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Acene-thiophene compounds are disclosed that are useful as organic semiconductors. The compounds, when used as the semiconductor layer in organic thin-film transistors exhibit device characteristics, like charge-carrier mobilities and current on/off ratios, that are comparable to those of pentacene. Also described are semiconductor devices comprising at least one compound of the invention; and articles comprising the semiconductor devices such as thin film transistors or transistor arrays, and electroluminescent lamps.
1. A method of making an organic thin-film transistor device comprising:
a) providing a substrate;
b) depositing a gate electrode material on the substrate;
c) depositing a gate dielectric on the gate electrode material;
d) depositing an organic semiconductor layer comprising acene-thiophene compounds, and
e) providing a source electrode and a drain electrode contiguous to the organic semiconductor layer adjacent to the gate dielectric layer;
wherein said acene-thiophene compounds are of the formula:
wherein Ac is a substituted or unsubstituted acenyl group selected from 2-anthracenyl, and 2-tetracenyl, R1 is Ac, an alkyl group or H, each of R2 and R3 is independently selected from H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof, and n is 1 to 4, and/or of the formula:
wherein Ac′ is an acenyl group selected from substituted or unsubstituted 2,6-anthracenyl or 2,8-tetracenyl; R1 is an acenyl group selected from substituted or unsubstituted 2-anthracenyl or 2-tetracenyl, an alkyl group or H; each of R2 and R3 is independently selected from H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof, and n is 1 to 4.
2. The method of
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wherein each Ac is an acenyl group selected from 2-anthracenyl, and 2-tetracenyl, and each of R2 and R3 is independently selected from H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof, and n is 1 to 4.
11. The method of
wherein Ac is an acenyl group selected from a substituted or unsubstituted 2-anthracenyl, and 2-tetracenyl, R1 is Ac, an alkyl group or H, each of R2 and R3 is independently selected from H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof, and n is 1 to 4, with the proviso that when Ac is anthracenyl and n=2, then R1 is Ac or an alkyl group.
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Special Information: This application claims priority to U.S. application Ser. No.10/641,730, recently allowed.
This invention relates to organic compounds that are useful as semiconductors and, in another aspect, to devices comprising the compounds, and to methods of preparing devices comprising the compounds.
Traditionally, inorganic silicon and gallium arsenide semiconductors, silicon dioxide insulators, and metals such as aluminum and copper have dominated the semiconductor industry. In recent years, however, there has been an increasing research effort in using organic thin-film transistors (OTFTs) as an alternative to the traditional devices based on inorganic material sets. Among other benefits, the use of organic materials may enable lower cost manufacturing of electronic devices, large area applications, and the use of flexible circuit supports for display backplanes or integrated circuits.
A variety of materials have been considered as organic semiconductors, with the most common being fused acenes such as tetracene and pentacene, oligomeric materials containing thiophene or fluorene units, and polymeric materials like regioregular poly(3-alkylthiophene). While polymers may be coated from solution, device performance is poor when compared to well-ordered thin films prepared by high vacuum vapor deposition. Positive charge-carrier mobility (p-type) as high as 3.3 cm2 V−1 s−1 (Kelley, T. W.; Boardman, L. D.; Dunbar, T. D.; Muyres, D. V.; Pellerite, M.; Smith, T. P. J. Phys. Chem. B 2003, 107, 5877-5881), on/off current ratios greater than 108 (Knipp, D.; Street, R. A.; V÷lkel, A.; Ho, J. J. Appl. Phys. 2003, 93, 347-355), and sub-threshold voltages of less than 0.5 V (Klauk, H.; Halik, M.; Zschieschang, U.; Schmid, G.; Radlik, W.; Weber, W. J. Appl. Phys. 2002, 92, 5259-5263), have been reported for pentacene-based transistors. These values are comparable or superior to those of amorphous silicon-based devices.
However, there are several areas where an alternative semiconductor material could offer improvements. The device architecture, choice of materials and substrate roughness all affect device performance. In pentacene-based devices, these variations have, in part, been attributed to the existence of several polymorphs (Mattheus, C. C.; de Wijs, G. A.; de Groot, R. A.; Palstra, T. T. M. J. Am. Chem. Soc. 2003, 125, 6323-6330). The alignment or structural order of the pentacene molecules differs for each polymorph or crystallographic phase, and this structural order determines the electronic properties of the device. The crystallographic phase adopted by pentacene depends on the process and conditions under which the crystals are formed. The thin film form of pentacene can be converted to the bulk phase by exposure to solvents such as isopropanol, acetone or ethanol. (See, for example, Gundlach et al., Appl. Phys. Lett., 2000, 74(22) 3302.) Additionally, the long term oxidative and thermal stability of pentacene is unknown, as is the lifetime of pentacene-based semiconductor devices. The ease of synthesis and purification is another factor that must be considered in regard to the utility of an organic semiconductor. In particular, soluble materials may be purified by recrystallization or chromatography, familiar techniques that are not available for fused acenes like pentacene. The ability to construct devices using solution processing techniques is potentially key for realizing a low cost manufacturing process. And lastly, it is likely that a variety of organic semiconductor materials possessing a range of physical and chemical properties may be required for specific applications.
In view of the foregoing, we recognize there is a need for new organic semiconductors that provide stable and reproducible electrical characteristics.
Briefly, the present application discloses acene-thiophene compounds that are useful as organic semiconductors. It has been discovered that the acene-thiophene compounds, when used as the active layer in OTFTs exhibit device characteristics, like charge-carrier mobilities and current on/off ratios that are comparable to those of pentacene. With these hybrid acene-thiophene materials, we have combined the desirable properties of both fused acenes and oligothiophenes into single and novel class of high performing organic semiconductor. The compounds of the present invention are reliably prepared, and purified to semiconductor grade by either gradient sublimation, and/or recrystallization, and/or chromatography, depending on the specific material. Thus, the disclosed compounds meet the need in the art for new organic semiconductors that provide useful performance and stability in devices and be viable alternatives to amorphous silicon or pentacene-based devices.
Also disclosed are semiconductor devices comprising at least one compound of the invention, and articles comprising the semiconductor devices. For example, specifically preferred devices include thin film transistors or transistor arrays, and electroluminescent lamps.
As used herein, ōlayerö refers to any layer that can be formed on a substrate from precursor compounds using a solution coating process or vapor deposition process, for example. The term ōlayerö is meant to include layers specific to the semiconductor industry, such as ōbarrier layer,ö ōdielectric layer,ö ōinsulating layer,ö and ōconductive layer.ö (The term ōlayerö is synonymous with the term ōfilmö frequently used in the semiconductor industry.) The term ōlayerö is also meant to include layers found in technology outside of semiconductor technology, such as coatings on glass. ōDielectric layerö or ōgate dielectricö as used herein refers to a layer (or film) having a relatively high dielectric constant.
Acene-thiophene compounds disclosed herein are useful as organic semiconductors. The acene-thiophene compounds are of the formula I:
Compounds with fused aromatic ring systems are commonly given a numbering sequence in which each carbon atom that is a member of only one ring is numbered. (See, for example, James E. Banks, NAMING ORGANIC COMPOUNDS: A PROGRAMMED INTRODUCTION TO ORGANIC CHEMISTRY, Saunders College Publishing, p. 124, PA (1976).) The numbering sequence that is generally used for the acenes is shown below
The thiophene ring(s) are numbered as follows:
The (oligo)thiophene moiety may be unsubstituted or substituted at each of the 3 - and/or 4-positions of each thiophene ring. The terminal ring of the acene group, i.e. the ring distal from the (oligo)thiophene, may be substituted or unsubstituted, and is preferably unsubstituted. With respect to the numbering convention above, the terminal or distal ring of the acene group would be defined by carbon 5, 6, 7 and 8 carbons of the naphthalene or anthracene rings, or the 7, 8, 9 and 10 carbons of the tetracene ring. Where substituted, symmetrical substitution is preferred, although it is recognized that asymmetric analogs may provide the same utility.
As previously noted, the 2- and/or 5-position of the thiophene ring(s) of the (oligo)thiophene moiety is attached to the 2-position of the acene ring(s). The acene(s) may be further substituted at the 5-, 6-, 7-, or 8-position of the naphthalene ring, the 5-, 6-, 7-, or 8-position of the anthracene ring, or the 7-, 8-, 9-, or 10-position of the tetracene ring. One or more of these positions may be substituted. Where the acene is singly substituted at the terminal ring, it is preferred that the substitution is at the 6-position of the naphthalene or anthracene rings, or the 8-position of the tetracene ring. One or more acene rings may be substituted.
Where present, each substituent of the acene ring is independently selected from the group consisting of alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, (oligo)thiophene groups (which may be further substituted) and combinations thereof. More preferably, each substituent is independently an alkyl group, an alkoxy group, an (oligo)thiophene group or a combination thereof. Most preferably, each substituent is independently an alkyl group or an (oligo)thiophene group. Useful alkyl groups, alkoxy groups, and thioalkoxy groups may include, for example C1-C18 alkyl groups, alkoxy groups, and thioalkoxy groups.
It is most preferred that the terminal acene ring of the acene-thiophene compounds are unsubstituted, due to the relative ease of synthesis.
With respect to Formula I, each thiophene ring of the (oligo)thiophene moiety may be substituted, as indicated by substituents R2 and R3. Each R2 and R3 may be selected from the group consisting of H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof. More preferably, each substituent is independently an alkyl group, an alkoxy group, or a combination thereof. Most preferably, each substituent is independently an C1-C18 alkyl group of alkyl groups. It is particularly advantageous if the substituted thiophenes consist of oligomers of regioregular poly(3-alkylthiophenes).
Where the acene substituent is an (oligo)thiophene group, compounds of the following formula are provided:
wherein Ac′ is an acenyl group selected from 2,6-anthracen-diyl, and 2,8-tetracendiyl; R1 is an acenyl group selected from substituted or unsubstituted 2-anthracenyl or 2-tetracenyl, an alkyl group or H; each of R2 and R3 is independently selected from H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof, and n is 1 to 4.
Where R1 is an acene group, compounds of the following formula are provided:
wherein Ac is an acenyl group selected from 2-naphthyl, 2-anthracenyl, and 2-tetracenyl; and each of R2 and R3 is independently selected from H, alkyl groups, alkoxy groups, thioalkoxy groups, halogen atoms, and combinations thereof, and n is 1 to 4. The terminal rings of the acene groups may be further substituted as previously described.
Some preferred compounds, along with their chemical names and abbreviations are shown below:
The acene-thiophene compounds may be prepared by a Stille coupling of the appropriate mono- or dihaloacene with the appropriate mono- or bis(trialkylstannyl)thiophene. The halogen substituents on the acene starting material are typically bromine or chlorine, although it is recognized that other halogens may also be used. The Stille coupling may be performed as outlined in Littke, A. F.; Schwarz, L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 6343-6348. Additional information regarding reaction conditions may be found in Farina, V.; Krishnamurthy, V., Organic Reactions; Paquette, L. A., Ed.; John Wiley & Sons, Inc., 1997; Vol. 50, p 1-652. The examples below also provide detail regarding some of the specific materials reported herein. The products may be purified to semiconductor grade by either gradient sublimation, and/or recrystallization, and/or chromatography, depending on the specific material.
Depicted below is an example of a Stille coupling reaction as described above:
Other synthetic strategies can be employed to construct acene-thiophene compounds. For example, a palladium catalyzed Suzuki coupling has been used to couple 2-bromoanthracene (see Ito, K.; Suzuki, T.; Sakamoto, Y.; Kubota, D.; Inoue, Y.; Sato, F;
Tokito, S. Angew. Chem., Int. Ed. 2003, 42, 1159-1162). A review of synthetic methods for organic semiconductors has been recently published (see Katz, H. E.; Bao, Z.; Gilat, S. L. Acc. Chem. Res. 2001, 34, 359-369).
The terminal ring substituted acene-thiophene compounds may be prepared by a Stille coupling of a terminal ring-substituted 2-chloro- or 2-bromo acene, such as 2-halo-6-alkyl naphthalene or anthracene, with a mono- or bis-(trialkylstannyl)thiophene. The terminal ring-substituted 2-chloro- or 2-bromo acenes may be prepared by methods known in the art, and reference may be made to the synthetic schemes described in Applicant's copending application U.S. Ser. No. 10/256,616, published as U.S. 2003-0105365, and incorporated herein by reference.
The tri-n-butylstannyl (oligo)thiophene compounds may be prepared by treatment of the mono- or dilithiated (oligo)thiophene with 1 or 2 eq of tri-n-butylstannyl chloride, respectively. For example, 5,5″-bis(tri-n-butylsannyl)-2,2′:5′,2″-terthiophene (Bu3SnŚT3ŚSnBu3), may be prepared as shown below and described in Miller, L. L.; Yuan, Y J. Org. Chem. 1995, 60, 6813-6819. Although we have preferred use of the tri-n-butylstannyl substituent, other trialkylstannyl groups are known to work in Stille coupling reactions.
The 3- and/or 4-substituted (oligo)thiophene starting materials may be prepared using established methodologies. For example, 3,4′-dihexyl-2,2′-bithiophene (T2h) was prepared by a Stille coupling between 2-(tri-n-butylstannyl)-4-hexylthiophene and 2-bromo-3-hexylthiophene, as shown be
The disclosed compounds can be used as the semiconductor layer in semiconductor devices. Although there are numerous types of semiconductor devices, common to all is the presence of one or more semiconductor materials. Semiconductor devices have been described, for example, by S. M. Sze in Physics of Semiconductor Devices, 2nd edition, John Wiley and Sons, New York (1981). Such devices include rectifiers, transistors (of which there are many types, including p-n-p, n-p-n, and thin-film transistors), light emitting semiconductor devices (for example, organic light emitting diodes), photoconductors, current limiters, thermistors, p-n junctions, field-effect diodes, Schottky diodes, and other devices known in the art. In each semiconductor device, the semiconductor material is combined with one or more conductors or insulators to form the device. Semiconductor devices can be prepared or manufactured by known methods such as, for example, those described by Peter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill, New York (2000).
Electronic devices include components such as transistors, arrays of transistors, diodes, capacitors, embedded capacitors, and resistors that are used to form circuits. Electronic devices also include arrays of circuits that perform an electronic function. Examples of these arrays, or integrated circuits, are amplifiers, receivers, transmitters, inverters, and oscillators.
Applications of these devices and arrays include radio frequency identification devices (RFIDs), smart cards, lamps, displays, and the like. The present invention is not limited by the type of device. Particularly preferred types of devices include thin film transistors.
A particularly useful type of transistor device, the thin-film transistor (TFT), generally includes a gate electrode, a gate dielectric on the gate electrode, a source electrode and a drain electrode adjacent to the gate dielectric, and a semiconductor layer adjacent to the gate dielectric and adjacent to the source and drain electrodes (see, for example, S. M. Sze, Physics of Semiconductor Devices, 2nd edition, John Wiley and Sons, page 492, New York (1981)). These components can be assembled in a variety of configurations. More specifically, an organic thin-film transistor (OTFT) has an organic semiconductor layer.
Typically, a substrate supports the OTFT during manufacturing, testing, and/or use. Optionally, the substrate can provide an electrical function for the OTFT. Useful substrate materials include organic and inorganic materials. For example, the substrate can comprise inorganic glasses, ceramic foils, polymeric materials (for example, acrylics, epoxies, polyamides, polycarbonates, polyimides, polyketones, poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) (sometimes referred to as poly(ether ether ketone) or PEEK), polynorbornenes, polyphenyleneoxides, poly(ethylene naphthalenedicarboxylate) (PEN), poly(ethylene terephthalate) (PET), poly(phenylene sulfide) (PPS)), filled polymeric materials (for example, fiber-reinforced plastics (FRP)), and coated or uncoated metallic foils.
The gate electrode can be any useful conductive material. For example, the gate electrode can comprise doped silicon, or a metal, such as aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, and titanium. Conductive polymers also can be used, for example polyaniline or poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS). In addition, alloys, combinations, and multilayers of these materials can be useful. In some OTFTs, the same material can provide the gate electrode function and also provide the support function of the substrate. For example, doped silicon can function as the gate electrode and support the OTFT.
The gate dielectric is generally provided on the gate electrode. This gate dielectric electrically insulates the gate electrode from the balance of the OTFT device. Useful materials for the gate dielectric can comprise, for example, an inorganic electrically insulating material or a polymeric dielectric layer.
Specific examples of materials useful for the gate dielectric include strontiates, tantalates, titanates, zirconates, aluminum oxides, silicon oxides, tantalum oxides, titanium oxides, silicon nitrides, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, and zinc sulfide. In addition, alloys, combinations, and multilayers of these materials can be used for the gate dielectric.
Alternatively, the gate dielectric may comprise an organic polymeric dielectric layer. A number of organic polymers have been considered as dielectric materials. These include polyimides, parylene C, crosslinked benzocyclobutene, and cyanoethylpullulan. See, for example, C. D. Sheraw et al., ōSpin-on polymer gate dielectric for high performance organic thin film transistorsö, Materials Research Society Symposium Proceedings v 558, Materials Research Society, Warrendale, Pa., USA, pages 403-408 (2000); U.S. Pat. No. 6,265,243 (Katz); and U.S. Pat. No. 5,347,144 (Garnier).
A preferred group of organic polymeric dielectrics comprise polymers having a cyano-functional portion and a portion that provides a relatively high dielectric constant to the overall polymer, which portions may be the same or different. The polymers can be homopolymers or copolymers. Copolymers are those polymers prepared from two or more different monomers and include terpolymers, tetrapolymers, and the like. The monomers can join to form random, block, segmented copolymers, as well as any of a variety of other structural arrangements.
Such polymeric dielectric may a substantially nonfluorinated organic polymer having repeat units of the formulas:
The source electrode and drain electrode are separated from the gate electrode by the gate dielectric, while the organic semiconductor layer can be over or under the source electrode and drain electrode. The source and drain electrodes can be any useful conductive material. Useful materials include most of those materials described above for the gate electrode, for example, aluminum, barium, calcium, chromium, gold, silver, nickel, palladium, platinum, titanium, polyaniline, PEDOT:PSS, other conducting polymers, alloys thereof, combinations thereof, and multilayers thereof. Some of these materials are appropriate for use with n-type semiconductor materials and others are appropriate for use with p-type semiconductor materials, as is known in the art.
The thin film electrodes (that is, the gate electrode, the source electrode, and the drain electrode) can be provided by any useful means such as physical vapor deposition (for example, thermal evaporation or sputtering) or ink jet printing. The patterning of these electrodes can be accomplished by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, and pattern coating.
One particularly useful method of preparing thin film transistors or integrated circuits is by means of a flexible, repositionable polymeric aperture masks to create integrated circuits or integrated circuit elements. The techniques involve sequentially depositing material through a number of polymeric aperture masks formed with patterns that define layers, or portions of layers, of the circuit. In some embodiments, circuits can be created solely using aperture mask deposition techniques, without requiring any of the etching or photolithography steps typically used to form integrated circuit patterns. The techniques can be particularly useful in creating circuit elements for electronic displays such as liquid crystal displays and low-cost integrated circuits such as radio frequency identification (RFID) circuits. In addition, the techniques can be advantageous in the fabrication of integrated circuits incorporating organic semiconductors, which typically are not compatible with photolithography or other wet processes.
In various embodiments, different repositionable aperture masks such as flexible aperture masks, free-standing aperture masks and polymeric aperture masks formed with patterns may be used to define a layer or a portion of a layer of an integrated circuit. Repositionable polymeric aperture masks may have a thickness of approximately between 5 and 50 microns or approximately between 15 and 35 microns. The various deposition apertures in the aperture masks may have widths less than approximately 1000 microns, less than approximately 50 microns, less than approximately 20 microns, less than approximately 10 microns, or even less than approximately 5 microns. Apertures of these sizes are particularly useful in creating small circuit elements for integrated circuits. Moreover, one or more gaps between deposition apertures may be less than approximately 1000 microns, less than approximately 50 microns, less than approximately 20 microns or less than approximately 10 microns, which is also useful in creating small circuit elements. Also, aperture masks that include a pattern having a width greater than approximately 1 centimeter, 25 centimeters, 100 centimeters, or even 500 centimeters are also described. Patterns having these widths can be useful in creating various circuits over a larger surface area as described in greater detail below. In some embodiments, layer may be deposited on a substrate through repositionable polymeric aperture masks.
Various laser ablation techniques may be used to facilitate the creation of polymeric aperture masks having patterns of deposition apertures. In addition, stretching techniques and other techniques may be used to facilitate alignment of flexible polymeric aperture masks. Furthermore, methods of controlling sag in aperture masks may be used which can be particularly useful in using masks that include a pattern that extends over a large width.
The aperture masks can provide a number of advantages. For example, the aperture masks can facilitate the creation of relatively small circuit elements using deposition processes. The aperture masks can facilitate circuit elements having widths less than approximately 1000 microns, less than approximately 50 microns, less than approximately 20 microns, less than approximately 10 microns, or even less than approximately 5 microns. Also, the aperture masks can facilitate the creation of relatively large circuit patterns, in some cases having circuit elements of the relatively small widths mentioned above that cover large areas (such as 10 square centimeters, 50 square centimeters, 1 square meter, or even larger areas). In addition, the aperture masks can reduce costs associated with circuit fabrication, and in the case of organic semiconductors, can even improve device performance. Polymeric aperture masks can be created using a laser ablation process that may be faster and less expensive than other techniques. Also, inexpensive polymeric materials can allow the polymeric masks to be disposable, although reusable embodiments are also described.
In addition, polymeric material may be well suited to be impregnated with magnetic material. In that case, the magnetic material may be used to reduce sag in the mask as described below. Furthermore, polymeric material is often stretchable, which allows the mask to be stretched to either reduce sag or to align the mask.
Further details may be made with reference to Applicant's copending U.S. Ser. No. 10/196,997, published as 03-0094959-A1, incorporated herein by reference.
The present invention further provides a thin film transistor comprising a surface treatment layer disposed between the described organic semiconductor and the gate dielectric. The surface treatment layer may be selected from a nonfluorinated polymeric layer, a self-assembled monolayer or a siloxane polymeric layer. The surface treatment layer provides organic thin film transistors with one or more improvements over known devices, including improvements in properties such as threshold voltage, subthreshold slope, on/off ratio, and charge-carrier mobility. In addition, large improvements in at least one property, such as charge-carrier mobility, can be achieved with the surface treatment layer, while maintaining other OTFT properties within desirable ranges. The improvements in device performance provided by the present invention enable the production by simpler processing conditions of complex circuits having higher operating speeds than an OTFT made without the surface treatment layer. This surface treatment layer also enables the production of larger circuit elements having comparable performance to devices with very small features. Devices with larger feature sizes can be less expensive as they do not require expensive precision patterning methods.
Any known thin film transistor configuration may be used with the surface treatment layer. For example, the source and drain electrodes may be adjacent to the gate dielectric with the organic semiconductor layer over the source and drain electrodes, or the organic semiconductor layer may be interposed between the source and drain electrodes and the gate dielectric. In each embodiment, the thin film transistor may include a surface treatment layer between the organic semiconductor layer and the gate dielectric.
In one embodiment, the present invention provides an organic thin film transistor (OTFT) comprising a substantially nonfluorinated polymeric layer interposed between a gate dielectric and the organic semiconductor layer of the invention, the substantially nonfluorinated polymeric layer having a thickness less than about 400 Å.
In one embodiment, the present invention provides a method of making an OTFT comprising providing a substrate, forming a gate electrode on the substrate, forming a gate dielectric on the gate electrode, applying a substantially nonfluorinated polymeric layer (having a thickness less than about 400 Å) interposed between the gate dielectric and an organic semiconductor layer, depositing an organic semiconductor layer adjacent to the polymeric layer, and depositing a source electrode and a drain electrode contiguous to the organic semiconductor layer. An integrated circuit comprising a plurality of OTFTs is also provided.
The polymeric surface treatment layer has a maximum thickness less than about 400 Angstroms (Å), more preferably less than about 200 Å, and most preferably less than about 100 Å. The polymeric surface treatment layer generally has a thickness of at least about 5 Å, more preferably at least about 10 Å. The thickness can be determined through known methods, e.g., ellipsometry.
The polymeric surface treatment layer is selected from many options. For example, a substantially nonfluorinated polymeric layer having a thickness within the range set forth above may be used. In this document, ōsubstantially nonfluorinatedö means that less than about 5% (more preferably less than about 1% and even more preferably 0%) of the carbons in the polymeric layer have fluorine substituents.
As used herein, ōsubstitutedö means substituted by substituents that do not interfere with the desired performance of the OTFT. Examples of suitable substituents include halogen (e.g., Cl, Br, I), cyano, C1-C20 aliphatic, aryl, and arylalkyl groups, and the like. As used in this document, ōheteroatomö means a non-carbon atom such as O, P, S, N and Si.
The polymeric layer may comprise a polymer having interpolymerized units according to the formula:
In these formulas, each R1 and R2 comprises, independently, a group selected from hydrogen; C1-C20 aliphatic; chloro; bromo; carboxy; acyloxy; nitrile; amido; alkoxy; carboalkoxy; aryloxy; chlorinated aliphatic; brominated aliphatic; C6-C20 aryl; C7-C20 arylalkyl; hydroxy when R1 and X are different; and combinations thereof which may contain one or more heteroatom(s) and/or one or more functional group(s). Each X, independently, comprises a functional group capable of bonding to the gate dielectric. In addition, any combination of at least two R1, R2, and/or X groups may together form a cyclic or polycyclic, aliphatic or aromatic group.
Particular selections for R1 and/or R2 include groups selected from hydrogen, C1-C20 aliphatics, which may be linear or branched, saturated or unsaturated; C6-C20 aryl; and C7-C20 arylalkyl which also may contain linear or branched, and saturated or unsaturated segments. Specific polymers may be derived from precursor monomers such as methyl (meth)acrylate, straight-chain or branched C2-C18 aliphatic or arylalkyl (meth)acrylates, (meth)acrylic acid, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, vinyl chloride, vinyl acetate, ethylene, straight-chain or branched C3-C18 α-olefins, isoprene, chloroprene, 1,3-butadiene, diethyl fumarate, allyl acetate, methyl vinyl ketone, and styrene.
The functional group capable of bonding to the gate dielectric includes groups known to form chemical bonds to the selected gate dielectric. Particular selections for X groups include ŚPO3R2 or ŚOPO3R2 wherein each R is, independently, hydrogen or a C1-C12 aliphatic group or a C6-C18 aryl or arylalkyl group; ŚSO3H; alkoxysilyl; chlorosilyl; acetoxysilyl; benzotriazolyl (ŚC6H4N3); ŚCONHOH; ŚCOOH; ŚOH; ŚSH; ŚCOSH; ŚCOSeH; ŚC5H4N; ŚSeH; ŚNC; amino; and phosphinyl. Benzotriazolyls include, for example, benzotriazolylcarbonyloxy (ŚOC(═O)C6H4N3), benzotriazolyloxy (ŚOŚC6H4N3), and benzotriazolylamino (ŚNHŚC6H4N3) groups. Specific preferred groups include ŚPO3H2, ŚOPO3H2, and trimethoxysilyl.
Combinations of at least two R1, R2, and/or X groups may together form a cyclic or polycyclic group that can be aliphatic or aromatic. Specific examples are copolymers incorporating comonomers such as norbornene and substituted norbornenes, maleic anhydride, acenaphthylene, and itaconic anhydride. Also useful are polymers and copolymers which can form crosslinked networks by vinyl-type polymerizations, including those derived from divinylbenzenes, and (meth)acrylate-derived cinnamates.
Thus, the polymeric layer having interpolymerized units of Formula I and, optionally, Formula II, includes a broad array of materials. Specific examples include homopolymers such as polystyrene, poly(1-hexene), poly(methyl methacrylate), poly(acenaphthylene), poly(vinylnaphthalene), poly(butadiene), poly(vinyl acetate), and those derived from α-methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. In such homopolymer examples, the polymeric layer comprises 0% of said interpolymerized units according to Formula II.
A preferred polymeric layer is comprised of a polymer having styrenic interpolymerized units. Styrenic interpolymerized units include those derived from styrene and substituted styrenes, such as α-methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-(phosphonomethyl)styrene, and divinyl benzene.
Copolymers, such as block, random, and alternating, are also useful in the polymeric layer described in this invention. Useful copolymers comprise interpolymerized units of Formula I and optionally Formula II. Preferred examples include copolymers of at least two different monomers selected from styrene, α-methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. Other preferred examples include those materials having units of Formula II. Specific examples of monomers useful to form Formula II units include vinylphosphonic acid and other phosphonic acid-containing comonomers such as 4-(phosphonomethyl)styrene, and trialkoxysilane-containing comonomers such as 3-(trimethoxysilyl)propyl methacrylate. Preferred examples include a variety of copolymers of styrene and vinylphosphonic acid, copolymers of styrene and other phosphonic acid-containing comonomers, copolymers of styrene and phosphonate-containing comonomers, copolymers of styrene and phosphate-containing comonomers, a copolymer of styrene and 4-(phosphonomethyl)styrene, a copolymer of styrene and trimethoxysilylpropyl methacrylate, and copolymers of styrene and silyl-containing comonomers.
A class of polymers useful in the present invention includes hydrocarbon olefin homo- and co-polymers of ethylene, propylene, and higher α-olefins. These olefins can be represented by the general structure ŚCH2CHRŚ, wherein R is hydrogen or a C1-C10 (preferably C1-C6) aliphatic radical. Copolymers may comprise one or more ethylenically-unsaturated comonomers which are copolymerizable with such olefins. These include vinyl esters, such as vinyl acetate; acrylic and α-alkyl acrylic acids and their alkyl esters, amides, and nitriles, such as methyl methacrylate and acrylonitrile; vinyl aromatics, such as styrene and vinylnaphthalene; anhydrides and alkyl esters of maleic and fumaric acids; vinyl alkyl ethers; vinylpyridine; N-vinylcarbazole; and dienes, such as 1,3-butadiene.
Polymers useful for this invention may also be prepared by the introduction of functional groups. These can be provided through the use of a variety of materials, typically referred to as functional initiators, functional chain transfer agents, or functional chain terminators. Examples of these materials include phosphorus oxychloride, mercaptopropyltrialkoxysilanes, chlorotrialkoxysilanes, and tetrachlorosilane. The introduction of these species typically introduces a functional group at the end or midpoint of a polymer chain. Examples of useful polymeric species prepared using these reactants include α-(triethoxysilyl)propylthio polystyrene, and ω-(phosphonic acid) polystyrene.
The polymer surface treatment layer may be derived from a ring-opening polymerization. A wide variety of monomers may be used in this embodiment. Examples of suitable monomers include cyclic ethers, cyclic amides, cyclic amines, cyclic sulphides, and inorganic ring compounds such as phosphonitrilic chlorides. The repeat units of the polymer in these materials are joined by links similar to those found in the monomer, but rearranged to provide a linear rather than cyclic chain. These polymerizations may proceed by a variety of mechanisms. One specific type of ring-opening polymerization is a ring-opening metathesis polymerization, or ROMP. Suitable monomers that can be polymerized in this fashion include norbornenes, C4-C10 cyclic alkenes, and C4-C10 cyclic non-conjugated dienes. These ROMP monomers may be substituted with one or more C1-C20 straight-chain or branched aliphatic groups, aromatic groups, or arylalkyl groups, any of which may include one or more heteroatoms. As is known, aliphatic groups may be saturated or may contain one or more carbon-carbon multiple bonds, while arylalkyl groups contain both aliphatic and aromatic structures. Specific materials useful in this aspect of the invention include straight-chain or branched C1-C18 alkyl-substituted norbornenes, trialkoxysilyl-substituted norbornenes, esters of 5-norbornene-2-carboxylic acid, esters of 2-phosphono-5-norbornene, 1,4-cyclooctadiene, and dicyclopentadiene.
The polymeric surface treatment layer may be derived from monomeric precursors, monomers, and oligomers comprising an aromatic-functional segment. Such polymeric materials are found in the class of aromatic thermosets. A preferred class of aromatic thermosets is the polyarylenes, for example, polyphenylene and polynaphthalene. Such polyarylenes include polymers containing heteroatoms, for example, polyarylene ethers. Polyarylenes can be prepared in a variety of ways. One useful means of preparing polyarylene compositions is by applying suitable monomeric or oligomeric precursors to the dielectric layer and subsequently polymerizing these materials through exposure to an energy source, such as by heating or irradiation. A preferred class of oligomer is a low molecular weight aromatic thermosetting composition comprised of cyclopentadienone and acetylene-substituted materials. The molecular weight is sufficiently low to permit spin coating of these oligomers. Such materials are commercially available as SiLKÖ resin from Dow Chemical Co. Midland, Mich. The SiLKÖ resin is more fully described in ōDevelopment of a Low-Dielectric-Constant Polymer for the Fabrication of Integrated Circuit Interconnectö, Martin J. P. et al., Adv. Mater. 2000, 12(23), 1769-1778 and references therein, and U.S. Pat. Nos. 5,956,679 and 6,288,188, which are all herein incorporated by reference. The SiLKÖ resin can be spin-coated onto surfaces and then subsequently cured by heating to form an insoluble polyarylene film.
Other useful oligomeric compositions are polyfunctional o-phenylethynyl-substituted aromatic monomers which crosslink upon exposure to an energy source, especially thermal radiation, to form polynaphthalenes. Other examples of classes of monomeric precursors that form aromatic thermoset polymers include: cinnamates, divinylbenzenes, diacetylenes, benzocyclobutenes, and substituted derivatives thereof.
Other preferred classes of polyarylenes are the parylenes (i.e., poly(p-xylylene) polymers) and the polyfluorenes. The parylenes are semicrystalline polymers prepared by simultaneous adsorption and polymerization of reactive p-xylylene monomers from their vapor onto a surface. The vapor deposition of the monomer and its polymerization results in the formation of a thin film of uniform thickness conformal to the substrate surface that is effectively free of pinholes. Useful parylenes include parylene N, parylene C, and parylene D.
In another aspect, useful polymers and copolymers of the surface treatment layer are substantially non-polar, glassy solids at room temperature. Preferably, the polymer comprises 80 mole % or more of alkyl, aryl, or arylalkyl monomer units, wherein said monomer units are substantially free of heteroatoms. The polymer has fewer than about 20 mole % of monomer units containing heteroatoms (more preferably, fewer than about 10 mole %). Furthermore, said polymer preferably has a glass transition temperature (Tg) measured in the bulk of at least about 25░ C., more preferably of at least about 50░ C., and most preferably at least about 100░ C. Examples of these types of polymers include many of those described above, including linear and thermoset materials. Specific examples include polystyrene, polyfluorene, polynorbornene, poly(acenapthylene), and alkyl-substituted derivatives thereof, and functionalized copolymers. In addition, blends of two or more polymeric or copolymeric materials may be used.
In another aspect, the OTFT of the invention has a substantially nonfluorinated polymeric layer having a thickness less than about 400 Å and the OTFT has a charge carrier mobility at least 50% greater than the charge carrier mobility of a similar OTFT lacking the polymeric layer. In another aspect of the invention, the OTFT has a charge carrier mobility at least 0.02 cm2/Vs, preferably at least 0.10 cm2/Vs, more preferably at least 1.0 cm2/Vs, greater than the charge carrier mobility of a similar OTFT lacking the polymeric layer. In this document, all charge carrier mobility values are room temperature values.
The polymers and copolymers useful in the surface treatment layer can be prepared by any known means, for example, by free-radical, ring-opening, anionic, cationic, or coordination polymerization of monomers such as those described above. The polymer may also be modified by subsequent reactions to introduce functional groups.
The polymeric surface treatment layer is provided on the gate dielectric by any known method. For example, the polymeric surface treatment layer can be provided through a coating process such as spray, spin, dip, knife, gravure, microcontact printing, ink jet printing, stamping, transfer printing, and vapor deposition. The polymeric surface treatment layer can be provided on the gate dielectric via a solvent-based or solventless method. Presently preferred routes to the polymeric layer include solvent-based methods. When a solution of a polymeric surface treatment layer precursor is provided on the gate dielectric layer, the solvent is removed by a method compatible with the materials involved, for example by heating.
In one embodiment, the source and drain electrodes are deposited adjacent to the gate dielectric before providing the polymeric layer. Then, the polymeric surface treatment layer is applied. After the layer comprising a polymer is complete, the organic semiconductor layer is deposited over the source and drain electrodes and over the polymeric layer adjacent to the gate dielectric. Before deposition of the semiconductor, the material deposited on the gate dielectric to provide the polymeric layer may be rinsed so the source and drain electrodes are essentially free of the polymeric layer. That is, less than about 5 Å of polymeric layer, more preferably less than 1 Å and most preferably no polymeric layer, is present on the source and drain electrodes.
Further details regarding the polymeric layer may be had with reference to Applicant's copending application U.S. Ser. No. 10/012654, filed Nov. 5, 2001, and incorporated herein by reference.
The surface treatment layer may also comprise a substantially siloxane polymeric layer having a thickness less than about 400 Å interposed between a gate dielectric and an organic semiconductor layer in an OTFT. The polymeric surface treatment layer comprises a substantially nonfluorinated polymer having interpolymerized units according to the formula:
wherein each R comprises, independently, a group selected from hydrogen, C1-C20 aliphatic, C4-C20 alicyclic, arylalkyl, or aryl, and a combination thereof which may contain one or more heteroatom(s) and/or one or more functional group(s). As used in this document, ōheteroatomö means a non-carbon atom such as O, P, S, N and Si. In this document, ōsubstantially nonfluorinatedö means that less than about 5% (more preferably less than about 1% and even more preferably 0%) of the carbons in the polymeric layer have fluorine substituents.
The polymeric surface treatment layer of the invention has a maximum thickness less than about 400 Angstroms (Å), more preferably less than about 200 Å, most preferably less than about 100 Å. The polymeric layer of the invention generally has a thickness of at least about 5 Å, more preferably at least about 10 Å. The thickness can be determined through known methods, e.g., ellipsometry.
Particular selections for R groups include, for example, methyl, phenyl, 2-phenylethyl, C2-C18 aliphatic groups, and functional group-containing moieties including, but not limited to, hydroxyl, vinyl, 5-hexenyl, hydrogen, chloro, 3-(meth)acryloxypropyl, 3-mercaptopropyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-aminopropyl, 3-acetoxypropyl, 3-chloropropyl, 3-carboxypropyl, 3-cyanopropyl, chlorophenyl, C1-C6 2-(dialkylphosphono)ethyl.
Examples of useful polymeric materials include poly(dimethylsiloxane), poly(dimethylsiloxane-co-diphenylsiloxane), poly(methylphenylsiloxane-co-diphenylsiloxane), and poly(dimethylsiloxane-co-methylphenylsiloxane).
Siloxane polymers useful in the practice of this invention may be prepared by any of a number of methods familiar to those skilled in the art, including, for example, anionic, condensation, or ring-opening polymerization. Siloxane polymers useful for this invention may also be prepared with the introduction of functional end-groups or functional pendant groups. This may be accomplished through the use of functional monomers, functional initiators, or functional chain terminators, for example, the termination of an anionically polymerized polydiorganosiloxane with a chlorotrialkoxysilane. They may also be prepared by modification of existing siloxane polymers, for example, the reaction of an olefinically functional polydiorganosiloxane with a silicon hydride, e.g., trichlorosilane.
While this invention emphasizes the use of linear polydiorganosiloxanes in which each unit in the siloxane polymer is derived from a difunctional precursor, it is considered within the scope of this invention to employ polyorganosiloxanes that incorporate small amounts of siloxane units derived from trifunctional or tetrafunctional precursors. The number of trifunctionally- and tetraftunctionally-derived siloxane units should not exceed about 10 percent, preferably about 5 percent or less, of the total average number of siloxane units in the polymer.
Useful polymeric materials may additionally include block copolymers comprising blocks of Formula (I) connected with blocks of interpolymerized units derived from an ethylenically unsaturated monomer such as styrene, butadiene, or isoprene. In addition, blends of two or more polymeric or copolymeric materials may be used.
In another aspect, the present invention provides a method of making an OTFT comprising providing a substrate, forming a gate electrode on the substrate, forming a gate dielectric on the gate electrode, applying a substantially nonfluorinated polymeric layer having a thickness less than about 400 Å interposed between the gate dielectric and an organic semiconductor layer, depositing the instant organic semiconductor layer adjacent to the polymeric surface treatment layer, and depositing a source electrode and a drain electrode contiguous to the organic semiconductor layer. An integrated circuit comprising OTFTs is also provided.
The surface treatment layer may also comprise a self-assembled monolayer interposed between a gate dielectric and an organic semiconductor layer, the monolayer being a product of a reaction between the gate dielectric and a precursor to the self-assembled monolayer, the precursor comprising a composition having the formula:
wherein X is H or CH3;
Y is a linear or branched C5-C50 aliphatic or cyclic aliphatic connecting group, or a linear or branched C8-C50 group comprising an aromatic group and a C3-C44 aliphatic or cyclic aliphatic connecting group;
Z is selected from ŚPO3H2, ŚOPO3H2, benzotriazolyl (ŚC6H4N3), carbonyloxybenzotriazole (ŚOC(═O)C6H4N3), oxybenzotriazole (ŚOŚC6H4N3), aminobenzotriazole (ŚNHŚC6H4N3), ŚCONHOH, ŚCOOH, ŚOH, ŚSH, ŚCOSH, ŚCOSeH, ŚC5H4N, ŚSeH, ŚSO3H, ŚNC, ŚSiCl(CH3)2, ŚSiCl2CH3, amino, and phosphinyl;
In another aspect, the present invention provides a method of making a thin film transistor comprising the steps of providing a substrate, providing a gate electrode material on the substrate, providing a gate dielectric on the gate electrode material, providing a self-assembled monolayer (SAM) adjacent to the gate dielectric, the monolayer being a product of a reaction between the gate dielectric and a precursor to the self-assembled monolayer, providing the instant organic semiconductor layer adjacent to the monolayer, and providing a source electrode and a drain electrode contiguous to the organic semiconductor layer. The precursor is as described above with the organic thin film transistor article. An integrated circuit comprising organic thin film transistor articles is also provided.
Self-assembled monolayer precursors provide molecules that form self-assembled films, typically, monolayer films on the target surface. Self-assembled thin films are often prepared by coating a substrate of interest in a dilute solution of the self-assembling precursor or by exposure to a vapor phase containing the precursor, and allowing film formation to proceed. The precursor molecules form a generally organized molecular film on the substrate. Once formed, the film does not redissolve in the solvent from which it was deposited.
Generally, materials that form crosslinks independently of monolayer formation, which may be in competition with the adsorption or bonding reaction to the gate dielectric, such as trifunctional silanes, are not desired for the monolayer precursor of the present invention. However, materials that have functional groups effective to bond to the gate dielectric and have other groups that may form crosslinks after formation of the SAM can be used.
Herein, the reaction between any gate dielectric and a functional group within the self-assembled monolayer precursor is preferably a bonding interaction (e.g. covalent or ionic). Herein, a self-assembled monolayer refers to a mono-molecular layer on the order of about 5 Angstroms to about 30 Angstroms thick.
In preferred embodiments, Y can be a saturated aliphatic group, an unsaturated aliphatic group, a saturated cyclic aliphatic group, and an unsaturated cyclic aliphatic group, or a combination thereof, each of which may be linear or branched. The monolayer precursor may comprise a composition of the formula: CH3(CH2)PO3H2 wherein m is an integer from 4 to 21.
Particular examples for the monolayer precursor include 1-phosphonooctane, 1-phosphonohexane, 1-phosphonohexadecane, and 1-phosphono-3,7,11,15-tetramethylhexadecane.
One member of a class of branched hydrocarbon monolayer precursors useful in the practice of the present invention is 1-phosphono-3,7,11,15-tetramethylhexadecane. Other members of this class include 1-phosphono-2-ethylhexane, 1-phosphono-2,4,4-trimethylpentane, and 1-phosphono-3,5,5-trimethylhexane. The 1-phosphono-3,7,11,15-tetramethylhexadecane can be prepared from a commercially available allylic alcohol precursor by reduction of the alkene double bond, conversion of the alcohol to the corresponding bromide, and then conversion of the bromide to the corresponding phosphonic acid. More specifically, 1-phosphono-3,7,11,15-tetramethylhexadecane can be obtained by reducing 3,7,11,15-tetramethyl-2-hexadecen-1-ol to 3,7,11,15-tetramethyl-1-hexadecanol, converting the 3,7,11,15-tetramethyl-1-hexadecanol to 1-bromo-3,7,11,15-tetramethylhexadecane, and then converting the 1-bromo-3,7,11,15-tetramethylhexadecane to 1-phosphono-3,7,11,15-tetramethylhexadecane. These synthetic transformations are accomplished using materials and methods familiar to those skilled in the art. Starting materials other than 3,7,11,15-tetramethyl-2-hexadecen-1-ol and individual reaction sequences other than that described above may also be used to synthesize 1-phosphono-3,7,11,15-tetramethylhexadecane, as well as other members of this class of branched hydrocarbon monolayer precursors, and the specifically exemplified monolayer precursor and method of preparation should not be construed as unduly limiting.
The compounds of the invention can be used alone or in combination as the organic semiconductor layer of the OTFT (or other semiconductor device). The layer can be provided by any useful means, such as, for example, vapor deposition and printing techniques.
The compounds of the invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles. Such articles include, for example, radio-frequency identification (RFID) tags, backplanes for flexible displays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, and the like.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
Starting materials were prepared using published procedures as follows:
5-tri-n-butylstannyl-2,2′-bithiophene: Zhu, S. S.; Swager, T. M. J. Am. Chem. Soc. 1997, 119, 12568-12577.
5,5′-bis(tri-n-butylstannyl)-2,2′-bithiophene: Wei, Y.; Yang, Y.; Yeh, J.-M. Chem. Mater. 1996, 8, 2659-2666.
5-tri-n-butylstannyl-5′-hexyl-2,2′-bithiophene: Sotgiu, G.; Zambianchi, M.; Barbarella, G.; Botta, C. Tetrahedron 2002, 58, 2245-2251.
3,4′-dihexyl-2,2′-bithiophene: Kirschbaum, T.; Briehn, C. A.; Bõuerle, P. J. Chem. Soc., Perkin Trans. 1 2000, 1211-1216.
2,6-dibromoanthracene: This material was prepared by a Meerwein-Pondorf reduction of 2,6-dibromoanthraquinone (48%), which in turn was prepared from commercially available 2,6-diaminoanthraquinone by a Sandmeyer reaction (Ito, K.; Suzuki, T.; Sakamoto, Y.; Kubota, D.; Inoue, Y.; Sato, F.; Tokito, S. Angew. Chem. Int. Ed. 2003, 42, 1159-1162). Prior to coupling reactions, the 2,6-dibromoanthracene was purified by gradient sublimation.
A 1-L, 3-necked flask was fitted with a distillation head and purged with N2. The system was charged with 2-bromoanthraquinone (29.0 g, 101 mmol), cyclohexanol (350 mL), and aluminum tri-sec-butoxide (140 mL, 550 mmol). The mixture was heated and became deep amber as distillate was collected until the pot temperature was 162░ C. The reaction was heated at 160░ C. for 16 h and then cooled to room temperature. The mixture was mixed with tetrahydrofuran (100 mL) and poured onto a 2 L filter frit to isolate the black solid. The solid was stirred on the frit with 6 M HCl (100mL) and then further washed with water (500 mL). The gray crude product was air-dried overnight. The solid was purified further by gradient sublimation at a source temperature of 120░ C. to afford 12.6 g (48%) of off-white product. DSC data: peak temp 220░ C. (ΔH=126 Jg−1. IR (KBr, strong abs only): 892, 741, 474 cm−1. 1H NMR (500 MHz, d6-Me2SO, internal TMS). δ 7.56 (m, 6 lines, 6-H, 8-H), 7.60 (dd, J=2.0, 9.0 Hz, 7-H), 8.09 (m, 1-H, 3-H, 4-H), 8.39 (ædÆ, J=1 Hz, 9-H), 8.57 (s, 5-H), 8.63 (s, 10-H).
Synthesis of 2-chlorotetracene
A 2-necked, 500 mL round-bottomed flask was fitted with a distillation head and receiver, and charged with 2-chloro-5,12-tetracenequinone (11.5 g, 39.4 mmol), cyclohexanol (100 mL), and Al(O-sec-Bu)3 (50 mL) under nitrogen. The mixture was heated until distillate began collecting in the receiver at a pot temperature of ca. 115░ C. The distillation was continued until the temperature of the dark orange mixture reached 162░ C., and the solution was then heated at 159░ C. for 36 h. The mixture was cooled to 50░ C., an equal volume of dry THF was added, and then it was heated up to 80░ C. and stirred. The hot mixture was poured onto a 10-20 μm frit to isolate a bright orange solid that was washed with water (150 mL), 5% HCl (150 mL), and additional water (150 mL). The filtrate was mixed with some additional water and conc. HCL, stirred, and allowed to sit overnight. The solid was air-dried for a couple of hours to afford 5.04 g of material. Purification by gradient sublimation at 130-150░ C. afforded 4.0 g of fluorescent orange product. An additional crop of crude material was isolated from the filtrate above and afforded another 1.37 g after sublimation. Net yield 52%. DSC (20░ C./min): 361░ C. (ΔH=96 Jg−1, decomp). EIMS: 262 ([M]+, 100%), 226 ([M-HCl]+, 23%). Anal. Calcd. for C18H11Cl: C, 82.3; H, 4.22. Found: C, 82.5; H, 4.27.
Synthesis of 5,5′-bis(tri-n-butylstannyl)-3,4′-dihexyl-2,2′-bithiophene. (Bu3SnŚT2hŚSnBu3)
A cold (−70░ C.) THF (60 mL) solution of 3,4′-dihexyl-2,2′-bithiophene (3.12 g, 9.33 mmol) was treated dropwise with BuLi (2.5 M in hexane, 7.5 mL, 19 mmol). The mixture became faintly yellow and was allowed to warm to ambient temperature overnight. The solution was cooled (−70░ C.) and Bu3SnCl (5.1 mL, 19 mmol) was added. The mixture was warmed to room temperature with the cold bath in place, and after several hours, water (50 mL) was added. The mixture was thoroughly mixed and the aq phase separated. The organic was washed with 3 portions of brine, dried with MgSO4, filtered, and the volatile materials removed under reduced pressure. The crude oil was mixed with a few mL of hexanes and chromatographed on a column of grade II neutral alumina eluting with neat hexanes to afford 5.1 g (60%) of yellow oil. 1H NMR (400 MHz, d6-Me2CO): δ 7.17 (s, JHsn=7 Hz, 1 H), 7.06 (s, JHSn=23 Hz, 1 H), 2.82 (t, J=8 Hz, 2 H), 2.63 (t, J=8 Hz, 2 H), 1.7-1.1 (m, methylene H, 16 H), 0.91 (m, methyl H, 6 H).
Synthesis of 5,5′-bis(2-anthracenyl)-2,2′-bithiophene (An-T2-An)
A 100 mL Schlenk flask was loaded with 5,5′-bis(tri-n-butylstannyl)-2,2′-bithiophene (3.16 g, 4.25 mmol), DMF (40 mL), 2-bromoanthracene (2.19 g, 8.50 mmol), and Pd(PPh3)4 (114 mg, 98.7 mmol, 2.3 mmol %). The suspension was bubbled through with N2 for 20 min, and then warmed with a hot oil bath. At 80░ C., all solids dissolved and the mixture became homogenous; at 105░ C., a bright, fine orange ppt formed. The reaction was stirred at 110░ C. for 14 h and then cooled to room temperature. The mixture was poured on to a glass filter frit (10-20 μm pores) and successively washed with water, 1N HCl, acetone, and then air dried to yield 2.012 g of orange product. The material was purified by gradient sublimation at a source temperature of 320░ C. to afford 1.60 g (73%) of product. DSC data: peak temp 420░ C. (reversible mp, ΔH=246 Jg−1). LDMS. m/z 518.1276 (M+), no other ions were detected in the sample. Fluorescence spectrum (saturated toluene, right angle geometry, excitation at 400 nm): λmax=476 nm. Excitation spectrum (saturated toluene, monitoring fluorescence at 476 nm, λmax (relative spectral response)): 359 (1.0), 416 (0.78). Elemental analysis consistent with desired structure.
Synthesis of 5,5′-bis(2-tetracenyl)-2,2′-bithiophene (Tet-T2-Tet)
A vessel was successively charged with Pd2(dba)3 (103 mg, 0.112 mmol, 1.5%), CsF (2.54 g, 16.7 mmol, 2.2 eq), dioxane (120 mL), 2-chlorotetracene (2.00 g, 7.61 mmol), 5,5′-tri-n-butylstannyl-2,2′-bithiophene (2.83 g, 3.81 mmol), P(t-Bu)3 (1.3 mL, 0.45 mmol, 5.9%), and heated at 100░ C. for 36 h. The mixture was cooled and poured onto a glass frit (20 μm pores) to isolate a red solid. The crude product was washed with water (100 mL), 5% HCl (aq) (100 mL), additional water, and then air-dried. Gradient sublimation at a source temperature of 400-500░ C. afforded 1.25 g (53%) of deep red product. From the coolest zone was isolated 0.33 g of 2-chlorotetracene starting material (17% on input). EIMS: 618 ([M]+, 100%), 309 ([M]2+, 52%). DSC (20░ C./min): 533░ C., (mp, ΔH=183 Jg−1). Anal. Calcd. for C44H26S2: C, 85.4; H, 4.23. Found: C, 84.6; H, 4.25. Fluorescence spectrum (saturated CHCl3, right angle geometry, excitation at 400 nm): λmax=476 nm. Excitation spectrum (saturated toluene, monitoring fluorescence at 430 nm, λmax/nm (relative spectral response)): 360 (1.0), 430 (0.80, sh).
Synthesis of 5-(2-tetracenyl)-2,2′-bithiophene (Tet-T2)
Pd2(dba)3 (21 mg, 0.023 mmol, 1.5%), CsF (511 mg, 3.37 mmol, 2.2 eq), dioxane (25 mL), 2-chlorotetracene (403 mg, 1.53 mmol), 5-tri-n-butylstannyl-2,2′-bithiophene (766 mg, 1.68 mmol), P(t-Bu)3 (0.26 mL, 0.090 mmol, 6%) were mixed, bubbled with N2 via cannula for 30 min, and then heated at 100░ C. for 16 h. An additional charge of 10 mg of Pd[P(t-Bu)3]2 and 140 mg 5-tri-n-butylstannyl-2,2′-bithiophene and heated at 100░ C. for another 24 h. Cooled the mixture and poured on a glass filter frit (10-15 μm pores) and washed the reddish crude with Et2O, water, and air-dried. Gradient sublimation at a source temperature of 250-270░ C. afforded 443 mg (74%, on 2-chlorotetracene) of bright orange-red product. DSC: 341░ C. (mp, ΔH=87 Jg−1). EIMS: 392 ([M]+, 100%), 196 ([M]2+, 20%). Anal. Calcd. for C26H16S2: C, 79.6; H, 4.1. Found: C, 80.0; H, 4.34.
Synthesis of 5,5′-bis(2-anthracenyl)-3,4′-dihexyl-2,2′-bithiophene (An-T2h-An)
A vessel was successively charged with Pd2(dba)3 (87 mg, 0.095 mmol, 2 mol %), CsF (1.1 g, 7.0 mmol), 2-bromoanthracene (821 mg, 3.19 mmol), dioxane (20 mL), 5,5′-bis(tri-n-butylstannyl)-3,4′-dihexyl-2,2′-bithiophene (1.46 g, 1.60 mmol), and P(t-Bu)3 (0.28 mL, 0.096 mmol, 10% wt in hexanes). The mixture was bubbled with N2 via cannula while stirring for 30 min, and then heated to 89░ C. overnight. The reaction mixture was stripped dry and the orange-brown solid was extracted with THF (200 mL). After filtering to remove gray ppt, the organic was washed with 3ū50 mL brine, dried with MgSO4, filtered, and stripped dry. The crude was recrystallized from CH2Cl2 (ca. 40 mL at −35░ C.) to afford 445 mg (40%). 1H NMR consistent with the desired structure. EIMS: 686 ([M]+, 100%), 343 ([M]2+, 35%). UV-vis (CHCl3), λmax/nm (ε): 259 (1.1ū105), 353 (4.3ū104), 410 (3.0ū104). Fluorescence (CHCl3), λmax: 490 nm. DSC: peak temp/░ C. (ΔH/Jg−1), 60 (10), 83 (−22), 138 (−8.2), 170 (26).
Synthesis of 2,6-bis(2,2′-bithien-5-yl)-anthracene (T2-An-T2)
A reaction vessel was charged with Pd(PPh3)4 (70 mg, 0.061 mmol, 1.3 mol %), 2,6-dibromoanthracene (800 mg, 2.38 mmol), DMF (20 mL), and 5-tri-n-butylstannyl-2,2′-bithiophene (2.17 g, 4.77 mmol). The mixture was bubbled through with N2 for 20 min and then stirred for 20 h at 90░ C. After cooling, the suspended solid was isolated on a glass filter frit (10-20 μm pores), washed with acetone (20 mL), water (50 mL), and air dried overnight. Gradient sublimation of the crude powder at a source temperature of 275-350░ C. afforded 550 mg (46%) of bright orange product. EIMS: 506 ([M]+, 100%), 253 ([M]2+, 30%). UV-vis (saturated CHCl3): λmax/nm (absorbance), 348 (0.12), 418 (0.06), 440 (0.06, sh), 519 (0.009). Fluorescence (CHCl3), λmaxnm (relative intensity: 469 (1.0), 495 (0.69 sh). DSC: peak temperature (ΔH), 360░ C. (131 J/g). Anal. Calcd. for C30H18S4: C, 71.1; H, 3.58; S, 25.3. Found: C, 70.5; H, 3.52; S, 25.2.
Synthesis of 5-(2-anthracenyl)-5′-hexyl-2,2′-bithiophene (An-T2-C6-H13)
A vessel was charged with Pd2(dba)3 (77 mg, 84 μmol, 2 mol %), CsF (1.41 g, 9.29 mmol), 2-bromoanthracene (1.09 g, 4.22 mmol), 1,4-dioxane (20 mL), 5-(tri-n-butylstannyl)-5′-hexyl-2,2′-bithiophene (2.28 g, 4.22 mmol), and P(t-Bu)3 (0.74 mL of a 10 wt % solution in hexanes, 0.25 mmol). The mixture was heated at 95░ C. for 36 h and then the volatile materials were removed under reduced pressure. The residue was extracted with 450 mL methylene chloride and the filtered extract was washed with 2ū150 mL of brine. After drying with MgSO4, the bright orange solution was filtered, concentrated, and then cooled overnight at −35░ C. Bright orange product (1.35 g, 75%) was isolated by filtration and dried under vacuum. The material may be purified further by gradient sublimation at a source temperature of 175-200░ C. 1H NMR was consistent with the desired structure. UV-vis spectrum in CHCl3, 17.3 μg/mL: λmax (ε), 246 (53,500), 259 (54,700), 342 (40,200), 356 (42,900), 397 (27,600). ΔEoptś2.8 eV. Fluorescence spectrum in CHCl3, excitation at 400 nm: λmax=464 (1.4ū106 CPS). DSC (20░ C./min): 204░ C., (mp, ΔH=36 Jg−1).
Synthesis of 2,6-bis(5′-hexyl-2,2′-bithien-5-yl)-anthracene (C6H13-T2-An-T2-C6H13)
A Stille coupling between 2 eq of 5-(tri-n-butylstannyl)-5′-hexyl-2,2′-bithiophene and 1 eq of 2,6-dibromoanthracene was done in an analogous manner as described in example 6. The crude product was purified to device grade by gradient sublimation at a source temperature of 250-260░ C. DSC (20░ C./min): 320░ C., (mp, ΔH=19 Jg−1).
The table below lists the melting points for some of the new materials reported here. Melting points (mp) are reported as the peak temperature of the melting endotherm in the differential scanning calorimetry (DSC) trace, and the decomposition points are recorded as the temperature in the TGA curve at which the weight loss exceeded 1%. In all cases except for Tet-T2-Tet, which decomposed as it melted, the compounds showed reversible melting behavior.
The addition of pendant alkyl groups, at the ends of the molecule (compounds from examples 6 and 7) or internally (compound from example 4), greatly lowers the mp of the material, while, in some cases, not greatly affecting its thermal stability. For example, adding hexyl groups to the 5′ positions of ihe outer thiophene rings of T2-An-T2 lowers the mp by 40░ C. (compounds from examples 7 and 5). The decomposition point is 405░ C. for both materials. This structure-property relationship is even more pronounced when alkyl groups are placed on internal thiopens. For example the mp of An-T2-An (compound from example 1, 419░ C.) is lowered by nearly 250░ C. by adding hexyl groups to the 3- and 4′ positions of the internal bithiophene. As a further illustration of typical thermal behavior for this class of materials.
All new materials were characterized by optical spectroscopy. In some cases, extremely low solubility prevented the collection of acceptable UV-vis absorption spectra, and in these cases qualitative excitation spectra were collected. An interesting comparison may be made between An-T2-An (Ex. 1) and An-T2h-An (Ex. 4). While the former material is virtually insoluble, the dihexyl material may be recrystallized from chlorinated solvents like methylene chloride or chloroform, and also purified by column chromatography. Optical spectra of An-T2-An are shown in
TFTs were characterized using an HP Semiconductor Parameter Analyzer by sweeping the gate voltage, Vg (+10 V to −40 V), and allowing the drain voltage, Vd, to remain constant at −40 V. A linear fit to the Id 1/2−Vg trace permits the extraction of saturation mobility and threshold voltage (Vt), and a linear fit to the Id−Vg trace allows the subthreshold slope (S) and the current on/off ratio to be calculated.
X-ray diffraction patterns (Cu Kα radiation) for thin films of An-T2-An and Tet-T2-Tet coated on SiO2 substrates are shown in
An atomic force microscopy image (AFM) of a thin film (ca. 300 Å) of Tet-T2 that was vacuum deposited at a rate of 0.5 Å/s on an Al2O3 substrate is shown in
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This article is part of the continuing online course, Electric and magnetic field calculations with finite-element methods. We'll advance to an actual application, a concept for a capacitive position sensor. Rather than using prepared input files, we'll build the entire solution from scratch. This article covers the initial steps in building a 3D assembly with Geometer. Following articles will cover mesh generation, the FEM solution and analysis techniques. The example emphasizes the internal parametric models of Geometer and MetaMesh rather than the STL models created with CAD programs discussed in a previous article.
Figure 1 shows a view of the detector geometry. A dielectric object of known shape and size drops through the assembly along the y direction. A shaped drive electrode with an applied AC voltage creates a time-varying electric field that varies in the x-direction. Changes in the mutual capacitance between the drive electrode and detector is sensed with a bridge network. The function of the detector is to confirm the presence of the object and its approximate position in x. The purpose of our calculation is find numerical values for the relative changes in mutual capacitance with the size and position of the object to gauge the accuracy requirements for the detector circuit.
Figure 2 gives an alternate 3D view of the assembly. For reference, we will use the following dimensions:
- the solution volume covers the region -2.50 cm ≤ x,y ≤ 2.50 cm and -0.25 cm ≤ z ≤ 3.00 cm.
- the metal case of thickness 0.25 cm encloses all sides of assembly except for a cut to house the detector and the upper boundary in z. We'll discuss the physical meaning of this open boundary in a following article.
- the test object is a sphere of radius 0.375 cm.
- the detector is a rectangular plate with dimensions Wx = 1.75 cm, Wy = 3.25 cm and Wz = 0.25 cm.
- the cutout for the detector has dimensions Wx = 2.00 cm and Wy = 3.50 cm.
- the drive electrode is an extrusion of length Wy = 4.0 cm with a cross-section in the z-x plane defined by an outline of lines and arcs.
To start, you should decide on a working directory for the input/output files. Run the AMaze program launcher and point the Data folder to the directory. Run Geometer and click File/New script. In the opening dialog, type in the values shown in Fig. 3 to define the dimensions of the solution volume. When you click OK, Geometer automatically creates the first Part[1], a box that fills the solution volume. By default, the part is named SolutionVolume and is assigned to Region 1. The program displays a default orthogonal view in the x-y plane. The programs turns off the visibility of the first Part because it would obscure the view of additional parts.
At this point, we need to make a strategy decision. We could associate the first Part with air and add five parts to build up the metal case wall. On the other hand, it is easier to start with a block of metal that fills the solution volume and then to carve out an internal air volume. We'll take this approach. To start, let's define the physical regions that will be needed for the electrostatic solution and give them names that will help to remember their functions. Click Edit/Edit region names to bring up the dialog of Fig. 4. Replace the default region names with the ones shown and click OK.
Click the command Edit/Edit part, select SolutionVolume (the only one available) and click OK. The dialog of Fig. 5 (left) shows the properties of the parametric model. The Part is a Box that fills the solution volume. The box length in z is Wz = 3.25 cm. The part has been shifted a distance 1.375 cm so that it fills the region -0.25 cm ≤ z ≤ 3.00 cm. Note that the name of the associated region has been changed to MetalWall. Change the default Part name to MetalWall and then click OK to exit.
Next, we shall add a part that carves out the air volume. Choose Edit/Add part to open the model parameter dialog. Under Part type, choose Box from the popup menu. Set the Part name to Air and pick the Region Air. To leave metal walls of thickness 0.25 cm, the box should have lengths Lx = Ly = 4.50 cm and Lz = 3.00 cm. We need to set ZShift = 1.50 cm to fill in the region from 0.0 cm ≤ z ≤ 3.0 cm. Figure 5 (right) shows the final state of the dialog. When you exit, the boundary of the air region appears in the plot. Click View/Y normal axis to check that the length and displacement of the box are correct. At this point, it's a good idea save the work. Click File/Save script and accept the name DetectorStudy.MIN. The text file is in a format recognized as input to MetaMesh.
We need to include a slot in the wall to house the detector. Click on Edit/Add part and fill in the dialog with the following values
Type: Box Part name: DetectorWell Region: Air Lx = 2.00 Ly = 3.50 Lz = 0.25 ZShift = -0.125
If everything is correct, the plot looks like Fig. 6. Go ahead and add the detector and the test object using the following parameters
Type: Box Part name: Detector Region: Detector Lx = 1.75 Ly = 3.25 Lz = 0.25 ZShift = -0.125
Type: Sphere Part name: Object Region: Object Radius = 0.375 ZShift = 0.625
The spherical object is centered at x = y = 0.0 cm with center 0.625 cm from the surface of the detector.
Viewing the state of the assembly requires some effort and experience. The surfaces of selected parts are plotted using OpenGL. When an encompassing part (like the metal wall) is included, it obscures internal parts. The following options are useful to display internal parts:
- Turn off the visibility of encompassing parts.
- Use a wireframe display for the encompassing part.
- Assign clipping planes to the part display.
The Geometer Instruction Manual gives a complete description of the plot controls. To illustrate the current state of the setup, Fig. 7 shows a perspective view of the detector and object regions with the air region shown as a wireframe.
We need only define the drive electrode to complete the assembly. The Part is an extrusion, a shape that extends a given distance along one direction with an arbitrary shape in the plane normal to that direction. In comparison, a turning is an arbitrary shape rotated about an axis of symmetry. In both case, the shape is defined by a set of connected line and arc vectors. Extrusions and turnings are highly useful and versatile models that merit their own discussion. We'll cover the topic in the next article.
[1] It is important to understand the definitions of Parts and Regions. To review, see this previous article.
[2] Contact us : firstname.lastname@example.com.
[3] Field Precision home page: www.fieldp.com.

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Posted in Post 161 | Leave a Comment »
Posted in Post 161 | Leave a Comment »
Commander's Message:
As autumn arrives the trees and weather are changing' which bring many activities to our Post and community.
Our Fish Fries have gotten under way, thanks again to our fish fry chairmen Steve Ballard for getting this off to a good start. If you are unable to work, please come and support the Legion and let us make you a delicious dinner for you and your guests. Remember, the fish fries will be every Friday 4:30- 8pm until Nov.21th.
Like October, November will be busy month for our veterans, which play a big part in the Post activities. Once again the Holland Patent High School music department will be having its Veterans Concert on November 5th Wednesday at 7:00pm in the high school auditorium. Come see how these young people, who do a great job in honoring our veterans from the surrounding communities.
Saturday, November 8th will be our Veterans cover dish dinner at 7pm. Happy hour is 6-7 pm. A signup sheet will be near the bar at the Legion. Tuesday, November 11th at 11:00 am our Post will celebrate Veteran's day at the Legion with a service followed by a luncheon for all the Veterans within our area. Anyone wishing to bring in pictures or memorabilia of your time in the service to display and share with us would be appreciated.
As always we ask all of our members to look for and recruit new members that are eligible to belong to the American Legion. There are a lot of eligible people out there so please help us maintain strong by asking them to join us. Applications are available at the Post for the asking. This applies to the Auxiliary SAL as well as for the Legion.
Remember, November and December is coming faster than you think, Thanksgiving and Christmas will be time to spend with our families and friends to help bring in the New Year, let's not forget what we have done to help our veterans throughout the past year! So let's end the year on a good note ,remember the Veterans who have done so much for the freedom we have every day and to all the men and woman around the world who defend this great nation.
Special Date: Roberts Post 161 Annul Blood Drive, Date 12/15/14 – 1:00pm-6pm Monday at the Legion. Let's give for a friend, our family, and a veteran!
We also would like to extend to all our Post members and their families, a Happy Thanksgiving, a Merry Christmas and Happy New Year.
Veterans Serving Veterans,
Richard Roberts—Commander
Legion Membership:
Thank you to all the members who have paid their 2015 dues under the Early Bird program which ended 10/15. Currently we are at 65% of our membership quota. Our 2015 dues are payable through 12/31/14 to stay current. Please encourage friends and neighbors to pay dues by that date so the Post can be 100%.
We currently have 5 new members and look forward to welcoming more.
For God and Country and the Good of the Legion,
Gary Wedgewood, Membership
Ladies Auxiliary:
HAPPY FALL! We are off to a fairly busy one with the Fish Fries starting. They will end on Fri., Nov. 21, 2014. If you aren't able to work, please come and join us by having one of our delicious dinners on a Fri. night. We would love to see you.
Diane Money is working very hard on the raffle we are having for the month of Nov. Thank you Diane for all your hard work. After this fundraiser is over, we are thinking of doing an Auxiliary cookbook with recipes from our excellent cooks who are also valuable members. If you have a favorite recipe, please mail or e-mail it to me, or drop it off at the Post.
We just did the Sitrin's "Stars & Stripes" run/walk as part of Team Blaise. It was a wonderful experience and a big thank you to Linda Covich and Ruth Duheme for all the hours you spent on this. Many more of our Auxiliary were involved and I am so proud to be a member of such a great team of ladies.
Mary Briggs and Alice Shaler are planning the Juniors activity Christmas card making on Sat. Nov. 29, 2014, from 10:00 until ?, for our veterans who are in Oneida Co. nursing homes . It is a wonderful way to let these men and women know we care about them. Please feel free to come and join us in this event.
Alice is doing a really good job with membership, our quota was raised by county because last year we were fortunate enough to have ladies join our team and we hope this will continue. Remember the saying, "a woman's work is never done", and that is so true of the Auxiliary. The more members we have, the more we will be able to do for our veterans, our active military men and women, our children, and our community. Let's help Alice by getting the word out that Leon R. Roberts Unit 161 can never have too many members.
November is very a very important month. Don't forget to get out and vote. A Veteran's Concert will be held at the Holland Patent High School on Nov. 5th at 7:00 pm. The students and teachers put on an excellent show for our area veterans. It will be a lovely way to spend a night out. Nov. 11, the Legion will hold a Veterans Day ceremony starting at 11:00 am. This, too, is a heartwarming event in honor of our veterans.
December always brings busy times. We will be decorating the Legion for the holidays and all help would be appreciated. I don't have a date for that yet, but I will try to let many of you know when it will be. There will also be bookings for Christmas parties and we will be calling and asking for help with these.
I am so pleased with the number of ladies who come to the meetings. Sometimes a meeting goes longer than I would like, but that is usually because we have a lot of matters to tend to. Don't forget, our meetings are the first Monday of each month and they start at 7:00 pm.
I wish all of you a Happy Thanksgiving with family and friends, a very Merry Christmas, and a New Year that starts off with happiness and love for all of you.
Yours in Service,
Debbie Roberts
Sons of the American Legion:
S. A. L. 2015 membership is currently at 75%. We are always open to new members so encourage friends to join. There is a joint project this fall to refurbish the emblems on the end of the Post which we will contribute to. I want to thank the members who are participating in the NFL Sunday food sales, Friday fish fries and other Post functions. Keep up the good work!
For God and Country,
Commander John Bieksza
Posted in Post 161 | Leave a Comment »
Posted in Post 161 | Leave a Comment »
The Leon R. Roberts Post 161 is once again sponsoring our annual Cash Bash
Raffle. We want to give everyone an opportunity to win one (or more) of twenty seven (27) prizes. Only 2000 Tickets will be sold on a first come first serve basis. Odds of winning any prize is one out of seventy four. – . – .
Prizes for the Cash Bash Raffle are:
1 @ 3,000
1 @ 2,000
5 @ $500.
4 @ $250.
15 @ $100.
The drawing will be held at the Leon R. Roberts Post 161 on Sunday,
December 7, 2014 starting at 5:OO pm. You do not have to present to win, but everyone is welcome to join us for food and drink specials.
To acquire the application please write request to the Post Raffle Committee, PO Box 161, Holland Patent, NY 13354. After receiving the application just follow the instructions that are on each one.
Please use one application for each ticket, photo copies of applications are
acceptable. Your official ticket will be mailed to you.
Thanks for your support,
Post Raffle Committee.
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VA Takes Next Step to Modernize Scheduling System
Announces Request for Proposal for New Scheduling System
WASHINGTON – The Department of Veterans Affairs (VA) today announced plans to issue a Request for Proposal (RFP) for a new Medical Appointment Scheduling System; the next step in a series of actions VA has taken to replace its antiquated legacy scheduling system. The new system will improve access to care for Veterans by providing medical schedulers with cutting-edge, management-based scheduling software. The RFP will be made public by the end of September 2014; eligible vendors will have 30 days to respond from the day of issuance.
"We want this process to be open to all eligible vendors to make sure the Nation's Veterans have the full benefits the innovative marketplace has to offer," said VA Secretary Robert McDonald. "When we can put a solid scheduling system in place, this will free up more human resources to focus on direct Veterans' care. As VA recommits to its mission of caring for Veterans and evaluating our actions through the lens of what serves them best, we know a better scheduling system is necessary to provide them the timely, quality health care that they have earned and deserve."
VA will issue a draft RFP prior to releasing the full RFP to maximize industry and stakeholder input. The solicitation will require a two-part demonstration of capabilities: a written proposal and a technical demonstration to scheduling staff. VA hopes to award the contract by the end of the calendar year.
"VA chose a full- and open-competitive strategy to acquire a 'commercial, off-the-shelf' scheduling system," said Stephen Warren, VA's Chief Information Officer. "We want a system that is user-friendly and tailored specifically for our Veterans."
Even as VA issues an RFP to replace the existing system, efforts are underway to make the current system easier to use for schedulers and Veterans. Among those enhancements:
· VA recently awarded a contract to improve the existing scheduling interface, providing schedulers a calendar view of resources instead of the current text-based, multiple-screen view. This update is scheduled to begin roll out beginning in January 2015.
· VA is also developing mobile applications to allow Veterans to directly request certain types of primary care and mental health appointments (scheduled to begin deployment December 2014). Another application under development will give VA schedulers an easier-to-use interface to schedule medical appointments (scheduled to begin deployment December 2014).
· VA is also rolling out new clinical video telehealth capabilities in October 2014 to further enhance access to care.
As part of the current RFP preparation process, VA is working with Veteran Service Organizations (VSO) to incorporate the groups' feedback on requirements important to Veterans. VA's VSO partners are currently reviewing user experience and business process documentation, and VA will continue to consult with VSOs as it works toward publishing its acquisition solicitation.
VA's acquisition process will comply with recently established legislative requirements related to the Department's scheduling software.
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Commander's Message:
Summer is almost over and our Post is gearing up for an active fall. July and August have gone by so fast I hope everyone had time to enjoy these lazy days of summer! Again, I would like to thank the Legion for letting our members to attend this year's Department Convention in Albany, NY on July 16-19. Oneida County was represented well from many Posts in our area. Many resolutions were passed in dealing with our veterans and their needs. I will try to update these resolutions and try to put them on the our web site.
Again, congratulations to Anthony Palladino for being elected as County Commander. I know all the Posts in the county will work hard to support him on the up-coming year.
"Thanks" go out to our Legion Baseball team for another fine year. Our team was young but played very well against some veteran teams within the county. We were 19-12 and played in the District #5 playoffs. I'm proud of these young men who represented our Post with pride and honor. Again, thanks to Rich & Chris Hurlbut who have done so much to make this program so successful at Roberts Post and this community should be proud of giving these boys a place to play baseball, in making their school and parents proud.
Once again September & October will be here soon, so check the calendar in the newsletter for the up-coming events. Remember school will be in secession soon so watch out for our children and youth, they are a big part of our programs throughout the year!
Dues for our Legion members will now be $35.00 beginning with the 2015 cards. You may pay online or bring it in to the Legion addressed to membership chairmen Gary Wedgewood.
Fish Fries will be starting in October and as usual help is needed to make this a successful year. Anyone wanting to help, please come in and signup, or call 865-9921.
Also in October is The 3rd Annual Sitrin's Stars & Stripes Run-Walk at SUNY IT Campus, Marcy, NY. What a way to support our Nation's Heroes with the Sitrin's Military Rehabilitation Program which has helped many of our veterans. This year Roberts Post is going to be a part of "Team Blaise" with Upton Post 8259, Floyd F.D. and many businesses to support the Oleski family in this walk & run!
Dates to remember for our veterans who served: September 2nd, 1945 – V-J Day; September19th POW/MIA Recognition Day; September 28th "Gold Star Family Remembrance Sunday; October 7th 2001- Operation Enduring Freedom begins in Afghanistan; October 13th 1775—US Navy established.
In closing, I just want to thank everyone at Roberts Post for all the hard work we've done and must continue to do more for our Legion, Community, and, most of all, our Veterans.
Veterans Serving Veterans,
Richard Roberts, Commander
Legion Membership:
Membership for 2015 is coming along very well and I appreciate all your support. If you have not yet paid your dues, you can send them to the Post or pay online at www.MyLegion.org. Either way I will send your card out promptly. Dues received by October 15th will receive an "Early Bird" stamp.
For God and Country,
Gary Wedgewood, Membership
Ladies Auxiliary:
Hope your summer was awesome but it's that time of year – vacation is over. It's get back to Auxiliary business again. I will tell you this coming year will be busy with many items that are on the agenda for us to talk about and carry out.
To catch you up – our own Roberta "Bobbie" Owen was elected 5th District president and we are very proud of her. She is going to need our help and support this coming year so let's be there for her.
It is with deep sadness in my heart that I have to report we lost one very sweet lady, friend, and Auxiliary member "Gert" Buczkowski. Our love and condolences go out to Mike and the family.
This summer has seen some of our teammates on the DL [disabled list] due to injury, surgery, or illness. If you would like to send a "Thinking of you" card to Debbie Williams, Barbara Doucette, Ursula Walker, Coleen Leahy Firshing, or Karen McMahon – please get in touch with me for their addresses if you don't have them.
One of our Legion members who is a WWII veteran had his 90th birthday this summer. His name is Jack Boak and if you would like to send him belated birthday wishes I am sure it would make him very happy. I have his address if you need it.
The one BIG project on the agenda is the Sitrin's "Stars & Stripes" Walk/Run on Sat. Oct. 11, 2014, at SUNYIT in Marcy. This event funds the Sitrin's Military Rehabilitation Program for veterans. It is a marvelous program and has helped many and it will continue to help many, many more in the future. TEAM BLAISE has been formed for this walk with the support and tremendous amount of help and work from the Oleski family. It is our hope to get the entire community involved in the project. Right now we have team members from Roberts Legion Post 161, Upton VFW Post 8259, Floyd F.D., area businesses, and family and friends of Blaise. If you want to help but can't for whatever reason, a donation could always be given. There is still time to join this team – all are welcome! Any questions, please feel free to get in touch with me.
On Sat. Sept. 6, 2014, at Upton VFW there will be a "Stars & Stripes" Across the Land ceremony. It is part of the fundraising efforts for the Sitrin veterans program. Words are not going to be able to describe how much this will mean to all of us – you will have to be there to experience it. For further information, call Ruth Fallon Duheme.
Our first Auxiliary meeting will be Monday, Sept. 8, 2014, at 7:00 pm at the Legion. At this meeting we will vote on the standing rules that we worked on this summer and they will help govern us. I hope many of you will attend. The finance committee will be working on a budget before the first meeting, but it probably won't be ready to vote on until at least October. The purpose of the things we are doing is to help us run more efficiently and, hopefully, to shorten our regular meetings a little.
Don't forget: fish fries will start the first week of October, be ready for the call asking for a donation to the salad bar or to help work one. We always need help and yours will be greatly appreciated. Before the next newsletter comes out we will be having our Halloween Party for the children. I am not sure when it will be because Halloween falls on a Friday night this year and that is also the night of a fish fry. We will decide at the October meeting which night to have the party. Help is always needed for this and it is so much fun to see all the little trick or treaters in costume and having such a good time at our party.
Remember, school starts Sept. 4. So please watch out for the children and school buses. We want everyone to be safe when school opens.
Membership: Alice has the 2015 cards and you can renew any time now. Don't forget – dues are: Sr. Aux. $23.00 ; Jr. Aux. $7.00. Thank you.
Yours in service,
Debbie Roberts
Sons of the American Legion:
Hope everyone enjoyed their summer. Our Officers for this year are: John Bieksza, Commander; Peter Fenton, 1st Vice; Jim Owen, 2nd Vice; Bob Stanger, 3rd Vice, Treasurer, Membership; Rod Koenig, Adjutant; Peter Chambrone, Chaplain; Ted Heburn, Sergeant-at-Arms; and Art Stark Historian.
Please join us for our 1st meeting of the year Sept 8th at 7pm. Your ideas are always welcome. The SAL is sponsoring Team Blaise for the Stars & Stripes Walk in October. For more information or to sign up please see me. Fish fries are starting again in October. Help is always appreciated.
For God and Country
Commander John Bieksza
S.A.L. Membership:
If you have changed your address let me know. We currently have 87 members with 14 paid. Dues are $15 and $10. If you want to know where your money goes, $8 goes to state and $1.75 goes to county. If you pay late your current number of years will not be on your card.
For God and Country,
Bob Stanger, Membership
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Chilean copper,
copper production,
Corporacion Nacional del Cobre de Chile,
BHP Billiton,
Los Pelambres
SÃO PAULO Chiles copper production rose to about 480,000 tonnes in July, up 15.5 percent year on year from 415,300 tonnes, according to national copper commission Cochilco.
Output at Corporacion Nacional del Cobre de Chile (Codelco), the worlds top producer, totaled 150,800 tonnes for the month. Thats up 9 percent from 138,300 tonnes a year earlier but was down 2 percent from the prior month.
Also contributing to the increase were BHP Billiton Ltd.s Escondida Mine in Chile, which saw output increase 28.7 percent year on year to 79,200 tonnes; and Cia. Minera Dona Ines de Collahuasi SCMowned by a consortium consisting of Anglo American Plc (44 percent), Glencore Xstrata Plc (44 percent) and other investorssaw its output double in the year-on-year comparison, totalling 50,400 tonnes.
Anglo American Sur produced 36,900 tonnes of copper in July, up 22.1 percent from a year earlier;p and Antofagasta Plcs Los Pelambres Mine ended June with flat production of 34,300 tonnes.
Chilean copper output for the first seven months of the year stood at 3.25 million tonnes, up 7 percent from the same period last year.
A version of this article was first published in AMM sister publication Metal Bulletin.
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-- Charles C. Mitchell, Barstow city manager