (2k), the NDI cores are oriented parallel to each other, with -stacking along the a-axis (out of the page) and the closest intermolecular spacing in the -stacking direction equal to 3.147 (O2-C1).[27] Clearly, slight changes in structure induce considerably different packing motifs for these molecules. For compounds of family 3, two crystal structures have been determined.[33] The conjugated backbone of 3c adopts a substantially planar molecular conguration with a negligible interplanar twist angle. The molecular length is measured as 11.63 along the molecular backbone. The neighboring molecules are -stacked in a slipped cofacial orientation along the a-axis with an interplanar stacking distance of only 3.1401 . As expected, the peruoroalkyl end chains adopt a trans conguration with respect to each other. Furthermore, the relatively large uorine atoms are densely packed, which could in principle inhibit air penetration to the cores and thus serve as a kinetic barrier to improve air stability for these devices. Similarly, the anthacene core of molecule 3d is planar and extended stacking interactions are observed along the a-axis with an interplanar distance of 3.183 , whereas along the b-axis, two solvent molecules (toluene) are inserted between neighboring 3d molecules, so that the minimum distance between the closest arene rings is 6.387 . The planar cores, combined with the small interplanar distances observed in families 13, explain the efcient charge transport achieved in several of these compounds. 272

Table 1. OFET device data for vacuum-deposited lms of naphthalene, benzene, and anthracene tetracarboxylic diimide small molecules.
Ts (C) 1 115 Max e (cm2 V1 s1) 0.079 (vac.) Ion/Ioff 106 Vth (V) 14 Device structure TC gold on Si/SiO2 treated with OTS; tested in vacuum or air Ref. 23

0.054 (air) 2a 2b 2c 70 70 104 0.16 (vac.) 106 (air) 0.05 0.1 2d 2e 2f 2g 2h 2i 70 98 140 70 40 22 106 0.12 0.57 <106 0.31 6.2 (Ar)

104

15 BC gold on Si/SiO2; tested in vacuum 2be: TC gold on Si/SiO2; tested in vacuum or air Tested in air 24 25 25 26 Tested in air Tested in air 25 25 27 25 28 29

105

107

1348 TC gold on Si/SiO2 treated with OTS; tested in air TC gold on Si/SiO2; tested in air

104107 108

3152 TC gold on Si/SiO2 treated with OTS; tested in air 58 2ij: TC gold on Si/SiO2 treated with OTS; tested in Ar or air

0.41 (air) 2j 2l 3a 22 110 90 0.7 0.11 0.03 (vac.)

105 106 103 106

71 55 -55 10 Tested in Ar TC gold on Si/SiO2; tested in air TC gold on Si/SiO2 treated with HMDS; tested in vacuum or air 29 30 31

0.02 (air) 3b 90 0.02

107 107

15 45 Tested in vacuum 31

Ts = substrate temperature; Vth = threshold voltage; TC = top contact; BC = bottom contact; OTS = octadecyltrichlorosilane; HMDS = hexamethyldisilazane; vac. = vacuum.

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Figure 5. Crystal structures of several benzene, naphthalene, and anthracene perylene diimides. 1b, reproduced with permission.[23] Copyright 2008, American Chemical Society. 2e, reproduced with permission.[32] Copyright 2001, Wiley-VCH. 2k, reproduced with permission.[27] Copyright 2008, American Chemical Society. 2m, reproduced with permission.[30] Copyright 2007, American Chemical Society.
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To our knowledge, thin lm transistors (TFTs) based on single crystals of families 13 have never been investigated. 3.2. Perylene and Higher Rylene Diimides Table 2 provides a summary of selected n-channel OFET data for the small-molecule PDIs in Figure 3.[3454] Horowitz et al. rst demonstrated electron mobilities of 105 cm2 V1 s1 with an N,N-diphenyl-substituted example (4a).[34] In 2001, Malenfant et al. reported n-channel OFETs based on N,N-dioctyl PDI (4b) having a substantial mobility of 0.6 cm2 V1 s1 under nitrogen, but with a high threshold voltage of 75 V, which was attributed to a large trap density.[35] Later, Chestereld et al. demonstrated that devices with a maximum mobility of 1.7 cm2 V1 s1, an
Table 2. OFET device data for vacuum-deposited lms of perylene tetracarboxylic diimide small molecules.
Ts (C) 4a Ion/Ioff Max e (cm2 V1 s1) 105 Vth (V) Device structure BC gold on glass with Al gate and PMMA dielectric; tested in air >105 107 75 1015 BC gold on Si/SiO2; tested in N2 Ref. 34

4b 4b 75

0.6 1.7

35

BC Ag on Si/SiO2 coated with 36 poly(-methylstyrene); tested in 104 Torr of H2 TC gold on Si/SiO2 coated with 37 PMMA; tested in air TC gold on Si/SiO2; annealing 38 at 140 C; tested in vacuum

4b 4c 4f 4g 140 125 90

0.11 2.1 0.51 0.1

105 105 106 105

11 60

2843 TC gold on Si/SiO2 treated with 43 OTS; tested in air 15 4gh: TC gold on Si/SiO2 treated with HMDS; tested in air 45

4h 4h

110

0.64 6 (vac.) 3 (air)

104 103 104 106 106 10

3

20

45

5 +5 TC gold on Si/SiO2 coated with 47 PMMA; SC; tested in vac. or air

4i 4j 4k 4l 4m 4n 4q 5a

125 125 125 125 125 130 125 140

0.58 0.052 3.3 105

1129 422 1425 1733 1123 28 28 20

4im:TC gold on Si/SiO2 50 treated with OTS; tested in air 50 50 50 50 TC gold on Si/SiO2; tested in air TC gold on Si/SiO2 treated with OTS; tested in air TC gold on Si/SiO2; tested in vac. 21 51 54

0.27 3.9 105 8.8 104

107 103 10
2

0.82 0.07

108 104

Ts = substrate temperature; Vth = threshold voltage; TC = top contact; BC = bottom contact; OTS = octadecyltrichlorosilane; HMDS = hexamethyldisilazane; PMMA = poly(methyl methacrylate); SC = single crystal; vac. = vacuum.

on/off ratio of 107, and threshold voltages of 1015 V can be obtained using 4b by coating the SiO2 gate dielectric with poly(-methylstyrene).[36] Coating of the dielectric with polymers also considerably improves the air stability of device operation for 4b, presumably by passifying acidic silanol groups that can act as electron traps on the SiO2 surface.[37] Ichikawa et al. demonstrated that the mobility of OFETs based on N,Nbis-tridecyl PDI 4c can be increased 103 times to 2.1 cm2 V1 s1 by thermal annealing;[38] the thermal treatments improve both the thin lm crystallinity and morphology. Discotic liquid crystals (LCs) that can self-assemble into highly ordered one-dimensional columnar stacks are promising candidates for use as charge-transport materials in organic electronics; intermolecular orbital overlap within the stacks is anticipated to enhance mobility compared to that in amorphous materials. Mobilities of 0.1 cm2 V1 s1 have been measured by pulseradiolysis time-resolved microwave conductivity (PR-TRMC) techniques for LC N,N-dioctadecyl-3,4:9,10-perylene diimide (4d).[39] Marder et al. found that at room-temperature, LC PDI (4e) displays a space-charge-limited current (SCLC) mobility as high as 1.3 cm2 V1 s1 under ambient conditions,[40] while even higher values (up to 6.7 cm2 V1 s1 for 6a) were found for closely related columnar discotic coronene-2,3:8,9-tetracarboxyli c diimides.[41,42] However, attempts to exploit the high mobilities of LC 4e and 6a have so far been unsuccessful, presumably at least in part due to the difculty of obtaining the desired alignment of the columnar stacks along the sourcedrain axis. Bao, Wrthner, and co-workers reported that OFETs based on N,N-bis(2,2,3,3,4,4,4-heptauorobutyl)-3,4:9,10-perylene diimide (4f) can exhibit mobilities as high as 0.72 cm2 V1 s1, which decrease only slightly after air exposure and remain stable for more than 50 days.[43] Since the partial uorination has only a small effect on the redox potential (LUMO energy) relative to N,N-dialkyl analogues, the stability was attributed to hindrance of O2 and H2O diffusion by dense packing of the cores and the uoroalkyl chains. On the other hand, 1,7-dicyano PDIs, rst synthesized by Wasielewski et al., are signicantly more readily reduced than their unsubstituted analogues (by ca. 0.36 V);[44] the associated high electron afnity is believed to be a factor contributing to the high electron mobility (0.10 cm2 V1 s1) achieved in air for OFETs based on 4g.[45] Combining partial uorination of the N,N substituents and 1,7-dicyano substitution in 4h affords a still higher electron mobility, 0.64 cm2 V1 s1.[45] The crystal structure of 4h provides a rationale for the high mobility of this material both in vacuum and in ambient conditions. Single crystals of 4h were grown by sublimation and the crystal structure (Figure 6) reveals a minimally twisted polycyclic core (torsion angle of about 58) with slip-stacked face-to-face molecular packing and a minimum interplanar spacing of 3.40 . This motif allows considerable intermolecular overlap, which results in good charge transport properties. The effects of 4h lm growth conditions on n-channel OFET performance have also been investigated;[46] dramatic enhancements of the on/ off ratio and the mobility are obtained with increased substrate temperature (Ts) during lm growth, with the increased mobility being correlated to higher levels of molecular order and to minimization of lm-surface irregularities.[46] In addition, the effects modifying the SiO2 surface of the gate dielectric with octadecyltrichlorosilane- or hexamethyldisilazane-derived

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Figure 6. Crystal structure of compound 4h viewed along two different crystallographic directions. Reproduced with permission.[45] Copyright 2004, Wiley-VCH.

monolayers, as well as with polystyrene, were investigated for 4h lms deposited at Ts = 130 C; the SiO2 surface treatments substantially modulate the mobility and growth morphology of 4h lms.[46] Recently, Morpurgo et al. fabricated OFETs based on 4h single crystals (Figure 7), with poly(methyl methacrylate) as the gate dielectric, that exhibit electron mobilities approaching 6 cm2 V1 s1, 10 times greater than those of the corresponding thin-lm devices, both in air and in vacuum.[47] Furthermore, these devices exhibit near-zero threshold voltage and subthreshold slopes and current on/off ratios (103104) comparable to the very best p-channel single-crystal devices when the same gate dielectric is employed. In related work, Weitz et al.[48] reported air-stable n-channel OFETs based on ve dicyano PDIs with uorinated linear and cyclic N,N-substituents (mobilities up to 0.1 cm2 V1 s1) and investigated the relationships between molecular structure, thin-lm morphology, substrate temperature during growth, device 1.50 performance, and air stability. Interestingly, Au (Drain) Au (Source) Vacuum the mobility degradation rate in air was Single-crystal +15 V 1.25 Air found to be similar for all compounds and PMMA (Dielectric) at all growth temperatures, raising the quesSiO2 1.00 tion of whether air stability can always be Doped Si (gate) explained on the basis of kinetic barriers to 0.75 O2/H2O diffusion formed by densely packed uorocarbon substituents.[48] +10 V 0.50 In addition to cyano groups, halo substituents can act as as perylene bay 0.25 substituents. Wrthner et al. reported that +5 V a 1,6,7,12-tetrachloro N,N-didodecyl PDI 0.00 exhibited PR-TRMC mobilities as high 0 10 20 30 as 0.1 cm2 V1 s1.[49] More recently, Bao, Wrthner et al. studied a series of core VSD (V) halogenated N,N-bis(heptauorobutyl) and N,N-bis(peruorophenyl) PDIs. While intro- Figure 7. Device structure (a), optical image (b), and electrical performance (c) of a singleduction of halogens in the bay positions crystal TFT based on perylene 4h. Reproduced with permission.[47] Copyright 2009, American facilitates reduction, with 1,6,7,12-tetrahalo Chemical Society.

derivatives being slightly more readily reduced than their 1,7dihalo analogues, the more highly substituted examples tend to exhibit lower mobilities. This can be attributed to disruption of core planarity and, therefore, of effective overlap, due to steric interactions.[50] The crystal structure of this homologous series combined with those of previously characterized PDIs provides important and general insights into the charge transport properties of perylene derivatives, and it is worth discussing them in detail. Figure 8 shows the crystal structures of N,Nbis(heptauorobutyl) functionalized perylenes 4f, 4i, and 4j and the N,N-bis(peruorophenyl) derivative 4p (molecular structures sketched in Figure 1). Similar to other core-unsubtituted perylenes, the crystal structure of a 4f shows a nearly planar -core (the torsion angles dened by the planes encompassing the atoms in positions 1, 12a, 12b and 12 and those in positions 6, 6a, 6b, and 7, i.e., the atoms that dene the PDI bays, are only 1.5). The crystal packing is characterized by having 4f molecules arrayed in a slipped -stack with the shortest interplanar distance only 3.31 (similar to that in graphite) and close perylene H-to-imide O contacts between stacks (2.46 ). The difluorinated derivative 4i also exhibits a substantially planar core (torsion angles 3.0), but signicantly different herringbone molecular packing (the shortest interplanar spacing is 3.33 within each stack and the closest intermolecular interaction is a perylene H-to-alkyl F contact of 2.49 ), resulting in considerably reduced face-to-face overlap. The presence of four bay uorine atoms in molecule 4j strongly distorts the core from planarity, resulting in a twisting of the two naphthalene imide subunits (the torsion angles dened as dened above, are 19.8 and 25.1). Although the naphthalene subunits of neighboring molecules are still orientated parallel to each other, two different minimum interplanar distances (3.18 and 3.28 ) are observed along the molecular stack. Because of the very high displacement parameters, negligible contact between neighboring molecules is observed. Finally, the solid-state packing of the diuoro core substituted PDI with N-peruorophenyl groups (4p) differs signicantly from that observed for the corresponding molecule 4i that

a.

c.

b.

ISD (A)

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Figure 8. Crystal structures of several perylenedimide semiconductors. Reproduced with permission.[50] Copyright 2009, American Chemical Society.

has NCH2C3F7 groups. Since the PDI cores are identical, the completely different packing of 4p must be assigned to the effect of the peruororomatic imide substituents, which are twisted with respect to the perylene plane. Despite the nonplanarity of these molecules, system 4p adopts a side-shifted brickwall-like packing which still allows close contacts (<3.28 ) due to an angular arrangement of the perylene backbones. However, the overlap among molecules is rather small, and only the diimide groups have signicant overlap with the neighboring cores. Furthermore, the twisted molecular arrangement results in a low crystal density (1.821 g cm3), signicantly smaller than that found for PDIs 4f, 4i, and 4j (1.889 g cm3, 1.995 g cm3, and 1.884 g cm3, respectively). Having analyzed how the molecular structure and packing vary in a uorine core-functionalized series, it is instructive to understand the evolution of the PDI core angles when larger Cl and Br halogen substituents are introduced into 4k and 4m, respectively (Figure 9). Single crystals of 4k, which have the four large chlorine atoms in the bay position, lead to large torsion angles of 34.8 and 36.4. Surprisingly, the carboncarbon bond lengths connecting the naphthalene subunits are rather small (1.43 and 1.44 ), even shorter than that in the unsubstituted dye 4f. Unfortunately

these crystals contain solvent molecules in the lattice, limiting any discussion of how stacking affects charge transport in the vapor-deposited lms. As in the case of 4f, molecule 4m crystallizes with benzene solvent molecules between the perylene cores. Interestingly, the torsion angle (37.2) increases only slightly compared to that of the tetrachlorinated compound 4k, in agreement with molecular orbital computations, which predict saturation of the core torsional angle with tetrachloro substitution. The structures of these derivatives, combined with X-ray evidence that vapor-deposited lms of these PDIs are polycrystalline, help rationalize the mobility trends in these PDI families. Thus, the PDI cores of both the diuoro compound 4i and the parent 4f are more or less planar (torsion angles <3.0), with the FET electron mobility of 4i being approximately half that of 4f. In contrast, the perylene core of 4j is distinctly nonplanar due to FF steric interactions (torsion angles 2025), leading to less dense and less regular packing and to mobility that is one order of magnitude lower than that of 4i.[50] Tetrabromo derivative 4m also exhibits a ca. 10 times lower mobility than its dibromo analogue, 4n.[21,50] Furthermore, 1,6,7,12tetrachloro and tetrabromo derivatives 4k and 4m exhibit mobilities 103 times lower than that of their tetrauoro

Figure 9. Diffraction derived molecular structures of tetrauoro, tetrachloro, and tetrabromo core-functionalized perylenedimides. Reproduced with permission.[50] Copyright 2009, American Chemical Society.

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counterpart 4j, presumably due to the increased bulk of the heavy halogen substituents.[50] Interestingly, replacing the N,N-uoroalkyl substiutents of the 1,6,7,12-tetrachloro PDI 4k with N,N-pentauorophenyl groups in 4l lead to an 104 times increase in the mobility (Table 2).[50] Very recently, Bao and Wrthner showed that PDI core planarity is not essential to achieve high eld-effect mobility by comparing two octachloro-substituted derivatives, 4q and 4r (Figure 1).[51] Compound 4q, which has free NH imide groups, was envisioned to enable close and directional hydrogen bonds between adjacent molecules. The crystal structure of 4q (Figure 10) exhibits a highly twisted perylene backbone with a dihedral angle of 37.28 between the naphthalene imide planes, in agreement with results for other octachloro-substituted perylene diimides. These molucules form NHO hydrogen bonds of length 2.95 . In the crystal, the molecules arrange in a slipped 2D -stacked layers with the shortest interactions of about 3.4 . This hydrogen-bond-enforced brickwall packing provides substantial overlap between each molecule and its four neighbors. The LUMO level of 4q, despite the heavily twisted core, is remarkably low (4.23 eV) and well within the air-stability window for ET materials.. Top-contact bottom-gate OTFTs on OTS-treated SiO2/Si substrates exhibit mobilities as high as 0.91 cm2 V1 s1 under nitrogen and 0.82 cm2 V1 s1 in air for lms vapor-deposited at 125 C. It is striking that such high mobilities are obtained from such nonplanar -conjugated molecules. Interestingly, hydrogen bonding apparently plays an important role in achieving high mobility since the corresponding octachloroperylene-3,4:9,10-tetracarboxylic dianhydride (4r) exhibits much lower mobility (105 cm2 V1 s1) in the same device structure. Most of studies of PDI-based FETs have been carried out Figure 10. Crystal structure of perylenedimide 4q. Reproduced with permission.[51] Copyright 2010, Wiley-VCH. using lms deposited by vacuum evaporation. However, recent studies demonstrate the great potential of these materials for solution-processed or printed FETs (Figure 11). For example, Dodabalapur et al. reported the rst organic complementary circuits (CMOS) fabricated on Si-SiO2 substrates using solution-deposited lms of 4o for the n-channel FETs and poly3-hexylthiophene (P3HT) for the p-channel FETs.[55] They reported ring oscillators operating at a frequency of 2 kHz without passivation or packaging. More recently, Facchetti et al. reported solution-processed FETs of 4o with mobilities 0.01 cm2 V1 s1 on Si-SiO2, as well as CMOS inverters and ring oscillators on plastic substrates operating at 50 Hz and using 4o and P3HT in combination with solution-processed polymer dielectrics.[56] Loi et al.[57,58] showed that uorocarbon functionalization of the aromatic skeleton in 4h leads to an enhancement of the electron mobility by one order of magnitude (up to Figure 11. Optical images of several devices based on rylenediimide derivatives. a) Ring oscil0.133 cm2 V1 s1) versus hydrocarbon-func- lator fabricated on PET by spin-coating compound 4o ( n-type FET) and P3HT ( p-type FET). b) FETs fabricated by inkjet printing compound 4o. c) FETs fabricated by gravure printing tionalized 4o for lms processed from solu- polymer 7d. d) An inkjet-printed inverter based on a perylene derivative. Panel (a) reproduced tion. Such a difference between the solution- with permission.[56] Copyright 2008, Wiley-VCH. Panel (c) reproduced with permission.[65] processed transistors is far larger than the Copyright 2009, Nature Publishing Group. Panel (d) reproduced with permission.[59] Copyright differences reported for the corresponding 2009, American Institute of Physics.

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vacuum-processed devices. To explain these differences, the authors carried out both morphological and spectroscopic analyses on the spin-coated lms of the two materials. By using time-resolved spectroscopy, they highlighted that the intermolecular interactions (excimer-like excitations) are more dominant in 4h than in 4o (Figure 12). The face-to-face molecular organization responsible for the excimer formation is also the optimum intermolecular organization motif for high charge carrier mobility due to the increased overlap, explaining the enchanced FET performance of the uorocarbon functionalized derivative. In related work, Arias et al. demonstrated inkjetpatterned FETs and complementary inverters based on a PDI derivative and a poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b] thiophene), and analyzed details of the bias stress response (a parameter related to FET operation in a circuit) for digital and analog electronic circuit applications.[59] Very recently, Salleo et al. investigated the effects of molecular-level structure on grain boundaries by engineering the growth microstructure of the N,N-dioctyl perylene diimide 4o and analyzed the consequences for charge transport.[60] A combination of advanced X-ray scattering, rst-principles computation, and transistor characterization applied to 4o lms reveals that grain-boundary orientation modulates carrier mobility by approximately two orders of magnitude (Figure 13). Anisotropic 4o lms were grown using a drop-casting technique where nucleation of 4o crystallites occurs at the pinned edge of the evaporating solution at the top of an incline. The slow-moving evaporation front of the high-boilingpoint solvent and a saturated solvent atmosphere promote the growth of elongated, oriented crystalline domains. For 4o it was shown that the molecular packing motif (that is, herringbone versus slip-stacked) plays a decisive role in grain-boundaryinduced transport anisotropy. These results show that the complete elimination of grain boundaries or, conversely, introduction of many grain boundaries, is unnecessary for device uniformity. Instead, device performance can be optimized by controlling grain-boundary orientation or reducing the energetic barrier associated with transport across less favorable boundaries, such as those of necessarily high misorientation in slip-stacked systems. Finally, Mllen et al. pioneered the synthesis of higher rylene diimide dyes and other species based on extended PDI cores, investigating in detail their thermotropic behavior and optical properties as well as the details of their microstructure.[52,53] However, exploitation of higher rylene diimides in organic electronics is limited to a report by Petit et al. on the FET properties of vapor-deposited lms of N,N-dipentylterrylene-3,4:11,12tetracarboxylic diimide derivative (5a) on Si-SiO2 substrates;[54] a maximum electron mobility of 0.07 cm2 V1 s1 and an on/off ratio in excess of 104 is obtained.

Figure 12. Intensity images of the spectrally and time resolved PL spectra of 4h (a) and 4o (b) thin lms (the intensity scale for the two images is the same). Rectangles delimit the temporal and spectral integration window over which the corresponding prole displayed on the right (spectra) and below (decay) are integrated. Right panels: emission spectra timeintegrated over the initial 0.2 ns after excitation (dark gray) and between 1.2 and 4.2 ns (light gray). Bottom panels: PL decays spectra integrated between 580 and 610 nm (dark gray) and between 720 and 820 nm (light gray). Reproduced with permission.[58] Copyright 2009, Springer.

4. Rylene Diimide Polymers in OFET Devices

Although the highest organic transistor performance is typically obtained using highly puried vacuum-deposited small molecules, solution-processing methods such as spin-coating and inkjet printing are attractive alternatives due to their low cost, as noted above. These solution phase deposition methods are also compatible with polymeric ET materials. Beyond the potential

for greater morphological stability (for example, with respect to crystallization and electrically non-connected crystallites), polymers are ideally suited for high-throughput processing methodologies, such as gravure and exographic printing, which require viscosity ranges that are difcult to achieve with any small molecules. While the application of rylene diimide polymers (Figure 14) in OFET applications is in an earlier stage of development than their small molecule counterparts, the development of main-chain and side-chain rylene diimide ET polymers is a rapidly advancing eld. Table 3 summarizes n-channel

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a
Parallel alignment

b
10
-1

c
10 10

-1

400 300

Temperature (K) 200

100

||
2

-2

Mobility (cm /Vs)

Mobility (cm /Vs)

10

-2

||

EA=125 meV

10

-3

2
-4

Perpendicular alignment

10 10 10 10 10

-3

Spin-coated, isotropic films

-4

10

-5

10

-5

-6

EA=468 meV
0.004 0.006

-7

Channel length = 600um

Batch #

1/T (K )

-1

0.008

0.010

Figure 13. Mobility and activation energy anisotropy for 4o lms. a) Optical micrographs of parallel (top), perpendicular (middle), and isotropic (bottom) TFT devices fabricated from 4o lms. Channel lengths are all 600 m. b) Derived mobility of aligned and isotropic 4o lms. Batch-to-batch variations are probably due to differences in device geometry and the time elapsed between substrate ultravioletozone treatment and lm growth, as this affects lm quality. c) Arrhenius plot of the temperature dependence of the TFT mobilities. In all cases blue corresponds to parallel devices, red to perpendicular, and black symbols to isotropic. Reproduced with permission.[60] Copyright 2009, Nature Publishing Group.

OFET data for solution-processed perylene and naphthalene diimide polymers. Zhan et al. reported the rst synthesis of soluble rylenebased fully conjugated polymers, i.e., polymers in which the rylene cores are bridged by other -conjugated units, rather than polymers in which rylenes are linked through the imide groups. This copolymer of PDI and dithienothiophene, 7a, exhibits a saturation electron mobility of 1.3 102 cm2 V1 s1 and a low threshold voltage of 4 V (Figure 15).[61] Very recently, a dithienopyrrole analgue, 7b, was reported to show an electron mobility of 7.4 104 cm2 V1 s1, which increases to 1.2 103 cm2 V1 s1 on annealing at 100 C for 60 min under inert atmosphere.[62] The lower mobility observed for 7b may be related to dilution of the PDI ET units by the additional N-substituents of the dithienopyrrole donors or to the disruption of PDIPDI interactions caused by these groups. Facchetti et al.[63]
C10H21 O N C12H25 O O N C10H21 C8H17 O O

have reported a PDI/bithiophene copolymer 7c with a mobility of 2 103 cm2 V1 s1. Thelakkat et al. reported that for OFETs based on polymers containing PDIs as pendant groups,[64] after thermal annealing at 210 C for 60 min, threshold voltage declines to 7 V, while the current and charge carrier mobility both increase by 100fold, with electron mobilities as high as 1.2 103 cm2 V1 s1 obtained in a device based on 7e. However, OFETs based on these PDI polymers are unstable under ambient conditions. Facchetti et al. have developed improved polymeric materials based on NDIs (Figure 15). Thus, a copolymer with bithiophene 7d achieves an electron mobility of 0.06 cm2 V1 s1 when measured in vacuum.[63] Furthermore, the devices exhibit good air stability and function well under ambient conditions for at least four weeks after fabrication ( 0.01 cm2 V1 s1). Later, top-gate bottom-contact transistors were fabricated from
C10H21 N C8H17 O Ph O O S
i Pr O N Ph n t Bu O (CH2)11

S Z O N O C12H25 C10H21 Z 7a 7b S N-C12H25

O N N 8

O N N n

S S O N

S O C8H17 C10H21

O C8H17 C10H21 7c

O 7d C7H15

O C7H15

7e

Figure 14. Chemical structure of some rylene diimide polymers.

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in bulk-heterojunction organic photovoltaic cells (OPVs), PDIbased small molecules and polymers have attracted interest as alternative ET materials since they exhibit large optical Device structure Ref. Ion/Ioff Vth (V) Max e absorptivities, high electron mobilities, and electron afni(cm2 V1 s1) ties similar to those of fullerenes. The work of Wasielewski 7a 0.013 4 7a and 7b: TC Al on Si/SiO2 treated 61 >104 et al. has shed light on photoinduced energy, charge, and spin with OTS; tested in vacuum; no transport, and elucidated the timescales of these processes annealing in PDI derivatives; this understanding is necessary for opti7b 9 62 >103 annealing at 100 C 1.2 103 mizing their use in solar energy conversion.[67,68] Efcient photoinduced charge separation is observed in blends of a 7c 7c and 7d: TC Au on Si/SiO2; tested 63 2 103 small molecule PDI (4e) with a variety of polythiophene donors, in vacuum; annealing at 110 C even when rather low thermodynamic driving forces are 7d 0.06 63 anticipated.[69] 7d BC gold on glass with ActivInk 65 0.85 106107 510 Many early studies of OPVs incorporating PDIs consisted of D2200 dielectric; tested in air layered structures fabricated by vapor deposition; for example, 7e 7 TC gold on Si/SiO2 treated with 104 64 1.2 103 a three-layer OPV consisting of the structure: phthalocyanine HMDS; annealing at 210 C; tested layer, phthalocyanine/9a blend layer, and 9a layer (Figure 16), in vacuum yielded a power conversion efciency (PCE) of 0.7%.[70] HowVth = threshold voltage; TC = top contact; BC = bottom contact; OTS = octadecylever, bulk heterojunction cells based on solution-processed trichlorosilane; HMDS = hexamethyldisilazane. blends of PDI-based materials with appropriate donor materials are attracting increasing attention (Table 4). Thus, Friend et al. 7d and polymeric dielectrics by spin-coating; these exhibit used a discotic liquid-crystalline hexaperihexabenzocoronene electron mobilities of 0.100.85 cm2 V1 s1 under ambient derivative in combination with PDI 9b to fabricate solutionconditions with on/off ratios >105. Furthermore, it was shown processed OPVs having a PCE of 1.95% at 490 nm.[71] Shin that this ET material can be processed using gravure, exoet al. fabricated OPVs using a blend of poly(3-hexylthiophene) graphic, and inkjet printing, as well as by spin-coating, dem(P3HT) with 9c.[72] A maximum PCE of 0.18% under simulated [65] onstrating great processing versatility. In this manner, the solar irradiation (AM1.5, 100 mW cm2) was achieved with a rst spin-coated and gravure-printed polymeric semiconductor P3HT: 9c ratio of 1:4 after annealing at 80 C for 1 h. Thus far, complementary inverters on PET substrates exhibiting large however, PCEs achieved for solution-processed OPVs based on gains (>2560) and operating in ambient conditions were blends of small molecule PDIs with small molecule or polymer realized.[65] donors have been modest. Finally, it is important to note that, although not strictly a Bulk-heterojunction solar cells incorporating diimide-based diimide, ladder polymer 8 is clearly very closely related to acceptor polymers are among the most efcient all-polymer NDIs and annealed lms of this material, processed from solar cells to be reported. The PDI-based polymer acceptor methanesulfonic acid, exhibit OFET electron mobilities up to (7a, Figure 14) synthesized by Zhan et al. and discussed in the 0.1 cm2 V1 s1 under ambient conditions.[66] previous section was also used as an acceptor in conjunction with a bis(thienylenevinylene)-substituted polythiophene donor and a PCE of 1% was achieved (Figure 15).[61] More recently, 5. Rylene and Aromatic Diimides for OPV Devices OPVs based on a related donor (a tris(thienylenevinylene)-substituted polythiophene) and a related acceptor (9d) were found, Although fullerenes, particularly the solution-processible derivaby optimizing the donor:acceptor ratio, to exhibit PCEs as tives known as PCBMs, are the most commonly used acceptors high as 1.5% (AM1.5, 100 mW cm2).[73] Using an alternating PDI-phenylenevinylene copolymer accceptor (9e) and poly(3-phenyl hydrazone thiophene) donor in OPVs, Mikroyannidis et al. obtained a PCE of 2.3% under white-light illumination calibrated to an AM1.5 intensity of 30 mW cm2 after annealing at 80 C for 10 min.[74] Very recently, Loo et al. investigated 7d in combination with P3HT, achieving PCEs approaching 0.6%; they also found that PCEs of these blends are more sensitive to the active layer lm morphology than are P3HT-PCBM blends.[75] The ladder polymer 8 (Figure 14) has also been used Figure 15. a) Current-voltage characteristics at several values of the gate voltage for a top conto fabricate efcient bilayer cells (PCE = tact device based on polymer 7a. b) Optical absorption spectra of lms of 7a (solid line) and 1.1% at 80 mW cm2 AM1.5) in conjuncof a 7a blend with a donor thiophene polymer (dashed line), spin-coated from chlorobenzene solution, and plot of incident photon to current conversion efciency (IPCE) as a function of tion with a poly(phenylene vinylene) donor.[76] wavelength. Reproduced with permission.[61] Copyright 2007, American Chemical Society.
Table 3. OFET device data for solution-processed lms of perylene and naphthalene tetracarboxylic diimide polymers.

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O R N O R 9a 9b C9H19 9c C9H19
tBu

O N R O O N

C10H21 C12H25 O H S

C6H13 n O S S 2 n O
iPr O mN Ph tBu O (CH2)6

CH3

O C12H25 C10H21 9d

O C9H19

O C9H19

O O N O O O OC6H13 N O C6H13O n
tBu

9f

9e

Figure 16. Chemical structure of some rylene diimide polymers for OPVs.

Several studies have employed donor-acceptor diblock copolymers in which a polyacrylate with pendant PDI units serves as the acceptor block; these materials undergo microscale phase segregation as single-component active layers in OPVs. Devices based on such block copolymers with a 4-(diphenylamino)styrene donor block were recently reported to exhibit efciencies of up to 0.11%,[77] while annealed devices based on 9f, in which the donor block is regioregular poly(3hexylthiophene), afford a PCE of 0.49%.[78] Very recently, molecules consisting of PDI small molecules substituted in one of the imide positions with well-dened alternating

uorenebithiophene oligomers have been shown to yield donor-acceptor lamellar nanostructures and, in conjunction with a PDI-based acceptor layer, yield PCEs up to 1.5% (AM1.5, 100 mW cm2).[79] Although the rylene-based polymers exhibit high mobilities and broad optical absorption,[61] the PCEs of rylene-based OPVs do not yet rival those of fullerene-based systems. The reason remains unclear at present, but an ideal morphology and appropriate electronic coupling with the donor component are issues that warrant further study. In general, the feature size of phase separation in polymer/polymer blend is

Table 4. Photovoltaic performance data for solution-processed OPVs based on PDIs under simulated AM 1.5, 100 mW/cm2 illumination unless stated otherwise.
Acceptor 9b 9c 7a 9d 9e 9f Donor HBC P3HT 2TV-PT 3TV-PT PPHT 9f Jsc (mA/cm2) 0.0335 1.32 4.2 5.02 2.98 2.57 Voc (V) 0.69 0.36 0.63 0.69 0.60 0.51 FF 0.40 0.38 0.39 0.43 0.39 0.37 PCE (%) 1.95 0.18 1.03 1.48 2.32 0.49 Irradiation 490 nm, 0.47 mW/cm2 AM1.5, 100 mW cm2 AM1.5, 100 mW cm2 AM1.5, 100 mW cm2 1.15 Sun, 30 mW/cm2 AM1.5, 100 mW cm2 Ref. 71 72 61 73 74 78

Jsc = short-circuit current density; Voc = open-circuit voltage; FF = ll factor; PCE = power conversion efciency; HBC = hexa(p-dodecylphenyl)hexaperihexabenzocoronene; P3HT = poly(3-hexylthiophene); 2TV-PT = bis(thienylenevinylene)-substituted polythiophene; 3TV-PT = tris(thienylenevinylene)-substituted polythiophene; PPHT = poly(3phenyl hydrazone thiophene).

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hundreds of nanometers due to the low entropy of mixing, while in the case of polymer/PCBM systems, the phase separation length scale is only tens of nanometers. Thus, the donoracceptor interfacial area in the polymer/PCBM systems is far larger than that in polymerpolymer systems. Given the fact that typical exciton diffusion lengths in disordered blend layers are ca. 10 nm, the greater phase separation length scale and smaller donoracceptor interfacial areas in polymerpolymer system is likely responsible for inefcient exciton dissociation and lower PCEs in these systems.[80] Very recently, Shuai et al. carried out a dynamic Monte Carlo simulation for the all-polymer solar cells based on a 7a/2TV-PT blend (Figure 17). The simulations indicate that a 5% PCE could be achieved with an optimum phase separation morphology (feature sizes 10 nm).[81] Compared to the spherical/ellipsoidal molecular shapes of fullerenes, the planar shapes of PDIs may lead to enhanced -stacking and more quasi 1D exciton and electron transport. As a result, if PDI-rich phases do not have high degrees of long-range order, there can be multiple orientations of stacked phases, which may lower long-range mobilities and therefore act as traps and recombination centers. In contrast, the roughly spherical shapes of the fullerenes may enable greater 3D exciton and electron transport, creating more extended pathways for the efcient exciton and electron diffusion. One signicant challenge in organic-based bulk-heterojunction OPVs involves the issue of splitting of photogenerated excitons into separated holes and electrons.[8284] The higher rylenes may prove helpful in this regard since it is expected[85] that their permittivities will increase with increased -system dimensions. Increased permittivity should decrease the energy penalty associated with the exciton dissociation into carriers, increasing the overall efciency of the carrier photogeneration process.

6. Conclusions and Outlook

Rylene diimides can exhibit impressive electron afnities and high electron mobilities, often arising from favorable molecular packing motifs, as well as good environmental and thermal stability. Rylene diimides are among the most promising ET materials for organic electronics. Progress in the past decade has been substantial but continued development of ET materials will require a far better understanding of the relationships between molecular architecture, electronic structure, materials microstructure, and optoelectronic properties than what is currently available. With this objective in mind, we have surveyed and analyzed what is currently known concerning rylene diimide architecture, electronic structure, and charge-transport property relationships. To summarize: (1) The -electron aromatic core in rylene diimides plays a key role in determining the charge transport properties of the corresponding molecular solids. Thus far, the rylene tetracarboxylic diimides have been found to exhibit much higher mobilities than pyromellitic diimides and anthracene tetracarboxylic diimides. (2) The solid-state packing and electron-transport properties of rylene diimides can be tailored by substituents in the imide N,N positions or on the aromatic core. (3) Ambient stability in rylene diimide-based devices can be achieved through the introduction of uorocarbon substituents at the N,N positions and/or introduction of electronwithdrawing core substituents, such as CN and F. (4) Compared to their small molecule counterparts, rylene diimide polymers exhibit better solution processability but somewhat lower electron mobilities. (5) Compared to simple small molecule PDIs, more complex systems such as PDI-functionalized polymers and oligomers have generally given higher power conversion efciencies when used as acceptors in solution-processed OPVs. Currently, a specic challenge to materials chemists is to design solution-processable air-stable organic semiconductors that have much better all-around performance in OFETs than amorphous silicon. To this end, the discovery of high-performance, air-stable, and solution-processable ET polymers would represent a major breakthrough towards polymeric complementary circuit technologies, where the combination of p- and n-channel transistors results in far greater circuit speeds, lower power dissipation, and more stable operation.

Acknowledgements
Work at CAS was supported by NSFC (Grants 21025418, 50873107, 20721061), MOST (Grants 2006AA03Z220, 2006CB932100) and CAS. Work at Ga. Tech. was supported by ONR (Grants N00014 03-1 0793, N00014 04-1 0120), Solvay, and the NSF through the STC Program (Grant DMR-0120967). Work at Northwestern was supported by AFOSR (Grant FA9550 08-1 0331), ONR (Grants N000140810923, N00014 05-1 0766, N00014 05-1 0021), Polyera Corp., ETRI, BP Solar, and the Northwestern MRSEC (NSF Grant DMR-0520513). Received: April 18, 2010 Published online: December 10, 2010

Figure 17. Contour plots showing the calculated power conversion efciency (PCE) for a 7abased blend versus the charge mobility and the characteristic feature size in the blend. The VOC and the ll factor used in the calculation are 0.63 V and 0.65, respectively. Reproduced with permission.[81] Copyright 2010, American Chemical Society.

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