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Patent US7504655 - Multilayer structures as stable hole-injecting electrodes for use in high ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsMultilayer anode structures (104) for electronic devices (100) such as polymer light-emitting diodes are described. The multilayer anodes include a high conductivity organic layer (114) adjacent to the photoactive layer (102) and a low conductivity organic layer (112) between the high conductivity organic...http://www.google.com/patents/US7504655?utm_source=gb-gplus-sharePatent US7504655 - Multilayer structures as stable hole-injecting electrodes for use in high efficiency organic electronic devicesAdvanced Patent SearchPublication numberUS7504655 B2Publication typeGrantApplication numberUS 11/116,500Publication dateMar 17, 2009Filing dateApr 28, 2005Priority dateJun 20, 2000Fee statusPaidAlso published asCA2408321A1, CN1437773A, CN1437773B, EP1292996A2, US20020036291, US20030146436, US20050184306, WO2001099207A2, WO2001099207A3Publication number11116500, 116500, US 7504655 B2, US 7504655B2, US-B2-7504655, US7504655 B2, US7504655B2InventorsIan D. Parker, Chi ZhangOriginal AssigneeE. I. Du Pont De Nemours & CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (43), Non-Patent Citations (2), Referenced by (6), Classifications (16), Legal Events (1) External Links: USPTO, USPTO Assignment, EspacenetMultilayer structures as stable hole-injecting electrodes for use in high efficiency organic electronic devicesUS 7504655 B2Abstract Multilayer anode structures (104) for electronic devices (100) such as polymer light-emitting diodes are described. The multilayer anodes include a high conductivity organic layer (114) adjacent to the photoactive layer (102) and a low conductivity organic layer (112) between the high conductivity organic layer and the anode's electrical connection layer (110). This anode structure provides polymer light emitting diodes which exhibit high brightness, high efficiency and long operating lifetime. The multilayer anode structure of this invention provides sufficiently high resistivity to avoid cross-talk in passively addressed pixellated polymer emissive displays; the multilayer anode structure of this invention simultaneously provides long lifetime for pixellated polymer emissive displays.
1. An array of polymer emissive diodes comprising an active emissive polymer layer having a first side in contact with a patterned cathode and a second side in contact with a patterned transparent anode, the patterning of said anode and cathode defining an array of emissive diodes, wherein a multilayer anode including a first layer comprising a patterned high conductivity inorganic contact layer, a nonpatterned second layer in physical contact with said first layer, said second layer comprising conjugated conductive organic polymer and having a high resistance and a nonpatterned transparent third layer in physical contact with said second layer and with said active emissive polymer layer, said third layer comprising a conductive organic polymer and having a lower resistance than said second layer.
2. The array of claim 1 wherein said second layer comprises a blend of conjugated conductive organic polymer with nonconductive polymer.
3. The array of claim 2 wherein said blend is a dispersion of one polymer in the other.
4. The array of claim 2 wherein said blend is a solution of one polymer in the other.
5. The array of claim 4 wherein said second layer comprises a mixture of conjugated conductive organic polymer with a nonconductive host polymer.
6. The array of claim 1 wherein the second layer comprises a blend of PANI with nonconductive polymer.
7. The array of claim 6 wherein the second layer has a bulk conductivity of from 10−4 S/cm to 1011 S/cm and wherein the bulk conductivity of the third layer is from about 5 times to about 106 times as great as the conductivity of the second layer.
8. The array of claim 7 wherein the second layer has a thickness of from about 500 Å to about 5000 Å.
9. The array of claim 7 wherein the third layer has a thickness of from about 2 Å to about 400 Å.
10. The array of claim 1 wherein said patterned high conductivity transparent inorganic contact layer is present on a support. Description
FIELD OF THE INVENTION This invention relates to organic electronic devices. More particularly it concerns multilayer hole-injecting electrodes (anodes) for electronic devices.
DESCRIPTION OF PRIOR ART Organic electronic devices, such as light emitting devices, photodetecting devices and photovoltaic cells, may be formed of a thin layer of electroactive organic material sandwiched between two electrical contact layers. Electroactive organic materials are organic materials exhibiting electroluminescence, photosensitivity, charge (hole or electron) transport and/or injection, electrical conductivity, and/or exciton blocking. The material may be semiconductive. At least one of the electrical contact layers is transparent to light so that light can pass through the electrical contact layer-to or from the electroactive organic material layer. Other devices with similar structures include photoconductive cells, photoresistive cells, photodiodes, photoswitches, transistors, capacitors, resistors, chemoresistive sensors (gas/vapor sensitive electronic noses, chemical and biosensors), writing sensors, and electrochromic devices (smart windows).
Light-emitting diodes (LEDs) fabricated with conjugated organic polymer layers as their emissive elements have attracted attention due to their potential for use in display technology [J. H. Burroughs, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, and A. B. Holmes, Nature 347, 539 (1990); D. Braun and A. J. Heeger, Appl. Phys. Lett. 58, 1982 (1991)]. Patents covering polymer LEDs include the following: R. H. Friend, J. H. Burroughs and D. D. Bradley, U.S. Pat. No. 5,247,190; A. J. Heeger and D. Braun, U.S. Pat. Nos. 5,408,109 and 5,869,350. These references as well as all additional articles, patents and patent applications referenced herein are incorporated by reference.
In their most elementary form, these diodes employ a layer of conjugated organic polymer bounded on one side by a hole-injecting electrode (anode) and on the other by an electron-injecting electrode (cathode), one of which is transparent to the light produced in the conjugated polymer layer when a potential is applied across it.
In many applications, especially in displays, arrays of these diodes are assembled. In these applications, there is typically a unit body of active polymer and the electrodes are patterned to provide the desired plurality of pixels in the array. With arrays based on a unit body of active polymer and patterned electrodes there is a need to minimize interference or �cross talk� among adjacent pixels. This need has also been addressed by varying the nature of the contacts between the active polymer body and the electrodes.
In U.S. Pat. No. 5,723,873 it is disclosed that it is advantageous to place a layer of conductive polyaniline (PANI) between the hole-injecting electrode and the layer of active material to increase diode efficiency and to lower the diode's turn on voltage.
Hole-injecting anodes which include conductive polyaniline can provide sufficiently high resistivity to avoid the disadvantage of cross talk in pixellated polymer emissive displays. However, the lifetime of such high resistivity polyaniline devices is not sufficient for many commercial applications. Moreover, devices fabricated with polyaniline-layer-containing anodes require high operating voltages.
Additional developments using a layer of polyaniline or blends comprising polyaniline, directly between the ITO and the light-emitting polymer layer, C. Zhang, G. Yu and Y. Cao [U.S. Pat. No. 5,798,170] demonstrated polymer LEDs with long operating lifetimes.
Despite the advantages of the polymer LED's described in U.S. Pat. No. 5,798,170, the low electrical resistivity typical of polyaniline inhibits the use of polyaniline in pixellated displays. For use in pixellated displays, the polyaniline layer should have a high electrical sheet resistance, otherwise lateral conduction causes cross-talk between neighboring pixels. The resulting interpixel current leakage significantly reduces the power efficiency and limits both the resolution and the clarity of the display.
Making the polyaniline sheet resistance higher by reducing the film thickness is not a good option since thinner films give lower manufacturing yield caused by the formation of electrical shorts. This is demonstrated clearly in FIG. 1, which shows the fraction of �leaky� pixels in a 96�64 array vs thickness of the polyaniline polyblend layer. Thus, to avoid shorts, it is necessary to use a relatively thick polyaniline layer with thickness �200 nm.
In polymer emissive displays, good operating lifetimes and relatively lower operating voltages have been demonstrated through the use of a layer of poly(ethylenedioxythiophene) (PEDT) between an indium/tin-oxide (ITO) anode layer and the emissive polymer layer. PEDT, as typically prepared, has intrinsically low electrical resistivity. However, for use in pixellated displays, the PEDT layer needs to have a high electrical sheet resistance, otherwise lateral conduction causes cross-talk between neighboring pixels, and the resulting inter-pixel current leakage significantly reduces the power efficiency and limits both the resolution and the clarity of the display.
Thus, there is a need for anode structures for light emitting devices which avoid inter-pixel cross-talk, and which exhibit the low operating voltages and the extended operating lifetimes consistent with the requirements of commercial applications:
SUMMARY OF THE INVENTION This invention relates generally a multilayer anode structure useful for organic electronic devices, such as diodes and pixellated displays.
The multilayer anode includes a first layer comprising a high conductivity contact layer having a first layer conductivity, a second layer in contact with the first layer, said second layer comprising a conductive organic material having a second layer conductivity, and a third layer in contact with the second layer, said third layer comprising a conductive organic polymer having a third layer conductivity greater than the second layer conductivity and less than the first layer conductivity.
The multilayer structure provides sufficiently high resistivity to avoid cross-talk in passively-addressed pixellated polymer emissive displays; the multilayer anode structure of this invention simultaneously provides the low operating voltages and the long operating lifetime required for pixellated polymer emissive displays in commercial applications.
This invention additionally provides an improved configuration for electronic devices such as pixellated polymer emissive displays. This configuration leads to high efficiency, long operating life PED's while at the same time avoids excessive cross talk. This invention relates generally to the use of the multilayer anode structure in such devices. Thus, in one aspect this invention provides an improved polymer emissive diode. This improved diode is made up of an active emissive polymer layer having a first side in contact with a cathode and a second side in contact with a transparent anode. The improvement involves a multilayer transparent anode itself made up of a high conductivity transparent first contact layer, a transparent second layer in contact with the first contact layer and a third layer in contact with the second layer and the active emissive polymer layer. The second layer contains conjugated conductive organic polymer blend and has a high resistance. The third layer is thin and contains a conductive organic polymer having a lower resistance than the material of the second layer.
While the multilayer electrode of the invention is useful in non-pixelated as well as pixelated electronic devices, the use of these improved multilayer anode structures is particularly advantageous when a plurality of diodes are arranged into an array as occurs in pixellated emissive displays as the anode structure leads to very low levels of cross talk while at the same time providing long life and high efficiency as compared to arrays described heretofore.
In this aspect this invention provides an improved array of polymer emissive diodes. This improved diode array is made up of an active emissive polymer layer having a first side in contact with a patterned cathode and a second side in contact with a patterned transparent anode, the patterning of the anode and cathode defining an array of emissive diodes, the improvement comprising a multilayer transparent anode including a first layer comprising a patterned high conductivity transparent contact layer, a nonpatterned transparent second layer in contact with said first layer, the second layer comprising a blend of conjugated conductive organic polymer and having a higher resistance (lower conductivity) and a nonpatterned transparent third layer in contact with the second layer and with the active emissive polymer layer, the third layer comprising a conductive organic polymer and having a lower resistance (higher conductivity) than the second layer.
As used herein, the term �organic electroactive material� refers to any organic material that exhibits the specified electroactivity, such as electroluminescence, photosensitivity, charge transport and/or charge injection, electrical conductivity and exciton blocking. The term �solution-processed organic electroactive material� refers to any organic electroactive material that has been incorporated in a suitable solvent during layer formation in electronic device assembly. The term �charge� when used to refer to charge injection/transport refers to one or both of hole and electron transport/injection, depending upon the context. The term �photoactive� organic material refers to any organic material that exhibits the electroactivity of electroluminescence and/or photosensitivity. The terms �conductivity� and �bulk conductivity� are used interchangeably, the value of which is provided in the unit of Siemens per centimeter (S/cm). In addition, the terms �surface resistivity� and �sheet resistance� are used interchangeably to refer to the resistance value that is a function of sheet thickness for a given material, the value of which is provided in the unit of ohm per square (ohm/sq). Also, the terms �bulk resistivity� and �electrical resistivity� are used interchangeably to refer to the resistivity that is a basic property of a specific materials (i.e., does not change with the dimension of the substance), the value of which provided in the unit of ohm-centimeter (ohm-cm). Electrical resistivity value is the inverse value of conductivity.
BRIEF DESCRIPTION OF THE DRAWINGS This invention will be described with�reference being made to the drawings. In these drawings,
FIG. 1 is a graph referenced in the Background which shows the fraction of �leaky� pixels (in a 96 by 64 array) vs thickness of a polyaniline layer.
FIG. 2A is a not-to-scale cross-sectional view of a pixel an organic electronic device of the invention containing a photoactive layer.
FIG. 2B is an enlarged cross section of the pixel of FIG. 2A focusing on the multilayer anode structure.
FIG. 2C is a schematic diagram of the architecture of a passively-addressed, pixellated, organic electronic device of the invention containing a photoactive layer.
FIG. 3 is a graph which shows the stress-induced degradation of three devices, one with a polyaniline (emeraldine-salt) layer (PANI(ES)), one with a layer made with a blend of polyaniline with polyacrylamide (PANI(ES)-PAM) and one with a layer of poly(ethylenedioxythiophene) (PEDT) layer at 70� C. Solid lines represent operating voltage and dashed lines represent light output.
FIG. 4 is a graph which shows the stress-induced degradation of devices having a PANI(ES)-PAM/PEDT double layer with different PEDT thickness at 70� C. Solid lines represent operating voltage and dashed lines represent light output.
FIG. 5 is a graph which shows the stress-induced degradation of a series of devices having PANI(ES)-PAM/PEDT double layers with different PANI(ES)-PAM blends at 80� C. Solid lines represent operating voltage and dashed lines represent light output.
DESCRIPTION OF PREFERRED EMBODIMENTS As best seen in FIGS. 2A, 2B, and 2C, an electronic device 100 of this invention comprises a layer of photoactive layer 102 between a cathode 106 and a multilayer anode 104. Anode 104 includes a conductive first layer 110 having a first layer conductivity, a low conductivity second layer 112 having a second layer conductivity and a high conductivity third layer 114 having a third layer conductivity greater than the second layer conductivity and less than the first layer conductivity. Anode 104 and the overall diode structure can be carried on a substrate 108.
Organic polymer-based diode 100 employs a relatively high work function anode; this high work function anode 104 serving to inject holes into the otherwise filled π-band of the semiconducting, luminescent polymer 102. Relatively low work function materials are preferred as the cathode 106; this low work function cathode serving to inject electrons into the otherwise empty π*-band of the semiconducting, luminescent polymer 102. The holes injected at the anode and the electrons injected at the cathode recombine radiatively within the active layer and light is emitted. The criteria for suitable electrodes in the art are described in detail by I. D. Parker, J. Appl. Phys, 75, 1656 (1994).
As best seen in FIG. 2C, each individual pixel of an organic electronic device 100 includes an electron injecting (cathode) contact 106 as one electrode on the front of a photoactive organic material 102 deposited on a multilayer anode 104 of the invention to serve as the second (transparent) electron-withdrawing (anode) electrode. The multilayer anode (made of layers 110, 112 and 114) is deposited on a substrate 108, which is partially coated with a first layer 110. Deposited on top of first layer 110 is the low conductivity second layer 112 and the high conductivity third layer 114. Cathode 106 is electrically connected to contact pads 80, and anode 110 is electrically connected to contact pads 82. The layers 102, 106, 108, 110, and 112 are then isolated from the environment by a hermetic seal layer 113. Where to electronic device is a light-emitting device, upon application of electricity via contact pads 80, 82, which pads are outside of the hermetic seal 70, light is emitted from the device in the direction shown by arrow 90. Where the electronic device is a photodetector, light is received by the deice in the direction opposite the row 90 (not shown).
This description of preferred embodiments is organized according to these various components. More specifically it contains the following sections:
The Photoactive layer (102) The Multilayer Anode (104)
The Conductive First Layer (110) The Low Conductivity Second Layer (112) The High Conductivity Third Layer (114) The Cathode (106) The Substrate (108) Contact Pads (80, 90) Optional Layers Fabrication Techniques
Depending upon the application of the electronic device, the photoactive layer 102 can be a light-emitting layer that is activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell), a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector). Examples of photodetectors include photoconductive cells, photoresistors, photos witches, phototransistors, and phototubes, and photovoltaic cells, as these terms are describe in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).
Where the electronic device is a light-emitting device, the photoactive layer 102 will emit light when sufficient bias voltage is applied to the electrical contact layers. Suitable active light-emitting materials include organic molecular materials such asanthracene, butadienes, coumarin derivatives, acridine, and stilbene derivatives, see, for example, Tang, U.S. Pat. No. 4,356,429, Van Slyke et al., U.S. Pat. No. 4,539,507, the relevant portions of which are incorporated herein by reference. Alternatively, such materials can be polymeric materials such as those described in Friend et al. (U.S. Pat. No. 5,247,190), Heeger et al. (U.S. Pat. No. 5,408,109), Nakano et al. (U.S. Pat. No. 5,317,169), the relevant portions of which are incorporated herein by reference. The light-emitting materials may be dispersed in a matrix of another material, with and without additives, but preferably form a layer alone. In preferred embodiments, the electroluminescent polymer comprises at least one conjugated polymer or a co-polymer which contains segments of π-conjugated moieties. Conjugated polymers are well known in the art (see, e.g., Conjugated Polymers, J. L. Bredas and R. Silbey edt., Kluwer Academic Press, Dordrecht, 1991). Representative classes of materials include, but are not limited to the following:
(i) poly(p-phenylene vinylene) and its derivatives substituted at various positions on the phenylene moiety; (ii) poly(p-phenylene vinylene) and its derivatives substituted at various positions on the vinylene moiety; (iii) poly(arylene vinylene), where the arylene may be such moieties as naphthalene, anthracene, furylene, thienylene, oxadiazole, and the like, or one of the moieties with functionalized substituents at various positions; (iv) derivatives of poly(arylene vinylene), where the arylene may be as in (iii) above, substituted at various positions on the arylene moiety;. (v) derivatives of poly(arylene vinylene), where the arylene may be as in (iii) above, substituted at various positions on the vinylene moiety; (vi) co-polymers of arylene vinylene oligomers with non-conjugated oligomers, and derivatives of such polymers substituted at various positions on the arylene moieties, derivatives of such polymers substituted at various positions on the vinylene moieties, and derivatives of such polymers substituted at various positions on the arylene and the vinylene moieties; (vii) poly(p-phenylene) and its derivatives substituted at various positions on the phenylene moiety, including ladder polymer derivatives such as poly(9,9-dialkyl fluorene) and the like; (viii) poly(arylenes) and their derivatives substituted at various positions on the arylene moiety; (ix) co-polymers of oligoarylenes with non-conjugated oligomers, and derivatives of such polymers substituted at various positions on the arylene moieties; (x) polyquinoline and its derivatives; (xi) co-polymers of polyquinoline with p-phenylene and moieties having solubilizing function; (xii) rigid rod polymers such as poly(p-phenylene-2,6-benzobisthiazole), poly(p-phenylene-2,6-benzobisoxazole), poly(p-phenylene-2,6-benzimidazole), and their derivatives; and the like. More specifically, the active materials may include but are not limited to poly(phenylenevinylene), PPV, and alkoxy derivatives of PPV, such as for example, poly(2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene) or �MEH-PPV� (U.S. Pat. No. 5,189,136). BCHA-PPV is also an attractive active material. (C. Zhang, et al, J. Electron. Mater., 22, 413 (1993)). PPPV is also suitable. (C. Zhang et al, Synth. Met., 62, 35 (1994) and references therein.) Luminescent conjugated polymer which are soluble in common organic solvents are preferred since they enable relatively simple device fabrication [A. Heeger and D. Braun, U.S. Pat. Nos. 5,408,109 and 5,869,350].
Even more preferred active light-emitting polymers and copolymers are the soluble PPV materials described in H. Becker et al., Adv. Mater. 12, 42 (2000) and referred to herein as C-PPV's. Blends of these and other semi-conducting polymers and copolymers which exhibit electroluminescence can be used. Where the electronic device 100 is a photodetector, the photoactive layer 102 responds to radiant energy and produces a signal either with or without a biased voltage. Materials that respond to radiant energy and is capable of generating a signal with a biased voltage (such as in the case of a photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes) include, for example, many conjugated polymers and electroluminescent materials. Materials that respond to radiant energy and are capable of generating a signal without a biased voltage (such as in the case of a photoconductive cell or a photovoltaic cell) include materials that chemically react to light and thereby generate a signal. Such light-sensitive chemically reactive materials include for example, many conjugated polymers and electro- and photo-luminescent materials. Specific examples include, but are not limited to, MEH-PPV (�Optocoupler made from semiconducting polymers�, G. Yu, K. Pakbaz, and A. J. Heeger, Journal of Electronic Materials, Vol. 23, pp 925-928 (1994); and MEH-PPV Composites with CN-PPV (�Efficient Photodiodes from Interpenetrating Polymer Networks�, J. J. M. Halls et al. (Cambridge group) Nature Vol. 376, pp. 498-500, 1995). The electroactive organic materials can be tailored to provide emission at various wavelengths.
Typical film thicknesses of the photoactive layers range from a few hundred Ångstrom units (200 Å) to several thousand Ångstrom units (10,000 Å) (1 Ångstrom unit=10−8 cm). Although the active film thicknesses are not critical, device performance can typically be improved by using thinner films. Preferred thickness are from 300 Å to 5,000 Å.
The Multilayer Anode (104)
The multilayer anode (104) includes the conductive first layer (110), a low conductivity second layer (112) and a high conductivity third layer (114).
The thickness of each layer 110, 112, 114 is determined by the desired transparency and resistivity of such layer, such transparency and resistivity factors are in turn dependent upon the composition of the layer.
As used herein, the term �transparent� is defined to mean �capable of transmitting at least about 25%, and preferably at least about 50%, of the amount of light of a particular wavelength of interest�. Thus a material is considered �transparent� even if its ability to transmit light varies as a function of wave length but does meet the 25% or 50% criteria at a given wavelength of interest. As is known to those working in the field of thin films, one can achieve considerable degrees of transparency with metals if the layers are thin enough, for example in the case of silver and gold below about 300 Å, and especially from about 20 Å to about 250 Å with silver having a relatively colorless (uniform) transmittance and gold tending to favor the transmission of yellow to red wavelengths. Similarly, for materials such as ITO, PANI and PEDT, transparency can be achieved with a layer ranging from 100 Å to 10,000 Å.
In addition to the desired transparency, the composition of layers in the multilayer anode 104 should also be chosen so that the third layer conductivity is less than the first layer conductivity and more than the second layer conductivity. Therefore, the choice of material for one layer of the multilayer anode depends upon the composition of the other layers in the anode and the corresponding conductivities of such other layers. Other factors in determining composition are described below in sections relating to the specific layers.
The Conductive First Layer (110)
The conductive first layer has low resistance: preferably less than 300 ohms/square and more preferably less than 100 ohms/square.
The conductive first layer (110) of the composite anode (104) provides electrical contact with an external electrical source (not shown) and is a conductive layer made of a high work function material, most typically an inorganic material with a work function above about 4.5 eV. The conductive first layer 110 is preferably made of materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide. Suitable metals include the Group 11 metals, the metals in Groups 4, 5, and 6, and the Group 8-10 transition metals. If the anode 104 is to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, are generally used. The IUPAC numbering system is used throughout, where the groups from the Periodic Table are numbered from left to right as 1-18 (CRC Handbook of Chemistry and Physics, 81st Edition, 2000). The first layer 110 may also comprise an organic material such as polyaniline as described in �Flexible light-emitting diodes made from soluble conducting polymer,� Nature vol. 357, pp 477-479 (11 Jun. 1992).
Typical inorganic materials which serve as anodes include metals such as aluminum, silver, platinum, gold, palladium, tungsten, indium, copper, iron, nickel, zinc, lead and the like; metal oxides such as lead oxide, tin oxide, indium/tin-oxide and the like; graphite; doped inorganic semiconductors such as silicon, germanium, gallium arsenide, and the like. When metals such as aluminum, silver, platinum, gold, palladium, tungsten, indium, copper, iron, nickel, zinc, lead and the like are used, the anode layer should be sufficiently thin to be semi-transparent. Metal oxides such as indium/tin-oxide are typically at least semitransparent.
Where the anode is transparent, the conductive metal-metal oxide mixtures can be transparent as well at thicknesses up to as high as 2500 Å in some cases. Preferably, the thicknesses of metal-metal oxide (or dielectric) layers is from about 25 to about 1200 Å when transparency is desired.
The Low Conductivity Second Layer (112)
The second layer 112 should have sufficient high resistivity to prevent cross talk or current leakage from the multilayer anode and provide sufficient hole injection/transport. The low conductivity second layer preferably has a bulk conductivity of from about 10−4 S/cm to 10−11 S/cm. More preferably, the second layer has a bulk conductivity of from 10−5 S/r to 10−8 S/cm.
The second layer 112 may comprise polyaniline (PANI) or an equivalent conjugated conductive polymer such as polypyrole or polythiophene, most commonly in a blend with one or more nonconductive polymers. Polyaniline is particularly useful. Most commonly it is in the emeraldine salt (ES) form. Useful conductive polyanilines include the homopolymer and derivatives usually as blends with bulk polymers (also known as host polymers). Examples of PANI are those disclosed in U.S. Pat. No. 5,232,631.
In another embodiment, the second layer may include conductive materials such as N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD) and bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP), and hole injection/transport polymers such as polyvinylcarbazole (PVK), (phenylmethyl)polysilane, poly(3,4-ethylenedioxythiophene) (PEDOT), and polyaniline (PANI);electron and hole injection/transporting materials such as 4,4′-N,N′-dicarbazole biphenyl (BCP); or light-emitting materials with good electron and hole transport properties, such as chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3).
When the terms �polyaniline� or PANI are used herein, they are used generically to include substituted and unsubstituted materials, as well as other equivalent conjugated conductive polymers such as the polypyrroles, or the polythiophenes, for example poly(ethylenedioxythiophene) (�PEDT�) unless the context is clear that only the specific nonsubstituted form is intended. It is also used in a manner to include any accompanying dopants, particularly acidic materials used to render the polyaniline conductive.
R is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfonyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more sulfonic acid, carboxylic acid, halo, nitro, cyano or epoxy moieties; or carboxylic acid, halogen, nitro, cyano, or sulfonic acid moieties; or any two R groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6 or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms. Without intending to limit the scope of this invention, the size of the various R groups ranges from about 1 carbon (in the case of alkyl) through 2 or more carbons up through about 20 carbons with the total of n Rs being from about 1 to about 40 carbons.
z is an integer equal to or greater than 1. The following listing of substituted and unsubstituted anilines are illustrative of those which can be used to prepare polyanilines useful in the practice of this invention.
2,5-Dibutylaniline
m-Ethylaniline
Tetrahydronaphthylamine
o-Cyanoaniline
m-Butylaniline
2-Thiomethylaniline
m-Hexylaniline
m-Octylaniline
3-(n-Butanesulfonic acid) aniline
2,4-Dimethoxyaniline
5-Chloro-2-methoxyaniline
5-Chloro-2-ethoxyaniline
Illustrative of useful R groups are alkyl, such as methyl, ethyl, octyl, nonyl, tert-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and the like; alkoxy such as propoxy, butoxy, methoxy, isopropoxy, pentoxy, nonoxy, ethoxy, octoxy, and the like, cycloalkenyl such as cyclohexenyl, cyclopentenyl and the like; alkanoyl such as butanoyl, pentanoyl, octanoyl; ethanoyl, propanoyl and the like; alkylsulfinyl, alkysulfonyl, alkylthio, arylsulfonyl, arylsulfinyl, and the like, such as butylthio, neopentylthio, methylsulfinyl, benzylsulfinyl, phenylsulfinyl, propylthio, octylthio, nonylsulfonyl, octylsulfonyl, methylthio, isopropylthio, phenylsulfonyl, methylsulfonyl, nonylthio, phenylthio, ethylthio, benzylthio, phenethylthio, naphthylthio and the like; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like, cycloalkyl such as cyclohexyl, cyclopentyl, cyclooctyl, cycloheptyl and the like; alkoxyalkyl such as methoxymethyl, ethoxymethyl, butoxymethyl, propoxyethyl, pentoxybutyl and the like; aryloxyalkyl and aryloxyaryl such as phenoxyphenyl, phenoxymethylene and the like; and various substituted alkyl and aryl groups such as 1-hydroxybutyl, 1-aminobutyl, 1-hydroxylpropyl, 1-hydyroxypentyl, 1-hydroxyoctyl, 1-hydroxyethyl, 2-nitroethyl, trifluoromethyl, 3,4-epoxybutyl, cyanomethyl, 3-chloropropyl, 4-nitrophenyl, 3-cyanophenyl, and the like; sulfonic acid terminated alkyl and aryl groups and carboxylic acid terminated alkyl and aryl groups such as ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, phenylsulfonic acid, and the corresponding carboxylic acids.
�(CH2)�n* wherein n* is an integer from about 3 to about 7, as for example �(CH2)−4, �(CH2)−3 and �(CH2)−5, or such moieties which optionally include heteroatoms of oxygen and sulfur such as �CH2SCH2� and �CH2�O�CH2�. Exemplary of other useful R groups are divalent alkenylene chains including 1 to about 3 conjugated double bond unsaturation such as divalent 1,3-butadiene and like moieties.
In more preferred embodiments of this invention, the polyamline is derived from unsubstituted aniline, i.e., where n is 0 and m is 5 (monomer) or 4 (polymer). In general, the number of monomer repeat units is at least about 50.
As described in U.S. Pat. No. 5,232,631, the polyaniline is rendered conductive by the presence of an oxidative or acidic species. Acidic species and particularly �functionalized protonic acids� are preferred in this role. A �functionalized protonic acid� is one in which the counter-ion has been functionalized preferably to be compatible with the other components of this layer. As used herein, a �protonic acid� is an acid that protonates the polyaniline to form a complex with said polyaniline.
A-R VI
In addition to these monomeric acid forms, R can be a polymeric backbone from which depend a plurality of acid functions �A.� Examples of polymeric acids include sulfonated polystyrene, sulfonated polyethylene and the like. In these cases the polymer backbone can be selected either to enhance solubility in nonpolar substrates or be soluble in more highly polar substrates in which materials such as polymers, polyacrylic acid or poly(vinylsulfonate), or the like, can be used.
R′ is the same or different at each occurrence and is alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsuldmyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen, cyano, or alkyl substituted with one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano, diazo or epoxy moieties; or any two R substituents taken together are an alkylene or alkenylene group completing a 3, 4, 5, 6 or 7 membered aromatic or alicyclic carbon ring or multiples thereof, which ring or rings may include one or more divalent heteroatoms of nitrogen, sulfur, sulEmyl, sulfonyl or oxygen. R′ typically has from about 1 to about 20 carbons especially 3 to 20 and more especially from about 8 to 20 carbons.
R′ is alkyl or alkoxy, having from 4 to 14, especially 12 carbon atoms, or alkyl substituted with one or more halogen, moieties. Preferred functionalized protonic acids are organic sulfonic acids such as dodecylbenzene sulfonic acid and more preferably poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (�PAAMPSA�).
The polyaniline can be conveniently used in the practice of this invention in any of its physical forms. Illustrative of useful forms are those described in Green, A. G., and Woodhead, A. E., J. Chem. Soc., 101, 1117 (1912) and Kobay.ashi, et al., J. Electroanl. Chem., 177, 281-91 (1984), which are hereby incorporated by reference. For unsubstituted polyaniline, useful forms include leucoemeraldine, protoemeraldine, emeraldine, nigraniline and tolu-protoemeraldine forms, with the emeraldine form being preferred.
Copending PCT Patent Application No. PCT/US00/32545 of Cao, Y. and Zhang, C. discloses the formation of low conductivity blends of conjugated polymers with non-conductive polymers and is incorporated herein by reference.
The materials can be blended by dispersing one polymer in the other, either as a dispersion of small-particles or as a solution of one polymer in the other. The polymer are typically admixed in a fluid phase and the layer is typically laid out of a fluid phase.
Organic solvents can be used with organic-soluble or organic dispensable conjugated polymers and bulk polymers. In addition, blends can be formed using melts of the two polymers or by using a liquid prepolymer or monomer form of the bulk polymer which is subsequently polymerized or cured into the desired final material.
In those presently preferred cases where the PANI is water-soluble or water dispersable and it is desired to cast the PANI layer from an aqueous solution, the bulk polymer should be water soluble or water dispersible. In such cases, it is selected from, for example polyacrylamides (PAM), poly(acrylic acid) (PAA) poly(vinyl pyrrolidone) (PVPd), acrylamide copolymers, cellulose derivatives, carboxyvinyl polymer, poly(ethylene glycols), poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA), poly(vinyl methyl ether), polyamines, polyimines, polyvinylpyridines, polysaccharides, end polyurethane dispersions.
In the case where it is desired to cast the layer from a non-aqueous solution or dispersion the bulk polymer may be selected from, for example liquefiable polyethylenes, isotactic polypropylene, polystyrene, poly(vinylalcohol), poly(ethylvinylacetate), polybutadienes, polyisoprenes, ethylenevinylene-copolymers, ethylene-propylene copolymers, poly(ethyleneterephthalate), poly(butyleneterephthalate) and nylons such as nylon 12, nylon 8, nylon 6, nylon 6.6 and the like, polyester materials, polyamides such as polyacrylamides and the like.
These materials include, without limitation, water mixed with methanol, ethanol, isopropanol, acetone methyl ethyl ketone and the like.
If desired, but generally not preferred, a solvent system of polar organic liquids could be used.
In the case of conducting polymers such as PAM and bulk polymers which are not water-soluble or water-dispersible, nonpolar solvents are most commonly used.
Illustrative of useful common nonpolar solvents are the following materials: substituted or unsubstituted aromatic hydrocarbons such as benzene, toluene, p-xylene, m-xylene, naphthalene, ethylbenzene, styrene, aniline and the like; higher alkanes such as pentane, hexane, heptane, octane, nonane, decane and the like; cyclic alkanes such as decahydronaphthalene; halogenated alkanes such as chloroform, bromoform, dichloromethane and the like; halogenated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and the like; higher alcohols such as 2-butanol, 1-butanol, hexanol, pentanol, decanol, 2-methyl-1-propanol and the like; higher ketones such as hexanone, butanone, pentanone and the like; heterocyclics such as morpholine; perfluorinated hydrocarbons such as perfluorodecaline, perfluorobenzene and the like.
The thickness of the second layer 112 will be chosen with the properties of the diode in mind. In those situations where the composite anode is to be transparent, it is generally preferable to have the layer of PANI as thin as practically possible bearing in mind the failure problem noted in FIG. 1. Typical thicknesses range from about 100 Å to about 5000 Å. When transparency is desired, thicknesses of from about 100 Å to about 3000 Å are preferred and especially about 2000 Å.
Where the second layer 112 comprises a PANI(ES) blend and a film thickness of 200 nm or greater, the electrical resistivity of the second layer should be greater than or equal to 104 ohm-cm to avoid cross talk and inter-pixel current leakage. Values in excess of 105 ohm-cm are preferred. Even at 105 ohm-cm, there is some residual current leakage and consequently some reduction in device efficiency. Thus, values of approximately from 105 to 108 ohm-cm are even more preferred. Values greater than 109 ohm-cm will lead to a significant voltage drop across the injection/buffer layer and therefore should be avoided.
The High Conductivity Third Layer (114)
The material for the third layer 114 should be chosen to match the energy level of the photoactive layer 102, or to improve hole injection/transport of the multilayer anode 104, or to improve the interfacial properties of the interface between the multilayer anode 104 and photoactive layer 102.
The third component of the hole-injecting electrode is a very thin layer of a highly conductive organic polymer having a resistance that is lower than the resistance of the material of the second layer 112 and higher than the first layer 110. A representative conductive organic polymer include pure PANI in its highly conductive forms, the polypyrroles and preferably polythiophenes such as PEDT, and any of the other organic materials described in the previous section for the second layer 112.
The material from which this layer (114) is formed should have a bulk conductivity with is from about five times to about 106 times as great as the bulk conductivity of the second layer (112) is formed. Similarly the bulk resistivity should be from five to 106 times lower. Where transparency of the multilayer anode 104 is desired and the layer comprises PEDT, this third layer is typically very thin, often so thin as to likely not be a completely continuous layer. The thickness should be in the range of from about 5 Å to about 500 Å with thicknesses in the range of 10 Å to 50 Å generally being preferred.
The addition of the high conductivity third layer (114) to second layer (112) yields a multilayer structure has a higher conductance than is observed with the second layer alone. The ratio of conductance of the bilayer (112 and 114) structure to the conductance of second layer 112 alone should range from about 1.25 to 20 with ratios of 1.5 to 15 and especially 2 to 10 being preferred.
Suitable materials for use as cathode materials are any metal or nonmetal having a lower work function than the first electrical contact layer (in this case, an anode). Materials for the cathode layer 106 (in this case the second electrical contact) can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals�commonly calcium, barium, strontium, the Group 12 metals, the rare earths�commonly ytterbium, the lanthanides, and the actinides. Materials such as aluminum, indium and copper, silver, combinations thereof and combinations with calcium and/or barium, Li, magnesium, LiF can be used. Alloys of low work function metals, such as for example alloys of magnesium in silver and alloys of lithium in aluminum, are also useful.
The thickness of the electron-injecting cathode layer ranges from less than 15 Å to as much as 5,000 Å. This cathode layer 106 can be patterned to give a pixellated array or it can be continuous and overlaid with a layer of bulk conductor such as silver, copper or preferably aluminum which is, itself, patterned.
In most embodiments, the diodes are prepared on a substrate. Typically the substrate should be nonconducting. In those embodiments in which light passes through it, it is transparent. It can be a rigid material such as a rigid plastic including rigid acrylates, carbonates, and the like, rigid inorganic oxides such as glass, quartz, sapphire, and the like. It can also be a flexible transparent organic polymer such as polyester�for example poly(ethyleneterephthalate), flexible polycarbonate, poly (methyl methacrylate), poly(styrene) and the like.
Contact Pads (80, 82)
Any contact pads 80, 82 useful to connect the electrode of the device 100 to the power source (not shown) can be used, including, for example, conductive metals such as gold (Au), silver (Ag), nickel (Ni), copper (Cu) or aluminum (Al).
Preferably, contact pads 80, 82 have a height (not shown) projected beyond the thickness of the high work function electrode lines 110 below the total thickness of layer.
Preferably, the dimensions of layers 102, 110, and 112 are such that contacts pads 80 are positioned on a section of the substrate 108 not covered by layers 102, 112 and 114. In addition, the dimensions of layer 106, 102, 110, and 112 are such that the entire length and width electrode lines 106 and electrode lines 110 have at least one layer 102, 112 intervening between the electrodes 106, 110, while electrical connection can be made between electrode 106 and contact pads 80.
Other Optional Layers
An optional layer including an electron injection/transport material may be provided between the photoactive layer 102 and the cathode 106. This optional layer can function both to facilitate electron injection/transport, and also serve as a buffer layer or confinement layer to prevent quenching reactions at layer interfaces. Preferably, this layer promotes electron mobility and reduces quenching reactions. Examples of electron transport materials for optional layer 140 include metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3); phenanthroline-based compounds, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA) or 4,7-diphenyl-1,10-phenanthroline (DPA), and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), polymers containing DDPA, DPA, PBD, and TAZ moiety and polymer blends thereof, polymer blends containing containing DDPA, DPA, PBD, and TAZ.
Alternatively, some or all of anode layers 110, 112, 114, the photoactive layer 102, and cathode layer 106, may be surface treated to increase charge carrier transport efficiency. The choice of materials for each of the component layers is preferably determined by balancing the goals of providing a device with high device efficiency.
The various elements of the devices of the present invention may be fabricated by any of the techniques well known in the art, such as solution casting, screen printing, web coating, ink jet printing, sputtering, evaporation, precursor polymer processing, melt-processing, and the like, or any combination thereof.
In the most common approach, the diodes are built up by sequential deposit of layers upon a substrate. In a representative preparation, the conductive first layer 110 of the composite electrode 104 is laid down first. This layer is commonly deposited by vacuum sputtering (RF or Magnetron), electron beam evaporation, thermal vapor deposition, chemical deposition or the like methods commonly used to form inorganic layers.
Next, the low conductivity second layer 112 is laid down. This layer is usually most conveniently deposited as a layer from solution by spin casting or like technique. In those preferred cases where the layer is formed from water-soluble or water-dispersible material water is generally used as the spin-casting medium. In cases where a non-aqueous solvent is called for are used such as toluene, xylenes, styrene, aniline, decahydronaphthalene, chloroform, dichloromethane, chlorobenzenes and morpholine. This layer can be heat-treated as described in commonly filed U.S. provisional patent application No. 60/212,934.
Next, the higher conductivity layer 114 is deposited. Again, this is typically done from solution with the solvent selected as described with reference to the deposit of layer 112.
Next, the photoactive layer 102 of conjugated polymer is deposited. The conjugated polymer can be deposited or cast directly from solution. The solvent employed is one which will dissolve the polymer and not interfere with its subsequent deposition.
When depositing various polymers on a substrate, the solution can be relatively dilute, such as from 0.1 to 20% w in concentration, especially 0.2 to 5% w. Film thicknesses of 500-4000 and especially 1000-2000 Å are typically used.
Finally the low work function electron-injecting contact is added. This contact is typically vacuum evaporated onto the top surface of the active polymer layer.
These steps can be altered and even reversed if an �upside down� diode is desired.
It will also be appreciated that the structures just described and their fabrication can be altered to include other layers for physical strength and protection, to alter the color of the light emission or sensitivity of the diodes or the like. It will further be appreciated that the present invention is further useful in organic electronic devices including the multilayer anode of the present invention do not contain a photoactive layer, such as transistors, capacitors, resistors, chemoresistive sensors (gas/vapor sensitive electronic noses, chemical and biosensors), writing sensors, and electrochromic devices (smart window).
EXAMPLE 1 PANI(ES) was prepared according to the following reference (Y. Cao, et al, Polymer, 30 (1989) 2307). The emeraldine salt (ES) form was verified by the typical green color. HCl in this reference was replaced by poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PAAMPSA) (Aldrich). First, 30.5 g (0.022 mole) of 15% PAAMPSA in water (Aldrich) was diluted to 2.3% by adding 170 ml water. While stirring, 2.2 g (0.022M) aniline was added into the PAAMPSA solution. Then, 2.01 g (0.0088M) of ammonium persulfate in 10 ml water was added slowly into the aniline/PAAMPSA solution under vigorous stirring. The reaction mixture was stirred for 24 hours at room temperature. To precipitate the product, PANI(ES), 1000 ml of acetone was added into reaction mixture. Most of acetone/water was decanted and then the PANI(ES)-precipitate was filtered. The resulting gum-like product was washed several times with acetone and dried at 40� C. under dynamic vacuum for 24 hours.
EXAMPLE 2 Four grams (4.0 g) of the PANI(ES) powder prepared in Example 1 was mixed with 400 g of deionized water in a plastic bottle. The mixture was rotated at room temperature for 48 hours. The solutions/dispersions were then filtered through 1 μm polypropylene filters. Different concentrations of PANI(ES) in water are routinely prepared by changing the quantity of PANI(ES) mixed into the water.
EXAMPLE 3 A poly(ethylenedioxythiophene), PEDT (Baytron P. special grade, commercially available from Bayer), solution was diluted with an equal amount deionized water. The solution was stirred at room temperature overnight. The PEDT content of the solution was 0.8%. PEDT solutions were also prepared in which the content of PEDT was 0.4, 0.2 and 0.16%, respectively. All these solutions can be filtered through a 0.23 1 μm filter.
EXAMPLE 4 Thirty grams (30 g.) of a PANI(ES)solution as prepared in Example 2 was mixed with 7 g of deionized water and 0.6 g of poly (acrylamide) (PAM)(M.W. 5,000,000-6,000,000, Polysciences) under stirring at room temperature for 4-5 days. The weight ratio of PANI(ES) to PAM in the blend solution is 1:2. Blend solutions were also prepared in which the weight ratio of PANI(ES) to PAM was 1:1, 1:1.5, 1:2.5, 1:3, 1:4, 1:5, 1:6 and 1:9, respectively.
EXAMPLE 5 Glass substrates were prepared with patterned ITO electrodes. Using the PANI, PEDT and PANI blend solutions as prepared in Examples 2, 3 and 4, layers were spin-cast on top of the patterned substrates and thereafter, baked at 90� C. in a vacuum oven for 0.5 hour. The films were then treated at 200� C. in a dry box for 30 minutes. The resistance between ITO electrodes was measured using a high resistance electrometer. Thickness of the film was measured by using a Dec-Tac surface profiler (Alpha-Step 500 Surface Profiler, Tencor Instruments). Table 1 compares the conductivity and thickness of PANI(ES),PANI(ES)-PAM blend and PEDT films. As can be seen from Table, the conductivity of PANI(ES) and PEDT is 10-4 and 10-3 S/cm respectively. Both values are too high for use in pixellated displays. The high temperature treated PANI(ES)-PAM blend has ideal conductivity and thickness for these materials to be used in pixellated displays.
This Example demonstrates that a high temperature-treated PANI(ES) blend has ideal conductivity and thickness for use in pixellated displays; i.e. sufficiently low that interpixel current leakage can be limited without need for patterning the PANI(ES) blend film.
Bulk conductivity of PANI(ES), PANI(ES)-PAM
blend and PEDT
5.1 � 10−4 PEDT
1.8 � 10−3 PANi-PAM (1:2)
200� C./30 min
7.4 � 10−7 EXAMPLE 6 Light emitting diodes were fabricated using soluble poly(1,4-phenylenevinylene) copolymer (C-PPV) (H. Becker, H. Spreitzer, W. Kreduer, E. Kluge, H. Schenk, I.D. Parker and Y. Cao, Adv. Mater. 12, 42 (2000) as the active semiconducting, luminescent polymer; the thickness of the C-PPV films were 700-900 Å. C-PPV emits yellow-green light with emission peak at �560 nm. Indium/tin oxide was used as the anode contact layer. A layer of PANI, PEDT or PANI-PAM blend was then applied using the solutions prepared in Examples 2, 3 and 4. These layers were spin-cast on top of the patterned substrates. The layers were baked at 90� C. in a vacuum oven for 30 minutes, then treated at 200� C. in dry box for 30 minutes. The active layer and a metal cathode were applied. The device architecture was ITO/Polyaniline blend/C-PPV/metal. Devices were fabricated using both ITO on glass (Applied ITO/glass) and ITO on plastic, polyethylene teraphthalate, PET, as the substrate (Courtauld's ITO/PET); in both cases, ITO/Polyaniline blend bilayer was the anode and the hole-injecting contact. Devices were made with a layer of either Ca or Ba as the cathode. The metal cathode film was fabricated on top of the C-PPV layer using vacuum vapor deposition at pressures below 1�10−6 Torr yielding an active layer with area of 3 cm2. The deposition was monitored with a STM-100 thickness/rate meter (Sycon Instruments, Inc.). 2,000-5,000 Å of aluminum was deposited on top of the 15 Å barium layer. For each of the-devices, the current vs. voltage curve, the light vs. voltage curve, and the quantum efficiency were measured. The measured operating voltage and efficiencies of the devices with different blend layer are summarized in the Table 2. As can be seen from the data, the lowest operating voltage and highest light output-were achieved from the device with the PEDT layer.
This Example demonstrates that highest performance polymer LEDs can be fabricated using PEDT as a hole injection (buffer) layer.
Performance of devices fabricated with PANI(ES),
PANI(ES)-PAM blend and PEDT
at 8.3 mA/cm2 Blend
PANi-PAM (1:2)
EXAMPLE 7 Devices produced in accord with Example 6 were encapsulated using a cover glass sandwiched by UV curable epoxy. The encapsulated devices were run at a constant current of 3.3 ma/cm2 in an oven at a temperature of 70� C. The total current through the devices was 10 mA with luminance of approx. 200 cd/cm2. Table 3 and FIG. 3 shows the light output and voltage increase during operation at 70� C. The light output 300-1, 302-1, 304-1 for devices 300, 302 and 304 respectively are shown in dashed lines in FIG. 3. The voltage output 300-2, 302-2, 304-2 for devices 300, 302 and 304 respectively are shown in solid lines in FIG. 3.
In contrast to devices with PANI(ES) and PANI(ES)-PAM blend as anode, which degrade within 160-190 hours of stress at 70� C., the half life of the devices with the PEDT layer reaches 300 hours with a very low voltage increase (4.3 mV/hour). It is almost twice longer than the device with PANI(ES)-PAM blend. However, PEDT layers alone do not have resistance sufficiently high to avoid inter-pixel current leakage and is not suitable for use in pixellated displays. From Ahrennius plots of the luminance decay and voltage increase data collected at 50, 70 and 85� C., the temperature acceleration factor was estimated to be ca. 25 at 70� C. Thus, the extrapolated stress life at room temperature was determined to be approximately 7,500 hours for devices with the PEDT layer.
This Example demonstrates that longest lifetimes can be obtained for polymer LEDS fabricated with PEDT layers. However, these layers do not have resistance sufficiently high to avoid inter-pixel current leakage.
Stress life of LED devices fabricated with PANI(ES), PANI(ES)-PAM
Stress Life at 70� C. at
3.3 mA/cm2 Ref. No.
mV/h
cd/m2*
*Initial Brightness
EXAMPLE 8 The resistance measurements of Example 5 were repeated, but the PANI(ES) layer was spin-cast from the blend solutions prepared in Examples 4 at 1400 rpm. The weight ratio of PANI(ES) to PAM in the blend solution is 1:2. The film was baked at 200� C. for 30 minutes in dry box after dried in 90� C. vacuum oven for 0.5 hour. The thin PEDT film was spinning cast on the top of the PANI blend layer from the solution prepared in Example 3. The thickness of the PEDT layer is ranged from 970 Å to �10 Å. The resistance between ITO electrodes was measured using a high resistance electrometer. Thickness of the film was measured by using a Dec-Tac surface profiler (Alpha-Step 500 Surface Profiler, Tencor Instruments). Table 4 shows the surface resistance of PANI(ES)-blend/PEDT double layer films with different PEDT thickness. As can be seen from Table, the surface resistance of the PANI(ES)-blend/PEDT double layer can be controlled over a wide range, from 107 to 109 ohm/sq by adjusting the thickness of PEDT layer. While the thickness of PEDT decrease to below 50 Å, the conductivity of the double layer is below 108 ohm/sq, which is ideal for use in pixellated displays.
This Example demonstrates that PANI(ES)-blend/PEDT double layer films can be prepared with conductivity less than 108 ohm/sq.
Surface Resistance of PANI(ES)-PAM/PEDT
double layer with different PEDT thickness
PEDT Solution
5.8 � 107 0.8
4.0 � 108 0.8
5.8 � 108 0.4
1.4 � 109 0.2
5.3 � 109 0.2
6.1 � 109 0.16
5.8 � 109 EXAMPLE 9 The device measurements summarized in Example 6 were repeated, but the PANI blend layer was replaced with PANI(ES)-blend/PEDT double layers prepared as in Examples 8. Table 5 shows the device performance of LEDs fabricated from polyblend films with various double layers. Devices fabricated with PANI blend/PEDT double layers exhibit the same operating voltage and light efficiency as devices made with PEDT layers.
This Example demonstrates that a PANI blend/PEDT double layer can be used to fabricate polymer LEDs with the same low operating voltage and high efficiency as devices made with a PEDT layer.
Performance of devices fabricated with PANI(ES)-PAM/PEDT double
layer with different PEDT thickness
at 8.3 mA/cm2 Concentration (%)
EXAMPLE 10 The stress measurements summarized in Example 7 were repeated, but the PANI blend layer (incorporated in device 300 in Table 3) was replaced by PANI blend/PEDT double layers prepared as in Examples 8. Table 6 and FIG. 4 show the stress life of devices fabricated with a PANI blend/PEDT double layer. In FIG. 4, the light output 302-1, 304-1, 402-1, 404-1, and 406-1 for devices 302 and 304 as shown in Table 3 and devices 402, 404 and 460 as shown in Table 6, respectively, are shown in dashed lines. The voltage output 302-2, 304-2, 402-2, 404-2, and 406-2 for devices 302 and 304 as shown in Table 3 and devices 402, 404 and 460 as shown in Table 6, respectively, are shown in solid lines.
As can be seen from the data, the voltage increase rate of the double layer device with an �10 Å to 20 Å layer of PEDT is slightly lower than that of device made from PEDT. The half-life time of the double layer device is even slightly longer than that of the PEDT device.
This Example demonstrates that the PANI blend/PEDT double layer can combine the high resistance of PANI blend and long life stress lifetime of PEDT in one device.
Stress life of LED devices fabricated with PANI(ES)-PAM/PEDT
Stress Life at 70� C.
at 8.3 mA/cm2 No.
EXAMPLE 11 The resistance measurements of Example 5 were repeated, but the PANI(ES) layer was spin-cast from the blend solutions prepared in Examples 4. The weight-ratio of PANI(ES) to PAM in the blend solution is 1:1.5, 1:2, 1:3,1:4 1:5 and 1:6. The film was baked at, 200� C. for 30 minutes in dry box after dried in 90� C. vacuum oven for 0.5 hour. The thin PEDT film was spinning cast on the top of the PANI blend layers from the solution prepared in Example 3. The concentration of PEDT solution is 0.16% and the spinning rate is 4000 rpm. The thickness of the PEDT layer is �10 Å. The resistance between ITO electrodes was measured using a high resistance electrometer. Thickness of the film was measured by using a Dec-Tac surface profiler (Alpha-Step 500 Surface Profiler, Tencor Instruments). Table 7 shows the surface resistance of PANI blend/PEDT double layer films with different PANI(ES) to PAM ratio. As can be seen from the Table, the surface resistance of the PANI blend/PEDT double layer can be controlled over a wide range, from 108 to 1015 ohm/sq by adjusting the weight ratio of PANI(ES)-PAM layer.
This Example demonstrates that PANI blend/PEDT double layer films can be prepared with conductivity less than 108 ohm/sq and even less than 1013 ohm/sq.
Surface Resistance of PANI(ES)-PAM/PEDT double
layer with different PANI(ES)-PAM blend
PANI Blend
PANI-PAM
6.6 � 108 PANI-PAM
5.7 � 109 PANI-PAM
2.1 � 1013 PANI-PAM
1.1 � 1015 PANI-PAM
9.0 � 1014 PANI-PAM
9.6 � 1014 EXAMPLE 12 The device measurements summarized in Example 6 were repeated, but the PANI blend layer was replaced with PANI blend/PEDT double layers. Table 8 shows the device performance of LEDs fabricated from polyblend films with different double layers. When the PANI to PAM ratio was larger than 1:4, devices fabricated with PANI blend/PEDT double layer exhibited the same operating voltage and light efficiency as devices made with a PEDT layer alone. The lower PANI(ES) to PAM ratios result in deterioration of device performance.
This Example demonstrates that PANI blend/PEDT double layers can be used to fabricate polymer LEDs with the same low operating voltage and high efficiency as devices made with a PEDT layer alone.
layer with different PANI(ES)-PAM blends
at 8.3 mA/cm2 PANI Blend
EXAMPLE 13 The stress measurements summarized in Example 7 were repeated, but the PANI(ES)-blend layer was replaced with PANI blend/PEDT double layers. Table 9 and FIG. 5 show the stress life of devices fabricated with the PANI(ES) blend/PEDT double layers at 80� C. The luminance 500-1, 502-1, 504-1, and 506-1 for devices 500, 502, 504 and 506 respectively are shown in dashed lines in FIG. 3. The voltage output 500-2, 502-2, 504-2, and 506-2 for devices 500, 502, 504 and 506 respectively are shown in solid lines in FIG. 5. When the PANI to PAM ratio is larger than 1:4, the voltage increase rate of the double layer device was lower than that of devices made from PEDT. The half-life time of the double layer device is even longer than that of the PEDT device at 80� C.
This Example demonstrates that the PANI(ES) blend/PEDT double layer can combine the high resistance of PANI blend and the long life stress life time of PEDT in one device.
double layers with different PANI(ES)-PAM blend
at 3.3 ma/cm2:
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS4720432Feb 11, 1987Jan 19, 1988Eastman Kodak CompanyElectroluminescent device with organic luminescent mediumUS5247190Apr 18, 1990Sep 21, 1993Cambridge Research And Innovation LimitedThin semiconductor between contactorsUS5254633Jul 10, 1991Oct 19, 1993Allied Signal Inc.Process for the preparation of conductive polymer blendsUS5399936Jul 25, 1994Mar 21, 1995Pioneer Electronic CorporationOrganic electroluminescent deviceUS5408109Feb 27, 1991Apr 18, 1995The Regents Of The University Of CaliforniaVisible light emitting diodes fabricated from soluble semiconducting polymersUS5698740Feb 12, 1997Dec 16, 1997Toyo Ink Manufacturing Co., Ltd.ElectroluminescenceUS5719467Jul 27, 1995Feb 17, 1998Hewlett-Packard CompanyOrganic electroluminescent deviceUS5723873Mar 3, 1994Mar 3, 1998Yang; YangBilayer composite electrodes for diodesUS5798170Feb 29, 1996Aug 25, 1998Uniax CorporationLong operating life for polymer light-emitting diodesUS5807627Jul 26, 1993Sep 15, 1998Cambridge Display Technologies Ltd.Electroluminescent devicesUS5844363Jan 23, 1997Dec 1, 1998The Trustees Of Princeton Univ.Vacuum deposited, non-polymeric flexible organic light emitting devicesUS5858561Mar 2, 1995Jan 12, 1999The Ohio State UniversityElectroluminescent organic light emitting material between two electrically insulating materials, each in contact with electrode connected to voltage sourceUS5869350Dec 20, 1994Feb 9, 1999The Regents Of The University Of CaliforniaFabrication of visible light emitting diodes soluble semiconducting polymersUS5879821Nov 13, 1997Mar 9, 1999Xerox CorporationElectroluminescent polymer compositions and processes thereofUS5902677Oct 21, 1996May 11, 1999Motorola, IncConductive polymer layer which is deposited over a conductive transparent metal oxide layer is selected from polypyrroles, polythiophenes, polyfurans, polyanilines, polycarbazoles, polyferrocenes etc.; organic electroluminescent displayUS5948552Aug 27, 1996Sep 7, 1999Hewlett-Packard CompanyHeat-resistant organic electroluminescent deviceUS5965979Apr 17, 1996Oct 12, 1999Cambridge Display Technology LimitedManufacture of organic light emitting devicesUS5993694May 30, 1997Nov 30, 1999Nippon Shokubai Co., Ltd.The aromatic rings of the skeleton thereof are substituted by an average of 0.1-4 sulfonic acid (salt) groups and an average of 0-3.9 h's or other substituents, doped with an external dopant.US6017644Sep 11, 1998Jan 25, 2000Canon Kabushiki KaishaOrganic compound, its polymer and light emitting deviceUS6127004Jan 29, 1999Oct 3, 2000Eastman Kodak CompanyProviding substrate having top surface coating with material including anode having indium-tin-oxide; forming amorphous conductive layer over anode by applying radio frequency field across fluorocarbon gas to deposit fluorocarbon polymer layerUS6208075 *Nov 5, 1998Mar 27, 2001Eastman Kodak CompanyElectoluminescent device having organic light-emitting structure formed over the anode including a hole transport layer of a fluorocarbon based conductive polymer prepared by plasma polymerization of a fluorocarbon gasUS6235414Mar 11, 1998May 22, 2001The Ohio State University Research FoundationColor variable bipolar/AC light-emitting devicesUS6249085Jun 25, 1999Jun 19, 2001Tdk CorporationOrganic electroluminescent device with a high-resistance inorganic hole injecting and transporting layerUS6384528Nov 20, 1998May 7, 2002Cambridge Display Technology LimitedElectroluminescent deviceUS6430033Jun 24, 1999Aug 6, 2002Nichicon CorporationMultilayer; electroconductive polymer over dielectricUS6593690 *Sep 3, 1999Jul 15, 20033M Innovative Properties CompanyLarge area organic electronic devices having conducting polymer buffer layers and methods of making sameUS6605483Apr 27, 2001Aug 12, 2003Add-Vision, Inc.Screen printing light-emitting polymer patterned devicesUS6727008 *Apr 30, 1997Apr 27, 2004Agilent Technologies, Inc.Light-emitting devices based on small organic moleculesUS6850003 *Sep 4, 1998Feb 1, 2005Cambridge Display Technology, Ltd.Self-assembled transport layers for OLEDsUS20010009690Feb 14, 2000Jul 26, 2001Choong Vi-EnOrganic electroluminescent device with enhanced performanceUS20020011779Oct 15, 2001Jan 31, 2002Cambridge Display Technology Ltd.Charge-carrier injecting layers for injecting positive and negative charge carriers, organic light-emitting layer located between charge-carrier injecting layers, conductive polymer layerUS20020012848Aug 30, 2001Jan 31, 2002Callahan Robert W.Electrochemical cell incorporating polymer matrix materialUS20030170456Feb 15, 2002Sep 11, 2003Eastman Kodak CompanyFirst conductive layer containing an intrinsically conductive polymer, a binder and a spacer element embedded in and projecting from the surface of first conductive layer, and a second conductive layer separated from first by spacerUS20050084713 *Oct 15, 2004Apr 21, 2005Junji KidoOrganic electroluminescent device and production process thereofUS20060186796 *Jan 31, 2006Aug 24, 2006Mitsubishi Chemical CorporationCompound, charge transporting material and organic electroluminescent elementEP0901176A2Aug 27, 1998Mar 10, 1999Cambridge Display Technology LimitedElectroluminescent deviceEP1020989A2Dec 13, 1999Jul 19, 2000Raytheon CompanyTemperature compensated amplifier and operating methodGB2329740A Title not availableJP2000030870A Title not availableJP2000160171A Title not availableWO1996031909A1Apr 5, 1996Oct 10, 1996Uniax CorpSmart polymer image processorWO2000006665A1Jul 23, 1999Feb 10, 2000Dow Chemical CoOrganic electroluminescent devicesWO2001041230A1Nov 30, 2000Jun 7, 2001Uniax CorpHigh resistance polyaniline useful in high efficiency pixellated polymer electronic displays* Cited by examinerNon-Patent CitationsReference1Braun. D. et al., Visible light emission from semiconducting polymer diodes, Appl. Phys. Lett., May 6, 1991, 1982-1984, 58(18), American Institute of Physics.2Burroughes, J. H. et al., Light-emitting diodes based on conjugated polymers, Nature, Oct. 11, 1990, 539-541, vol. 347.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7875841 *Nov 9, 2006Jan 25, 2011Siemens AktiengesellschaftOrganic pixeled flat detector having increased sensitivityUS8173995 *Dec 20, 2006May 8, 2012E. I. Du Pont De Nemours And CompanyElectronic device including an organic active layer and process for forming the electronic deviceUS8329505Jan 28, 2011Dec 11, 2012Lock Haven University Of PennsylvaniaMethod for deposition of cathodes for polymer optoelectronic devicesUS8563967 *Jul 7, 2008Oct 22, 2013Koninklijke Philips N.V.Organic functional device and manufacturing method thereforUS8742446 *Nov 3, 2010Jun 3, 2014Sony CorporationLight emitting element and method of manufacturing the sameUS20110108877 *Nov 3, 2010May 12, 2011Sony CorporationLight emitting element and method of manufacturing the same* Cited by examinerClassifications U.S. Classification257/40, 257/E25.008, 257/E51.004, 257/88, 257/E51.012, 257/103International ClassificationH05B33/26, H01L33/00, H01L27/32, H01L51/50, H01L51/52Cooperative ClassificationH01L51/5206, H01L51/5088, H01L27/3281European ClassificationH01L51/52B2, H01L51/50JLegal EventsDateCodeEventDescriptionAug 22, 2012FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google


text:
Tara D. Mangal - Semantic Scholar
R. Bruce Aylward9
Roland W. Sutter8
Nicholas C. Grassly8
Michael Mwanza6
Muhammad Ali Pate6
9Nicholas C. Grassly
6Philip D. Minor
6Yossi Manor
6R. Bruce Aylward
5Danit Sofer
Tara D. Mangal, Steve Paterson, Andrew Karl Fenton
BACKGROUND Many parasites of medical and veterinary importance are transmitted by cold-blooded intermediate hosts or vectors, the abundance of which will vary with ambient temperatures, potentially altering disease prevalence. In particular, if global climate change will increase mean ambient temperature in a region endemic with a human pathogen then it is… (More)
Tara D. Mangal, Raymond Bruce Aylward, Nicholas C. Grassly
The "endgame" for worldwide poliomyelitis eradication will entail eventual cessation of the use of oral poliovirus vaccine (OPV) in all countries to prevent the reintroduction of vaccine-derived polioviruses--exposing some populations to an unprecedented, albeit low, risk of poliovirus outbreaks. Inactivated poliovirus vaccine (IPV) is likely to play a… (More)
Tara D. Mangal, Raymond Bruce Aylward, +4 authors Nicholas C. Grassly
BACKGROUND The completion of poliomyelitis eradication is a global emergency for public health. In 2012, more than 50% of the world's cases occurred in Nigeria following an unanticipated surge in incidence. We aimed to quantitatively analyse the key factors sustaining transmission of poliomyelitis in Nigeria and to calculate clinical efficacy estimates for… (More)
The polio eradication programme in Nigeria has been successful in reducing incidence to just six confirmed cases in 2014 and zero to date in 2015, but prediction and management of future outbreaks remains a concern. A Poisson mixed effects model was used to describe poliovirus spread between January 2001 and November 2013, incorporating the strength of… (More)
www.thelancet.com/lancetgh Vol 2 June 2014 e316 but also the local media and relatives. Obtaining health infor mation via religious leaders strongly aff ected the probability that a child had received OPV, but health workers and town announcers also had a substantial effect on the probability of a child being vaccinated against poliovirus. Because targeted… (More)
OBJECTIVE We compiled the largest dataset of seroconverter cohorts to date from 25 countries across Africa, North America, Europe, and Southeast/East (SE/E) Asia to simultaneously estimate transition rates between CD4 cell stages and death, in antiretroviral therapy (ART)-naive HIV-1-infected individuals. DESIGN A hidden Markov model incorporating a… (More)

type: global

value: This website is an artificial-intelligence backed search engine for academic publications developed at the Allen Institute for AI and publicly released in November 2015. It uses advances in natural language processing to provide summaries for scholarly papers.


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Belvita Breakfast Biscuits, 1.76 Oz Pack, Golden Oat, 64/carton 44000029470 | eBay
(6) belVita Breakfast Biscuits, Golden Oat, 1.76 oz Pack
belVita Brown Sugar Cinnamon Biscuits (20
garnersupply (7932 )
Details about Belvita Breakfast Biscuits, 1.76 Oz Pack, Golden Oat, 64/carton
4 or more for $65.28/ea
US $68.72/ea
223414850932
Last updated on Aug 24, 2019 04:25:06 PDT View all revisions

value: This website is an American multinational e-commerce corporation based in San Jose, California, that facilitates consumer-to-consumer and business-to-consumer sales through its website.


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Fox's Pizza Den - Wikipedia, the free encyclopedia
Fox's Pizza Den is a pizzeria chain based in Murrysville, Pennsylvania, United States. It was founded in 1971 by Jim Fox in Pitcairn, Pennsylvania,[1] and currently has more than 300 locations in 28 U.S. states, all franchise-owned.
Fox's Pizza Den has consistently ranked among the Top 25 pizza chains in the world.[2] The Small Business Administration named Jim Fox as one of the country's top entrepreneurs during National Small Business Week, May 5–11, 2002.[3] Fox's Pizza was ranked "Best Pizza Franchise" in 2007[4]
^ "History of Fox's Pizza Den". FoxsPizzaFranchise.com. Retrieved 2007-07-26. ^ "Industry Headlines for April 3, 2006". PizzaToday.com. Archived from the original on 2007-03-01. Retrieved 2007-07-26. ^ "SBA Winners Credit Compaq Technology for Growth, Profitability During National Small Business Week". 2002-05-03. Retrieved 2007-0

value: This website is the English-language edition of the free online encyclopedia Wikipedia. It was founded on 15 January 2001 as Wikipedia's first edition and, as of October 2021, has the most articles of any edition, at 6,412,521.


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The daytime hosts have been trading pranks Salma Hayek looks chic in a blue, white and black floral-print dress to promote The Prophet in Beirut
Press conference for her new animated Beirut 'I just feel so violated': Kris Jenner's horror as she finds out she is being blackmailed over naked home surveillance footage on KUWTK
Sorry Victoria, David is the real fashion icon in the family! Mr Beckham comes third in poll of most stylish Brits of all time, while his wife limps in at number nine She's a mini Miley: Noah Cyrus, 15, is the spitting image of her famous sister as she attends red carpet event with dad Billy Ray
Would YOU eat ice-cream made from breast milk? Campaigner joins forces with dessert makers to create controversial treat just in time for the royal birth Baking prodigy who started making cakes age THREE has a cookbook, celebrity fans and a booming business... and she's only 17
Detox your kitchen and GLOW with health: Want to look slim AND healthy this summer? Our major new series shows it’s not you that needs a detox — it’s what’s in your fridge and cupboards... How new WNBA star took in her newborn niece fter her sister fell ill and is still caring for her 20 months later

value: This website is the website of the Daily Mail, a newspaper in the United Kingdom, and of its sister paper The Mail on Sunday. MailOnline is a division of dmg media, which is owned by Daily Mail and General Trust plc.


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Wool Hat | eBay
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Distortion (Outro): Phace: Amazon.co.uk: MP3 Downloads
See larger image Distortion (Outro)
Duration: 5:13 minutesGenres: Dance & Electronic ASIN: B00BJWNYJW


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Sport Science: Steph Curry's NBA DNA - ESPN Video - ESPN
Sport Science: Steph Curry's NBA DNA
Publish Date: Dec 11, 2013, 03:23 PM ETDuration: 00:39
Sport Science breaks down Warriors PG Steph Curry to determine the composition of his basketball DNA and how he compares to other greats in the NBA.Tags: NBA, Stephen Curry, Golden State Warriors

value: This website is the official website of ESPN. It is owned by ESPN Internet Ventures, a division of ESPN Inc.


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0 $1.59 The Everychurch Guide to Growth: How Any Plateaued Church Can Grow - eBook
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This website is a Christian catalog and internet retailer.
Christian Book Distributors was started in 1978 by Stephen Hendrickson, 19 years old and a sophomore at Central Bible College in Springfield, Missouri, out of his parents’ home in Lynn, Massachusetts.


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9780988111813: Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2) - AbeBooks - R. E. Donald: 0988111810
R. E. Donald Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2)
ISBN 13: 9780988111813
ISBN 10: 0988111810 ISBN 13: 9780988111813
Publisher: Proud Horse Publishing, 2012
Hunter's ex-wife maintains that by taking to the highway Hunter is running away from his past, but he believes that the solitude of days on the road is helping him to heal from guilt over the failure of his marriage and the suicide of his best friend. Tangled relationships and multiple suspects emerge throughout the novel, as Hunter butts heads with more than one officer of the law to solve the crime.
A 2012 Global Ebook Awards finalist, ... Ice on the Grapevine: A Hunter Rayne Highway Mystery is a tense murder mystery featuring tough-minded ex-homicide detective turned eighteen-wheel truck driver Hunter Rayne. ... [It] is a riveting mystery that will keep the reader guessing to the very end. - Midwest Book Review
This is a well spun yarn, full of plot detail and credible human response. Whodunit addicts will not be disappointed. - The Kindle Book Review
... a straightforward and uncomplicated story, well-told and tightly edited. ... Ice on the Grapevine is well worth having a look at. - Crime Fiction Lover, the Site for Die-Hard Crime & Thriller Fans (UK)
1. Ice on the Grapevine (Paperback or Softback)
Donald, R. E.
Published by Proud Horse Publishing 7/28/2012 (2012)
Book Description Proud Horse Publishing 7/28/2012, 2012. Paperback or Softback. Condition: New. Ice on the Grapevine. Book. Seller Inventory # BBS-9780988111813
2. Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2)
Published by Proud Horse Publishing (2018)
Book Description Proud Horse Publishing, 2018. Paperback. Condition: New. Never used! This item is printed on demand. Seller Inventory # 0988111810
3. Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2)
Book Description Condition: New. Seller Inventory # ria9780988111813_ing
4. Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2)
Published by Proud Horse Publishing (2012)
Book Description Proud Horse Publishing, 2012. Paperback. Condition: New. Seller Inventory # INGM9780988111813
5. Ice on the Grapevine (Paperback)
Published by Proud Horse Publishing, United States (2012)
Book Description Proud Horse Publishing, United States, 2012. Paperback. Condition: New. Language: English . Brand New Book ***** Print on Demand *****. Seller Inventory # APC9780988111813
6. Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2)
Book Description Proud Horse Publishing. PAPERBACK. Condition: New. 0988111810 Special order direct from the distributor. Seller Inventory # ING9780988111813
7. Ice on the Grapevine (Paperback)
8. Ice on the Grapevine (Paperback)
Book Description Proud Horse Publishing, United States, 2012. Paperback. Condition: New. Language: English . This book usually ship within 10-15 business days and we will endeavor to dispatch orders quicker than this where possible. Brand New Book. Seller Inventory # LIE9780988111813
9. Ice on the Grapevine: Volume 2 (Hunter Rayne Highway Mystery)
Book Description Proud Horse Publishing, 2012. Condition: New. This item is printed on demand for shipment within 3 working days. Seller Inventory # LP9780988111813
10. Ice on the Grapevine: A Hunter Rayne highway mystery (Volume 2)
Book Description Proud Horse Publishing, 2012. Condition: New. book. Seller Inventory # M0988111810

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