Patent Application
20070146426
This invention relates to the manufacture of thin film transistors by inkjet printing.
U.S. Pat. No. 6,690,029 B1 purportedly discloses certain substituted pentacenes and electronic devices made therewith.
WO 2005/055248 A2 purportedly discloses certain substituted pentacenes and polymers in top gate thin film transistors.
Briefly, the present invention provides a method of making a thin film transistor comprising the steps of: providing a substrate; applying a gate electrode ink by inkjet printing; applying a dielectric ink over by inkjet printing; applying a semiconductor ink by inkjet printing; and applying a source and drain electrode ink by inkjet printing. In some embodiments the gate electrode ink is applied directly to the substrate. In some embodiments the dielectric ink is applied over at least a portion of the gate electrode ink. In some embodiments the semiconductor ink is applied over at least a portion of the dielectric ink and the source and drain electrode ink is applied over at least a portion of the semiconductor ink. In some embodiments the source and drain electrode ink is applied over at least a portion of the dielectric ink and the semiconductor ink is applied over at least a portion of the source and drain electrode ink. In some embodiments the semiconductor ink is applied directly to the substrate, the source and drain electrode ink is applied over at least a portion of the semiconductor ink, the dielectric ink is applied over at least a portion of the source and drain electrode ink, and the gate electrode ink is applied over at least a portion of the dielectric ink. In some embodiments the source and drain electrode ink is applied directly to the substrate, the semiconductor ink is applied over at least a portion of the source and drain electrode ink, the dielectric ink is applied over at least a portion of the semiconductor ink, and the gate electrode ink is applied over at least a portion of the dielectric ink. In some embodiments the semiconductor ink comprises a solvent and a semiconducting material comprising:
1-99.9% by weight of a polymer; and
0.1-99% by weight of a compound according to Formula I:
where each R1 is independently selected from H and CH3 and each R2 is independently selected from branched or unbranched C2-C18 alkanes, branched or unbranched C1-C18 alkyl alcohols, branched or unbranched C2-C18 alkenes, C4-C8 aryls or heteroaryls, C5-C32 alkylaryl or alkyl-heteroaryl, a ferrocenyl, or SiR33 where each R3 is independently selected from hydrogen, branched or unbranched C1-C10 alkanes, branched or unbranched C1-C10 alkyl alcohols or branched or unbranched C2-C10 alkenes. In some embodiments the polymer has a dielectric constant at 1 kHz of greater than 3.3, and typically is selected from the group consisting of: poly(4-cyanomethyl styrene) and poly(4-vinylphenol).
Thin film transistors show promise in the development of lightweight, inexpensive and readily reproduced electronic devices. The present invention provides for all-ink-jet, all-additive manufacture of thin film transistors.
Thin films transistors are known in four principle geometries. With reference to each of
In the top gate designs depicted in
Inkjet printing is well known in the art, e.g., for printing graphics, including multi-color graphics. Inkjet printing enables precise positioning of very small drops of ink. Any suitable inkjet printing system may be used in the practice of the present invention, including thermal, piezoelectric, and continuous inkjet systems. Most typically a piezoelectric inkjet system is used. Inks useful in inkjet printing are typically free of particulates greater than 500 nm in size and more typically free of particulates greater than 200 nm in size. Inks useful in inkjet printing typically require suitable rheological properties.
Inkjet printing of thin film transistors requires the use of inks which may be applied without damage to previously applied inks. The inks and materials of the present invention enable the construction of a thin film transistor wherein every layer is made by inkjet printing. As a result, a relatively inexpensive yet precise technology can be used to generate electronic circuits. Furthermore, in some embodiments of the present invention, transistor manufacture requires only additive steps. That is, etching or other material removal steps may be eliminated.
Semiconductor inks useful in the present invention typically include a solvent and a semiconducting material, which typically includes a polymer and a semiconducting compound. Any suitable solvent may be used, which may include ketones, aromatic hydrocarbons, and the like. Typically the solvent is organic. Typically the solvent is aprotic.
Semiconductor inks useful in the present invention may include any suitable polymer. Typically, the polymer has a dielectric constant at 1 kHz of greater than 3.3, more typically greater than 3.5, and more typically greater than 4.0. The polymer typically has a M.W. of at least 1,000 and more typically at least 5,000. Typical polymers include poly(4-cyanomethyl styrene) and poly(4-vinylphenol). Cyanopullulans may also be used.
Typical polymers also include those described in U.S. Patent Publication No. 2004/0222412 A1, incorporated herein by reference. Polymers described therein include substantially nonfluorinated organic polymers having repeat units of the formulas:
wherein:
each R1 is independently H, Cl, Br, I, an aryl group, or an organic group that includes a crosslinkable group;
each R2 is independently H, an aryl group, or R4;
each R3 is independently H or methyl;
each R5 is independently an alkyl group, a halogen, or R4;
each R4 is independently an organic group comprising at least one CN group and having a molecular weight of about 30 to about 200 per CN group; and
n=0-3;
with the proviso that at least one repeat unit in the polymer includes an R4.
The semiconductor material in the ink contains the polymer in an amount of 1-99.9% by weight, more typically 1-10% by weight.
Semiconductor inks useful in the present invention may include any suitable semiconducting compound. The semiconducting compound may be a functionalized pentacene compound according to Formula I:
where each R1 is independently selected from H and CH3 and each R2 is independently selected from branched or unbranched C2-C18 alkanes, branched or unbranched C1-C18 alkyl alcohols, branched or unbranched C2-C18 alkenes, C4-C8 aryls or heteroaryls, C5-C32 alkylaryl or alkyl-heteroaryl, a ferrocenyl, or SiR33 where each R3 is independently selected from hydrogen, branched or unbranched C1-C10 alkanes, branched or unbranched C1-C10 alkyl alcohols or branched or unbranched C2-C10 alkenes. Typically each R1 is H. Typically, each R2 is SiR33. More typically each R2 is SiR33 and each R3 is independently selected from branched or unbranched C1-C10 alkanes. Most typically, the compound is 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), shown in formula II:
The semiconductor material contains the compound of Formula I or of Formula II in an amount of 0.1-99% by weight.
Any suitable dielectric ink may be used, including composistions disclosed in U.S. patent application Ser. No. 11/282,923, incorporated herein by reference.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
Unless otherwise noted, all reagents were obtained or are available from Aldrich Chemical Co., Milwaukee, Wis., or may be synthesized by known methods.
Materials were obtained from the following sources without further purification:
Polyethylene napthalate (PEN), Dupont Teijin films, Q65A PEN.
Cabot silver ink, Inkjet Silver Conductor, bulk resistivity 4-32 mW cm, from Cabot Printable Electronics and Displays, Albuqerque, N. Mex.
Perfluorothiophenol, Aldrich Chemical Company.
Toluene, EMD Chemicals, Inc. Gibbstown, N.J.
Cyclohexanone, EMD Chemicals, Inc. Gibbstown, N.J.
6,13-Di(triisopropylsilylethylnyl)pentacene (TIPS-pentacene) was synthesized as disclosed in U.S. Pat. No. 6,690,029 B1 at Example 1.
Poly(4-vinylphenol) MW 9,000 to 11,000 Sp.gr. 1.16 (PVP), Polyscience, Inc. Warrington, Pa.
Pentaerythritol tetraacrylate (SR444), Sartomer, West Chester, Pa.
Irgacure 819, Ciba specialty Chemicals, Basel Switzerland.
Polymer A is a nitrile-containing styrene-maleic anhydride copolymer that is described in U.S. Patent Publication No. 2004/0222412 A1, incorporated herein by reference. The synthesis is described therein at paragraphs 107 and 108 under the caption “Example 1, Synthesis of Polymer 1,” as follows:
A 250-milliliter (mL), three-necked flask fitted with magnetic stirrer and nitrogen inlet was charged with 8.32 grams (g) 3-methyl aminopropionitrile (Aldrich) and a solution of 20.00 g styrene-maleic anhydride copolymer (SMA 1000 resin available from Sartomer, Exton, Pa.) in 50 mL of anhydrous dimethylacrylamide (DMAc, Aldrich). After the mixture was stirred for 30 minutes (min) at room temperature, N,N-dimethylaminopyridine (DMAP) (0.18 g, 99%, Aldrich) was added and the solution was then heated at 110° C. for 17 hours (h). The solution was allowed to cool to room temperature and was slowly poured into 1.5 liters (L) of isopropanol while stirred mechanically. The yellow precipitate that formed was collected by filtration and dried at 80° C. for 48 h at reduced pressure (approximately 30 millimeters (mm) Hg). Yield: 26.0 g.
Twenty grams (20 g) of this material was dissolved in 50 mL anhydrous DMAc followed by the addition of 28.00 g glycidyl methacrylate (GMA) (Sartomer), 0.20 g hydroquinone (J. T. Baker, Phillipsburg, N.J.) and 0.5 g N,N-dimethylbenzylamine (Aldrich). The mixture was flashed with nitrogen and then was heated at 55° C. for 20 h. After the solution was allowed to cool to room temperature, it was poured slowly into 1.5 L of a mixture of hexane and isopropanol (2:1, volume:volume (v/v), GR, E.M. Science) with mechanical stirring. The precipitate that formed was dissolved in 50 mL acetone and precipitated twice, first into the same solvent mixture as used above and then using isopropanol. The solid (Polymer A) was collected by filtration and was dried at 50° C. for 24 h under reduced pressure. (approximately 30 mm Hg). Yield: 22.30 g. FT-IR (film): 3433, 2249, 1723, 1637, 1458, 1290, 1160, and 704 cm−1. Mn (number average molecular weight)=8000 grams per mole (g/mol), Mw (weight average molecular weight)=22,000 g/mol. Tg=105° C. Dielectric constant approximately 4.6.
An all inkjet-printed, all-additive array of transistors was printed on a piece of PEN film at 304 dpi using a Spectra inkjet print head SM-128 having a 50 pl drop volume for the silver ink and the dielectric (polymer A) ink and a Spectra inkjet print head SE-128 having a 30 pl drop volume for the semiconductor (TIPS-PVP) ink. Layers were printed in the order: 1. gate, 2. dielectric, 3. source/drain, and 4. semiconductor; according to the pattern depicted in
Gate electrodes (1×1 mm with probe pads 1×1 mm) were printed onto the PEN substrate with Cabot silver ink. This material was cured by heating to 125° C. for 10 minutes. The dielectric layer, a solution of 15 wt % Polymer A, 1.5 wt % Irgacure 819 photoinitiator and 1.5 wt % pentaerythritol tetraacrylate crosslinker (SR444) in isophorone, was printed on top of the gate electrodes so as to cover half of the strip and leave half exposed to make electrical contact. This layer was cured by placing under a bank of short wavelength UV lamps (254 nm) in a nitrogen environment for seven minutes. A pair of source and drain electrodes (1×1 mm) were printed aligned with each gate electrode so as to form a 100 micron channel between the source and drain electrodes over top of the gate electrode while minimizing the amount of overlap with the gate electrode. These electrodes were also printed by inkjet printing using Cabot silver ink followed by a heating step at 125° C. for 10 minutes. This sample was then treated with a 0.1 mmol solution of perfluorothiophenol in toluene for 1 hour. The sample was rinsed with toluene and dried. The semiconductor solution, a solution of 10 wt % PVP and 0.8 wt % TIPS in cyclohexanone, was printed by inkjet in a short line to cover the channel region between the source and drain electrodes but to not touch the semiconductor material form adjacent transistors. The sample was then heated at 120° C. for 10 minutes.
Ids=μC×W/L×(Vgs−Vt)2/2
the saturation field effect mobility was calculated from the linear portion of the curve using the specific capacitance of the gate dielectric (C), the channel width (W) and the channel length (L). The x-axis extrapolation of this straight-line fit was taken as the threshold voltage (Vt). In addition, plotting Id as a function of Vgs yielded a curve where a straight line fit was drawn along a portion of the curve containing Vt. The inverse of the slope of this line was the sub-threshold slope (S). The on/off ratio was taken as the difference between the minimum and maximum drain current (Ids) values of the Ids−Vgs curve. In
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and principles of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth hereinabove.
