WO2009115772A1 - Organic thin film transistor - Google Patents

Organic thin film transistor Download PDF

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Publication number
WO2009115772A1
WO2009115772A1 PCT/GB2009/000668 GB2009000668W WO2009115772A1 WO 2009115772 A1 WO2009115772 A1 WO 2009115772A1 GB 2009000668 W GB2009000668 W GB 2009000668W WO 2009115772 A1 WO2009115772 A1 WO 2009115772A1
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WO
WIPO (PCT)
Prior art keywords
source
thin film
film transistor
electrode
organic thin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2009/000668
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French (fr)
Inventor
Jonathan James Michael Halls
Craig Murphy
Kiyotaka Mori
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cambridge Display Technology Ltd
Panasonic Corp
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Cambridge Display Technology Ltd
Panasonic Corp
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Filing date
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Application filed by Cambridge Display Technology Ltd, Panasonic Corp filed Critical Cambridge Display Technology Ltd
Priority to JP2011500281A priority Critical patent/JP5596666B2/en
Priority to DE112009000610.8T priority patent/DE112009000610B4/en
Priority to US12/933,675 priority patent/US8829494B2/en
Priority to KR1020107023283A priority patent/KR101509420B1/en
Priority to CN200980116571.9A priority patent/CN102017211B/en
Publication of WO2009115772A1 publication Critical patent/WO2009115772A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H10K10/84—Ohmic electrodes, e.g. source or drain electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/30—Organic light-emitting transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H10K71/611—Forming conductive regions or layers, e.g. electrodes using printing deposition, e.g. ink jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof

Definitions

  • the present invention relates generally to organic thin film transistors and in particular to the physical and material properties of a source and drain electrode forming part of the organic thin film transistor.
  • Transistors can be divided into two main types: bipolar junction transistors and field-effect transistors. Both types share a common structure comprising three electrodes with a semiconductive material disposed therebetween in a channel region.
  • the three electrodes of a bipolar junction transistor are known as the emitter, collector and base, whereas in a field-effect transistor the three electrodes are known as the source, drain and gate.
  • Bipolar junction transistors may be described as current-operated devices as the current between the emitter and collector is controlled by the current flowing between the base and emitter.
  • field-effect transistors may be described as voltage- operated devices as the current flowing between source and drain is controlled by the voltage between the gate and the source.
  • Transistors can also be classified as p-type and n-type according to whether they comprise semiconductive material which conducts positive charge carriers (holes) or negative charge carriers (electrons) respectively.
  • the semiconductive material may be selected according to its ability to accept, conduct, and donate charge.
  • the ability of the semiconductive material to accept, conduct and donate holes or electrons can be enhanced by doping the material.
  • a p-type transistor device can be formed by selecting a semiconductive material which is efficient at accepting, conducting, and donating holes, and selecting a material for the source and drain electrodes which is efficient at injecting and accepting holes from the semiconductive material.
  • Good energy-level matching of the Fermi-level in the electrodes with the HOMO level of the semiconductive material can enhance hole injection and acceptance.
  • an n-type transistor device can be formed by selecting a semiconductive material which is efficient at accepting, conducting, and donating electrons, and selecting a material for the source and drain electrodes which is efficient at injecting electrons into, and accepting electrons from, the semiconductive material.
  • Good energy-level matching of the Fermi-level in the electrodes with the LUMO level of the semiconductive material can enhance electron injection and acceptance.
  • Transistors can be formed by depositing the components in thin films to form a thin film transistor (TFT).
  • TFT thin film transistor
  • ONTFT organic thin film transistor
  • OTFTs may be manufactured by low cost, low temperature methods such as solution processing. Moreover, OTFTs are compatible with flexible plastic substrates, offering the prospect of large-scale manufacture of OTFTs on flexible substrates in a roll-to-roll process.
  • the general architecture of a bottom-gate organic thin film transistor comprises a gate electrode 12 deposited on a substrate 10.
  • An insulating layer 11 of dielectric material is deposited over the gate electrode 12 and source and drain electrodes 13, 14 are deposited over the insulating layer 11 of dielectric material.
  • the source and drain electrodes 13, 14 are spaced apart to define a channel region therebetween located over the gate electrode 12.
  • An organic semiconductor (OSC) material 15 is deposited in the channel region for connecting the source and drain electrodes 13, 14.
  • the OSC material 15 may extend at least partially over the source and drain electrodes 13, 14.
  • a gate electrode at the top of an organic thin film transistor to form a so-called top-gate organic thin film transistor.
  • source and drain electrodes are deposited on a substrate and spaced apart to define a channel region therebetween.
  • a layer of an organic semiconductor material is deposited in the channel region to connect the source and drain electrodes and may extend at least partially over the source and drain electrodes.
  • An insulating layer of dielectric material is deposited over the organic semiconductor material and may also extend at least partially over the source and drain electrodes.
  • a gate electrode is deposited over the insulating layer and located over the channel region.
  • An organic thin film transistor can be fabricated on a rigid or flexible substrate.
  • Rigid substrates may be selected from glass or silicon and flexible substrates may comprise thin glass or plastics such as poly(ethylene-terephthalate) (PET), poly(ethylene-naphthalate) PEN, polycarbonate and polyimide.
  • PET poly(ethylene-terephthalate)
  • PEN poly(ethylene-naphthalate) PEN
  • polycarbonate and polyimide poly(ethylene-terephthalate)
  • the organic semiconductive material may be made solution processable through the use of a suitable solvent.
  • Exemplary solvents include mono- or poly-alkylbenzenes such as toluene and xylene; tetralin; and chloroform.
  • Preferred solution deposition techniques include spin coating and ink jet printing. Other solution deposition techniques include dip-coating, roll printing and screen printing.
  • the length of the channel defined between the source and drain electrodes may be up to 500 microns, but preferably the length is less than 200 microns, more preferably less than 100 microns, most preferably less than 20 microns.
  • the gate electrode can be selected from a wide range of conducting materials for example a metal (e.g. gold) or metal compound (e.g. indium tin oxide).
  • conductive polymers may be deposited as the gate electrode. Such conductive polymers may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above.
  • the insulating layer comprises a dielectric material selected from insulating materials having a high resistivity.
  • the dielectric constant, k, of the dielectric is typically around 2-3 although materials with a high value of k are desirable because the capacitance that is achievable for an OTFT is directly proportional to k, and the drain current ID is directly proportional to the capacitance. Thus, in order to achieve high drain currents with low operational voltages, OTFTs with thin dielectric layers in the channel region are preferred.
  • the dielectric material may be organic or inorganic. Preferred inorganic materials include SiO. 2 , SiNx and spin-on-glass (SOG).
  • Preferred organic materials are generally polymers and include insulating polymers such as poly vinylalcohol (PVA), polyvinylpyrrolidine (PVP), acrylates such as polymethylmethacrylate (PMMA) and benzocyclobutanes (BCBs) available from PVA.
  • PVA poly vinylalcohol
  • PVP polyvinylpyrrolidine
  • acrylates such as polymethylmethacrylate (PMMA) and benzocyclobutanes (BCBs) available from PVA
  • PMMA polymethylmethacrylate
  • BCBs benzocyclobutanes
  • the insulating layer may be formed from a blend of materials or comprise a multi-layered structure.
  • the dielectric material may be deposited by thermal evaporation, vacuum processing or lamination techniques as are known in the art. Alternatively, the dielectric material may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above.
  • the dielectric material is deposited from solution onto the organic semiconductor, it should not result in dissolution of the organic semiconductor. Likewise, the dielectric material should not be dissolved if the organic semiconductor is deposited onto it from solution. Techniques to avoid such dissolution include: use of orthogonal solvents for example use of a solvent for deposition of the uppermost layer that does not dissolve the underlying layer; and cross linking of the underlying layer.
  • the thickness of the insulating layer is preferably less than 2 micrometres, more preferably less than 500 nm.
  • the source and drain electrodes For ease of manufacture it is known to fabricate the source and drain electrodes from the same material. Typically a suitable material such as gold is deposited by thermal evaporation upon a suitable substrate and then patterned to define the source and drain electrodes using standard photolithography and lift off techniques as are known in the art.
  • a suitable material such as gold is deposited by thermal evaporation upon a suitable substrate and then patterned to define the source and drain electrodes using standard photolithography and lift off techniques as are known in the art.
  • an energy level diagram for a known OTFT represents a source and drain electrode 16, 17 formed of gold with a workfunction of 4.8eV.
  • An OSC material 18 such as a small molecule or polymer material is represented with a workfunction of 5.3eV.
  • the workfunction of the OSC 18 can be tuned to closely match the workfunction of both the source and drain electrodes 16, 17. In such an arrangement, there is no significant barrier to the injection or extraction of holes to and from the OSC 18. However, in reverse bias or non-use conditions there is no barrier between the OSC 18 and source or drain electrodes 16, 17 to leakage currents.
  • an organic thin film transistor comprising source and drain electrodes, an organic semiconductor disposed in a channel region between the source and drain electrodes, a gate electrode and a dielectric disposed between source and drain electrodes and gate electrode, wherein the source electrode and the drain electrode comprise at least one different physical and/or material property from each other.
  • the present invention therefore provides a source and drain electrode which differ from each other in some physical or material property. These differing or “asymmetric electrodes" can be individually tailored to have specific electronic properties. The asymmetry allows for improved charge injection from the source electrode while allowing optimisation of charge extraction at the drain electrode. Advantages include higher mobility, lower contact resistance, lower leakage and a higher on-off ratio.
  • the different physical and/or material property is a physical structure provided by a patterned surface feature.
  • the patterned surface features can be . raised surface features and/or indentations which encourage crystallisation of the organic semiconductor material.
  • Such patterned surface features are preferably selected from a sawtooth profile, castellations and concave or convex profiles.
  • the source electrode may comprise a patterned surface feature along an edge adjacent the channel region and the drain electrode comprises a patterned surface feature along an edge adjacent the channel region offset from the patterned surface feature of the source electrode such that raised surface features of one electrode are paired with indented surface features of the other electrode.
  • the different physical structures are formed by stamping or photolithography.
  • Other preferred different physical properties include a different surface area of electrode, a different shape of electrode and a different surface treatment of electrode.
  • the surface treatment comprises an addition of a self- assembled monolayer.
  • a preferred different material property is a different material composition of the source and drain electrodes which can provide a different workfunction of source and drain electrodes.
  • the source electrode has a workfunction greater than or equal to the workfunction of the organic semiconductor and the drain electrode has a workfunction lower than the organic semiconductor.
  • Preferred materials for the source and drain electrodes include metals and conducting organic materials such as a small molecule, a polymer or poly(ethylene dioxythiophene).
  • the conducting organic material may be deposited by any one of inkjet printing, spin coating or stamp printing.
  • the different material composition of the source and drain electrodes comprises oxidised portions of the source and drain electrodes.
  • oxidised portions may comprise an oxygen compound such as oxides of Mo, MoCr, W or V or more particularly oxidised portions comprise MoCr-oxide, MoO 3 , WO 3 or V 2 O 5 .
  • An asymmetric organic thin film transistor may comprise source and drain electrodes comprising a bilayer of at least two overlapping layers and wherein an upper layer of the bilayer is positionally offset from a lower layer.
  • an upper layer of the source electrode bilayer overlaps and is adjacent the channel region of the transistor and the lower layer of the drain electrode bilayer is adjacent the channel region of the transistor.
  • an upper layer of the drain electrode bilayer overlaps and is adjacent the channel region of the transistor and the lower layer of the source electrode bilayer is adjacent the channel region of the transistor.
  • Patterning of the source and/or drain electrode can provide a transistor with a larger effective channel width than if the source and/or drain electrode was not patterned.
  • an organic thin film transistor comprising source and drain electrodes, an organic semiconductor disposed in a channel region between the source and drain electrodes, a gate electrode and a dielectric disposed between source and drain electrodes and gate electrode, wherein one or both of the source electrode and the drain electrode are patterned to provide an increased effective channel width contact area at the interface between the organic semiconductor and patterned electrode.
  • the organic thin film transistor can be a top-gate or bottom-gate transistor.
  • a method of fabricating an organic thin film transistor comprising source and drain electrodes with a channel region therebetween, a gate electrode, a dielectric layer disposed between the source and drain electrodes and the gate electrode, and an organic semiconductor disposed in the channel region between the source and drain electrodes, the method comprising providing a source and drain electrode that have at least one different physical and/or material property from each other.
  • Figure 1 is a schematic diagram of a general architecture of a bottom-gate organic thin film transistor according to the prior art
  • Figure 2 is a first energy level diagram for an organic thin film transistor according to the prior art
  • Figure 3 is a second energy level diagram for an organic thin film transistor according to the prior art
  • Figure 4 is a first energy level diagram for an organic thin film transistor having asymmetric source and drain electrodes according to an embodiment of the present invention
  • Figure 5 is a second energy level diagram for an organic thin film transistor having asymmetric source and drain electrodes according to an embodiment of the present invention
  • Figure 6 is a schematic diagram of an asymmetric source and drain electrode according to an embodiment of the present invention
  • Figures 7a and 7b are schematic diagrams of a method of forming an asymmetric source and drain electrode using an offset source according to an embodiment of the present invention
  • Figures 8a and 8b are schematic diagrams of a method of forming an asymmetric source and drain electrode using an offset mask according to an embodiment of the present invention
  • Figures 9a and 9b are schematic diagrams of a patterned asymmetric source and drain electrode according to an embodiment of the present invention.
  • Figure 10 is a schematic diagram of a pixel comprising an organic thin film transistor and an adjacent organic light emitting device fabricated on a common substrate according to an embodiment of the present invention.
  • Figure 11 is a schematic diagram of an organic thin film transistor fabricated in a stacked relationship to an organic light emitting device according to an embodiment of the present invention.
  • a first energy level diagram for an organic thin film transistor having asymmetric source and drain electrodes comprises an organic semiconductor material 40 having a workfunction of 5.3eV.
  • Preferred organic semiconductor materials 40 include small molecules such as optionally substituted pentacene; optionally substituted polymers such as polyarylenes, in particular polyfluorenes and polythiophenes; and oligomers. Blends of materials, including blends of different material types (e.g. a polymer and small molecule blend) may be used.
  • a source electrode 42 is provided with a workfunction of 5.3eV matching that of the organic semiconductor material 40.
  • a drain electrode 44 is provided with a workfunction of 4.8eV below that of the organic semiconductor material 40.
  • a conductive organic material such as a conductive polymer is deposited as the source electrode 42 and the drain electrode 44 is deposited as a metal such as gold.
  • both electrodes can be conductive polymers with a workfunction tuned to the desired value.
  • An example of such a conductive polymer is poly(ethylene dioxythiophene) (PEDOT) although other conductive polymers are known in the art.
  • PEDOT poly(ethylene dioxythiophene)
  • Such conductive polymers may be deposited from solution using, for example, spin coating or ink jet printing techniques.
  • the source 42 and drain 44 electrodes can be appropriately selected from a high workfunction material, preferably a metal, with a workfunction of greater than 3.5eV, for example gold, platinum, palladium, molybdenum, tungsten, or chromium selected for the required workfunction.
  • a high workfunction material preferably a metal
  • a workfunction of greater than 3.5eV for example gold, platinum, palladium, molybdenum, tungsten, or chromium selected for the required workfunction.
  • Other suitable compounds, alloys and oxides such as molybdenum trioxide and indium tin oxide may also be used.
  • an organic semiconductor material 40 comprises a • workfunction of 4.8eV.
  • a source electrode 42 is selected as gold, Au, having a workfunction of 4.8eV matching that of the organic semiconductor material 40.
  • a drain electrode 44 is selected as silver, Ag, having a workfunction of 4.3eV.
  • the source electrode is selected to have a workfunction matching that of the organic semiconductor material for efficient charge injection and carrier mobility.
  • the drain electrode is selected to have a workfunction below that of the organic semiconductor material so that charge extraction is not impeded and so that there exists a barrier to leakage currents in reverse bias or non-use conditions.
  • the source and drain electrodes comprise a material, for example a metal having a workfunction of less than 3.5eV such as calcium or barium or a thin layer of metal compound, in particular an oxide or fluoride of an alkali or alkali earth metal for example lithium fluoride, barium fluoride and barium oxide.
  • a metal having a workfunction of less than 3.5eV such as calcium or barium or a thin layer of metal compound, in particular an oxide or fluoride of an alkali or alkali earth metal for example lithium fluoride, barium fluoride and barium oxide.
  • conductive polymers may be deposited as the source and drain electrodes.
  • One technique to deposit an asymmetric source and drain electrode is to firstly deposit a source electrode metal by evaporation through a first mask onto a substrate.
  • the source electrode metal may be gold and deposited by thermal evaporation.
  • a second deposition is performed of the drain electrode metal using a second mask to form the drain electrode.
  • the drain electrode may be silver and also deposited by thermal evaporation.
  • an organic semiconductor material is deposited by a solution deposition technique such as spin coating or ink jet printing into a conductive channel between source and drain electrodes.
  • the organic semiconductor layer is dried using a thermal treatment process.
  • a schematic diagram of a precursor 60 to an asymmetric source and drain electrode arrangement 72 comprises a patterned NiCr adhesion layer 62 (shown as a dashed outline) deposited upon a glass substrate 64.
  • the NiCr adhesion layer 62 serves to aid the subsequent adhesion of a further metal 70 (shown as hatched pattern) put down as identical source and drain electrodes 66, 68.
  • the NiCr adhesion layer 62 serves to both provide adhesion and also to form an asymmetric source electrode 66 and drain electrode 68.
  • NiCr could be replaced by any other suitable contact electrode material for the purpose of this embodiment.
  • the further metal 70 has been offset deposited upon the patterned NiCr adhesion layer 62. Accordingly, in the case of the source electrode 66 a portion of the underlying NiCr adhesion layer 62 protrudes from the overlying further metal 70 layer and in the case of the drain electrode 68, the overlying further metal 70 layer protrudes from the underlying NiCr adhesion later 62.
  • an organic semiconductor material (not shown in Figure 6) is deposited over the source and drain electrodes 66, 68 to fill a channel 70 between the source and drain electrodes 66, 68.
  • the metal closest to the channel 70 for the source electrode 66 is NiCr and the metal closest to the channel 70 for the drain electrode 68 is the further metal 70.
  • the metal closest to the channel 70 dominates the electrical characteristics of the electrode.
  • a glass substrate 64 is exposed to a first NiCr metal source 74 using known line of sight evaporation deposition techniques.
  • a shutter 76 is provided to regulate exposure time and a mask 78 is provided to pattern the NiCr metal upon the glass substrate 64. Following evaporation of the NiCr metal the substrate 64 is therefore provided with a patterned NiCr adhesion layer 62.
  • the glass substrate 64 is exposed to a further metal source 80 such as Au.
  • a further metal source 80 such as Au.
  • the location of the source of the further metal 80 is offset from that of the NiCr metal source 74 and so the Au is deposited over the patterned NiCr adhesion layer 62 in an offset manner also as a patterned layer 70 in order to provide an asymmetric source and drain electrode 66, 68 arrangement 72 as described in Figure 6.
  • a glass substrate 64 is exposed to a first NiCr metal source 74 using known line of sight evaporation deposition techniques.
  • a shutter 76 is provided to regulate exposure time and a mask 78 is provided to pattern the NiCr metal upon the glass substrate 64.
  • the substrate 64 is provided with a patterned NiCr adhesion layer
  • the position of the mask 78 is offset by a small amount and the glass substrate 64 is exposed to a further metal source 80 such as gold, Au.
  • the location of the further metal source 80 is fixed in the same position as the NiCr metal source 74.
  • This change of metal source without change of relative position can be achieved through use of a carousel arrangement.
  • the Au is deposited over the patterned NiCr adhesion layer 62 in an offset manner also as a patterned layer 70 in order to provide an asymmetric source and drain electrode 66, 68 arrangement 72 as described in Figure 6.
  • asymmetric electrodes in addition to providing asymmetric electrodes to promote the injection and extraction of charge in an organic thin film transistor, asymmetric electrodes can be used to control organic semiconductor material crystal growth by controlling the extent of nucleation on the surfaces of the source and drain electrodes and particularly along the channel edge.
  • Asymmetry in the crystal growth and domain size at source and drain electrodes can improve crystal growth across a channel and eliminate grain boundaries caused when crystals grow from each side of the channel and meet towards the middle of the channel.
  • a grain boundary represents an amorphous rather than ordered portion of a crystal and can present a barrier to the mobility of charge through the crystal.
  • the asymmetry in crystal growth can be introduced by differences in physical shape, patterning and surface chemistry between source and drain electrodes in addition to differences in material composition as described above.
  • the asymmetry in nucleation so that the nucleation of crystals is preferred at one of the source and drain electrodes and so that nucleation is promoted at one electrode and suppressed at the other electrode can also introduced by differences in physical shape, patterning and surface chemistry between source and drain electrodes in addition to differences in material composition as described above.
  • This asymmetry in nucleation can cause crystal formation to commence at one electrode, for example the source electrode and progress across the channel to the other electrode, the drain electrode.
  • Figure 9a is a schematic diagram of a patterned asymmetric source and drain electrode according to an embodiment of the present invention where the asymmetry between electrodes arises from a difference in the patterning of the electrodes.
  • a gold, Au source electrode 90 and gold, Au drain electrode 92 are provided having a channel 70 therebetween.
  • the source electrode 90 is patterned with a structure that promotes nucleation and growth of organic semiconductor crystals.
  • the drain electrode 92 has a linear edge. In this case and as illustrated in Figure 9a, both electrodes can be IB
  • Such patterns can be sawtooth, castellations, concave or convex semidiscs or other suitable shapes.
  • the source electrode 90 comprises an edge sawtooth pattern and the drain electrode 92 is provided with a complementary sawtooth pattern.
  • the drain electrode 92 is provided with a complementary sawtooth pattern.
  • the use of a physically patterned electrode structure provides a larger effective width for the transistor, for a given linear width on a device.
  • the larger effective width can allow a use of organic semiconductor materials with lower intrinsic mobility.
  • the chemical property or surface energy of the source and drain electrodes can be altered and optimised to promote organic semiconductor crystallisation nucleation and increase the efficiency of charge injection and extraction.
  • Application of a surface treatment to one or both of the source and drain electrodes can be by made by depositing a self-assembled monolayer (SAM) over the source and/or drain electrodes.
  • SAM molecules with polar end groups can be used to provide local wetting and nucleate crystallisation.
  • SAM molecules with hydrophobic end groups e.g. fluorinated molecules
  • SAM molecules can be deposited using ink jet printing.
  • a particularly preferred SAM molecule comprises F4TCNQ.
  • OTFTs according to embodiments of the present invention have a wide range of possible applications.
  • One such application is to drive pixels in an optical device, preferably an organic optical device.
  • optical devices include photoresponsive devices, in particular photodetectors, and light- emissive devices, in particular organic light emitting devices.
  • OTFTs are particularly suited for use with active matrix organic light emitting devices, e.g. for use in display applications.
  • Figure 10 shows a pixel comprising an organic thin film transistor 100 and an adjacent organic light emitting device 102 fabricated on a common substrate 104.
  • the OTFT 100 comprises gate electrode 106, dielectric layer 108, source and drain electrodes 110 and 112 respectively, and OSC layer 114.
  • the OLED 102 comprises anode 116, cathode 118 and an electroluminescent layer 120 provided between the anode 116 and cathode 118. Further layers may be located between the anode 116 and cathode 118, such as charge transporting, charge injecting or charge blocking layers.
  • the layer of cathode material 118 extends across both the OTFT 100 and the OLED 102, and an insulating layer 122 is provided to electrically isolate the cathode layer 118 from the OSC layer 122.
  • the active areas of the OTFT 100 and the OLED 102 are defined by a common bank material formed by depositing a layer of photoresist 124 on substrate 104 and patterning it to define OTFT 100 and OLED 102 areas on the substrate.
  • the drain electrode 112 is directly connected to the anode 116 of the organic light emitting device 102 for switching the organic light emitting device 102 between emitting and non-emitting states.
  • an organic thin film transistor 200 may be fabricated in a stacked relationship to an organic light emitting device 202.
  • the organic thin film transistor 202 is built up as described above in either a top or bottom gate configuration.
  • the active areas of the OTFT 200 and OLED are built up as described above in either a top or bottom gate configuration.
  • a planarisation layer 204 (also known as a passivation layer) is deposited over the OTFT 200.
  • Exemplary passivation layers 204 include BCBs and parylenes.
  • the organic light emitting device 202 is fabricated over the passivation layer 204 and the anode 116 of the organic light emitting device 202 is electrically connected to the drain electrode 112 of the OFTF 200 by a conductive via 206 passing through passivation layer 204 and bank layer 124.
  • pixel circuits comprising an OTFT and an optically active area (e.g. light emitting or light sensing area) may comprise further elements.
  • the OLED pixel circuits of Figures 10 and 11 will typically comprise least one further transistor in addition to the driving transistor shown, and at least one capacitor.
  • the organic light emitting devices described herein may be top or bottom-emitting devices. That is, the devices may emit light through either the anode or cathode side of the device. In a transparent device, both the anode and cathode are transparent.
  • a transparent cathode device need not have a transparent anode (unless, of course, a fully transparent device is desired), and so the transparent anode used for bottom-emitting devices may be replaced or supplemented with a layer of reflective material such as a layer of aluminium.
  • Transparent cathodes are particularly advantageous for active matrix devices because emission through a transparent anode in such devices may be at least partially blocked by OTFT drive circuitry located underneath the emissive pixels as can be seen from the embodiment illustrated in Figure 11.
  • Thicknesses of the gate electrode, source and drain electrodes may be in the region of 5 - 200nm, although typically 50nm as measured by Atomic Force Microscopy (AFM), for example.
  • AFM Atomic Force Microscopy
  • the dielectric surface in the channel region may be provided with a monolayer comprising a binding region and an organic region to improve device performance, e.g. by improving the organic semiconductor's morphology (in particular polymer alignment and crystallinity) and covering charge traps, in particular for a high k dielectric surface.
  • exemplary materials for such a monolayer include chloro- or alkoxy-silanes with long alkyl chains, eg octadecyltrichlorosilane.

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Abstract

An organic thin film transistor comprising source and drain electrodes (13, 14), an organic semiconductor (15) disposed in a channel region between the source and drain electrodes, a gate electrode (12) and a dielectric (11) disposed between source and drain electrodes and gate electrode, wherein the source electrode and the drain electrode comprise at least one different physical and/or material property from each other.

Description

Organic Thin Film Transistor
The present invention relates generally to organic thin film transistors and in particular to the physical and material properties of a source and drain electrode forming part of the organic thin film transistor.
Transistors can be divided into two main types: bipolar junction transistors and field-effect transistors. Both types share a common structure comprising three electrodes with a semiconductive material disposed therebetween in a channel region. The three electrodes of a bipolar junction transistor are known as the emitter, collector and base, whereas in a field-effect transistor the three electrodes are known as the source, drain and gate. Bipolar junction transistors may be described as current-operated devices as the current between the emitter and collector is controlled by the current flowing between the base and emitter. In contrast, field-effect transistors may be described as voltage- operated devices as the current flowing between source and drain is controlled by the voltage between the gate and the source.
Transistors can also be classified as p-type and n-type according to whether they comprise semiconductive material which conducts positive charge carriers (holes) or negative charge carriers (electrons) respectively. The semiconductive material may be selected according to its ability to accept, conduct, and donate charge. The ability of the semiconductive material to accept, conduct and donate holes or electrons can be enhanced by doping the material. For example, a p-type transistor device can be formed by selecting a semiconductive material which is efficient at accepting, conducting, and donating holes, and selecting a material for the source and drain electrodes which is efficient at injecting and accepting holes from the semiconductive material. Good energy-level matching of the Fermi-level in the electrodes with the HOMO level of the semiconductive material can enhance hole injection and acceptance. In contrast, an n-type transistor device can be formed by selecting a semiconductive material which is efficient at accepting, conducting, and donating electrons, and selecting a material for the source and drain electrodes which is efficient at injecting electrons into, and accepting electrons from, the semiconductive material. Good energy-level matching of the Fermi-level in the electrodes with the LUMO level of the semiconductive material can enhance electron injection and acceptance.
Transistors can be formed by depositing the components in thin films to form a thin film transistor (TFT). When an organic material is used as the semiconductive material in such a device, it is known as an organic thin film transistor (OTFT).
OTFTs may be manufactured by low cost, low temperature methods such as solution processing. Moreover, OTFTs are compatible with flexible plastic substrates, offering the prospect of large-scale manufacture of OTFTs on flexible substrates in a roll-to-roll process.
With reference to Figure 1 , the general architecture of a bottom-gate organic thin film transistor (OTFT) comprises a gate electrode 12 deposited on a substrate 10. An insulating layer 11 of dielectric material is deposited over the gate electrode 12 and source and drain electrodes 13, 14 are deposited over the insulating layer 11 of dielectric material. The source and drain electrodes 13, 14 are spaced apart to define a channel region therebetween located over the gate electrode 12. An organic semiconductor (OSC) material 15 is deposited in the channel region for connecting the source and drain electrodes 13, 14. The OSC material 15 may extend at least partially over the source and drain electrodes 13, 14.
Alternatively, it is known to provide a gate electrode at the top of an organic thin film transistor to form a so-called top-gate organic thin film transistor. In such an architecture, source and drain electrodes are deposited on a substrate and spaced apart to define a channel region therebetween. A layer of an organic semiconductor material is deposited in the channel region to connect the source and drain electrodes and may extend at least partially over the source and drain electrodes. An insulating layer of dielectric material is deposited over the organic semiconductor material and may also extend at least partially over the source and drain electrodes. A gate electrode is deposited over the insulating layer and located over the channel region.
An organic thin film transistor can be fabricated on a rigid or flexible substrate. Rigid substrates may be selected from glass or silicon and flexible substrates may comprise thin glass or plastics such as poly(ethylene-terephthalate) (PET), poly(ethylene-naphthalate) PEN, polycarbonate and polyimide. The organic semiconductive material may be made solution processable through the use of a suitable solvent. Exemplary solvents include mono- or poly-alkylbenzenes such as toluene and xylene; tetralin; and chloroform. Preferred solution deposition techniques include spin coating and ink jet printing. Other solution deposition techniques include dip-coating, roll printing and screen printing.
The length of the channel defined between the source and drain electrodes may be up to 500 microns, but preferably the length is less than 200 microns, more preferably less than 100 microns, most preferably less than 20 microns.
The gate electrode can be selected from a wide range of conducting materials for example a metal (e.g. gold) or metal compound (e.g. indium tin oxide). Alternatively, conductive polymers may be deposited as the gate electrode. Such conductive polymers may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above.
The insulating layer comprises a dielectric material selected from insulating materials having a high resistivity. The dielectric constant, k, of the dielectric is typically around 2-3 although materials with a high value of k are desirable because the capacitance that is achievable for an OTFT is directly proportional to k, and the drain current ID is directly proportional to the capacitance. Thus, in order to achieve high drain currents with low operational voltages, OTFTs with thin dielectric layers in the channel region are preferred. The dielectric material may be organic or inorganic. Preferred inorganic materials include SiO.2, SiNx and spin-on-glass (SOG). Preferred organic materials are generally polymers and include insulating polymers such as poly vinylalcohol (PVA), polyvinylpyrrolidine (PVP), acrylates such as polymethylmethacrylate (PMMA) and benzocyclobutanes (BCBs) available from
Dow Corning. The insulating layer may be formed from a blend of materials or comprise a multi-layered structure.
The dielectric material may be deposited by thermal evaporation, vacuum processing or lamination techniques as are known in the art. Alternatively, the dielectric material may be deposited from solution using, for example, spin coating or ink jet printing techniques and other solution deposition techniques discussed above.
If the dielectric material is deposited from solution onto the organic semiconductor, it should not result in dissolution of the organic semiconductor. Likewise, the dielectric material should not be dissolved if the organic semiconductor is deposited onto it from solution. Techniques to avoid such dissolution include: use of orthogonal solvents for example use of a solvent for deposition of the uppermost layer that does not dissolve the underlying layer; and cross linking of the underlying layer.
The thickness of the insulating layer is preferably less than 2 micrometres, more preferably less than 500 nm.
For ease of manufacture it is known to fabricate the source and drain electrodes from the same material. Typically a suitable material such as gold is deposited by thermal evaporation upon a suitable substrate and then patterned to define the source and drain electrodes using standard photolithography and lift off techniques as are known in the art.
With reference to Figure 2, an energy level diagram for a known OTFT represents a source and drain electrode 16, 17 formed of gold with a workfunction of 4.8eV. An OSC material 18 such as a small molecule or polymer material is represented with a workfunction of 5.3eV. A problem arises in that the greater workfunction of 5.3eV of the OSC 18 represents a barrier to an injection of holes from the gold source electrode 16 into the OSC 18. There is no significant barrier to an extraction of holes at the gold drain electrode 17 and at reverse bias or non-use conditions the difference in workfunction values between the OSC 18 and the drain electrode 17 acts as a barrier to leakage currents.
Alternatively and as illustrated in Figure 3, the workfunction of the OSC 18 can be tuned to closely match the workfunction of both the source and drain electrodes 16, 17. In such an arrangement, there is no significant barrier to the injection or extraction of holes to and from the OSC 18. However, in reverse bias or non-use conditions there is no barrier between the OSC 18 and source or drain electrodes 16, 17 to leakage currents.
There is therefore a need for an improved organic thin film transistor where the source and drain electrodes are both adapted to the properties of organic semiconductor material used. According to a first aspect of the present invention, there is provided an organic thin film transistor comprising source and drain electrodes, an organic semiconductor disposed in a channel region between the source and drain electrodes, a gate electrode and a dielectric disposed between source and drain electrodes and gate electrode, wherein the source electrode and the drain electrode comprise at least one different physical and/or material property from each other.
The present invention therefore provides a source and drain electrode which differ from each other in some physical or material property. These differing or "asymmetric electrodes" can be individually tailored to have specific electronic properties. The asymmetry allows for improved charge injection from the source electrode while allowing optimisation of charge extraction at the drain electrode. Advantages include higher mobility, lower contact resistance, lower leakage and a higher on-off ratio.
Preferably the different physical and/or material property is a physical structure provided by a patterned surface feature. The patterned surface features can be . raised surface features and/or indentations which encourage crystallisation of the organic semiconductor material. Such patterned surface features are preferably selected from a sawtooth profile, castellations and concave or convex profiles. In order to provide directed crystallisation growth, the source electrode may comprise a patterned surface feature along an edge adjacent the channel region and the drain electrode comprises a patterned surface feature along an edge adjacent the channel region offset from the patterned surface feature of the source electrode such that raised surface features of one electrode are paired with indented surface features of the other electrode.
Preferably, the different physical structures are formed by stamping or photolithography.
Other preferred different physical properties include a different surface area of electrode, a different shape of electrode and a different surface treatment of electrode. Preferably, the surface treatment comprises an addition of a self- assembled monolayer.
A preferred different material property is a different material composition of the source and drain electrodes which can provide a different workfunction of source and drain electrodes.
In order to provide a device with efficient charge injection and extraction in addition to low leakage the source electrode has a workfunction greater than or equal to the workfunction of the organic semiconductor and the drain electrode has a workfunction lower than the organic semiconductor.
Preferred materials for the source and drain electrodes include metals and conducting organic materials such as a small molecule, a polymer or poly(ethylene dioxythiophene). The conducting organic material may be deposited by any one of inkjet printing, spin coating or stamp printing.
Preferably, the different material composition of the source and drain electrodes comprises oxidised portions of the source and drain electrodes. Such oxidised portions may comprise an oxygen compound such as oxides of Mo, MoCr, W or V or more particularly oxidised portions comprise MoCr-oxide, MoO3, WO3 or V2O5.
An asymmetric organic thin film transistor may comprise source and drain electrodes comprising a bilayer of at least two overlapping layers and wherein an upper layer of the bilayer is positionally offset from a lower layer. Preferably, an upper layer of the source electrode bilayer overlaps and is adjacent the channel region of the transistor and the lower layer of the drain electrode bilayer is adjacent the channel region of the transistor. Alternatively, an upper layer of the drain electrode bilayer overlaps and is adjacent the channel region of the transistor and the lower layer of the source electrode bilayer is adjacent the channel region of the transistor.
Patterning of the source and/or drain electrode can provide a transistor with a larger effective channel width than if the source and/or drain electrode was not patterned. According to a second aspect of the present invention, there is therefore provided an organic thin film transistor comprising source and drain electrodes, an organic semiconductor disposed in a channel region between the source and drain electrodes, a gate electrode and a dielectric disposed between source and drain electrodes and gate electrode, wherein one or both of the source electrode and the drain electrode are patterned to provide an increased effective channel width contact area at the interface between the organic semiconductor and patterned electrode.
The organic thin film transistor can be a top-gate or bottom-gate transistor. According to a third aspect of the present invention, there is provided a method of fabricating an organic thin film transistor comprising source and drain electrodes with a channel region therebetween, a gate electrode, a dielectric layer disposed between the source and drain electrodes and the gate electrode, and an organic semiconductor disposed in the channel region between the source and drain electrodes, the method comprising providing a source and drain electrode that have at least one different physical and/or material property from each other.
Embodiments of the invention will now be described, by way of example only, and with reference to the accompanying drawings in which:
Figure 1 is a schematic diagram of a general architecture of a bottom-gate organic thin film transistor according to the prior art;
Figure 2 is a first energy level diagram for an organic thin film transistor according to the prior art;
Figure 3 is a second energy level diagram for an organic thin film transistor according to the prior art;
Figure 4 is a first energy level diagram for an organic thin film transistor having asymmetric source and drain electrodes according to an embodiment of the present invention;
Figure 5 is a second energy level diagram for an organic thin film transistor having asymmetric source and drain electrodes according to an embodiment of the present invention; Figure 6 is a schematic diagram of an asymmetric source and drain electrode according to an embodiment of the present invention;
Figures 7a and 7b are schematic diagrams of a method of forming an asymmetric source and drain electrode using an offset source according to an embodiment of the present invention;
Figures 8a and 8b are schematic diagrams of a method of forming an asymmetric source and drain electrode using an offset mask according to an embodiment of the present invention;
Figures 9a and 9b are schematic diagrams of a patterned asymmetric source and drain electrode according to an embodiment of the present invention;
Figure 10 is a schematic diagram of a pixel comprising an organic thin film transistor and an adjacent organic light emitting device fabricated on a common substrate according to an embodiment of the present invention; and
Figure 11 is a schematic diagram of an organic thin film transistor fabricated in a stacked relationship to an organic light emitting device according to an embodiment of the present invention.
Throughout the following description like reference numerals shall be used to identify like parts.
Referring to Figure 4, a first energy level diagram for an organic thin film transistor having asymmetric source and drain electrodes according to an embodiment of the present invention comprises an organic semiconductor material 40 having a workfunction of 5.3eV. Preferred organic semiconductor materials 40 include small molecules such as optionally substituted pentacene; optionally substituted polymers such as polyarylenes, in particular polyfluorenes and polythiophenes; and oligomers. Blends of materials, including blends of different material types (e.g. a polymer and small molecule blend) may be used.
A source electrode 42 is provided with a workfunction of 5.3eV matching that of the organic semiconductor material 40. A drain electrode 44 is provided with a workfunction of 4.8eV below that of the organic semiconductor material 40.
A conductive organic material such as a conductive polymer is deposited as the source electrode 42 and the drain electrode 44 is deposited as a metal such as gold. Alternatively both electrodes can be conductive polymers with a workfunction tuned to the desired value. An example of such a conductive polymer is poly(ethylene dioxythiophene) (PEDOT) although other conductive polymers are known in the art. Such conductive polymers may be deposited from solution using, for example, spin coating or ink jet printing techniques.
Alternatively or in combination for a p-channel organic thin film transistor, the source 42 and drain 44 electrodes can be appropriately selected from a high workfunction material, preferably a metal, with a workfunction of greater than 3.5eV, for example gold, platinum, palladium, molybdenum, tungsten, or chromium selected for the required workfunction. Other suitable compounds, alloys and oxides such as molybdenum trioxide and indium tin oxide may also be used. As best seen in Figure 5, an organic semiconductor material 40 comprises a • workfunction of 4.8eV. Accordingly, a source electrode 42 is selected as gold, Au, having a workfunction of 4.8eV matching that of the organic semiconductor material 40. Additionally, a drain electrode 44 is selected as silver, Ag, having a workfunction of 4.3eV.
In both of the examples discussed above in relation to Figures 4 and 5, the source electrode is selected to have a workfunction matching that of the organic semiconductor material for efficient charge injection and carrier mobility. The drain electrode is selected to have a workfunction below that of the organic semiconductor material so that charge extraction is not impeded and so that there exists a barrier to leakage currents in reverse bias or non-use conditions.
For an n-channel OTFT, preferably the source and drain electrodes comprise a material, for example a metal having a workfunction of less than 3.5eV such as calcium or barium or a thin layer of metal compound, in particular an oxide or fluoride of an alkali or alkali earth metal for example lithium fluoride, barium fluoride and barium oxide. Alternatively, conductive polymers may be deposited as the source and drain electrodes.
One technique to deposit an asymmetric source and drain electrode is to firstly deposit a source electrode metal by evaporation through a first mask onto a substrate. The source electrode metal may be gold and deposited by thermal evaporation. A second deposition is performed of the drain electrode metal using a second mask to form the drain electrode. The drain electrode may be silver and also deposited by thermal evaporation. Subsequently, an organic semiconductor material is deposited by a solution deposition technique such as spin coating or ink jet printing into a conductive channel between source and drain electrodes. The organic semiconductor layer is dried using a thermal treatment process.
Referring to Figure 6, a schematic diagram of a precursor 60 to an asymmetric source and drain electrode arrangement 72 comprises a patterned NiCr adhesion layer 62 (shown as a dashed outline) deposited upon a glass substrate 64. Typically the NiCr adhesion layer 62 serves to aid the subsequent adhesion of a further metal 70 (shown as hatched pattern) put down as identical source and drain electrodes 66, 68. However according to an embodiment of the present invention, the NiCr adhesion layer 62 serves to both provide adhesion and also to form an asymmetric source electrode 66 and drain electrode 68. As will be appreciated by a person skilled in the art, NiCr could be replaced by any other suitable contact electrode material for the purpose of this embodiment.
In Figure 6, the further metal 70 has been offset deposited upon the patterned NiCr adhesion layer 62. Accordingly, in the case of the source electrode 66 a portion of the underlying NiCr adhesion layer 62 protrudes from the overlying further metal 70 layer and in the case of the drain electrode 68, the overlying further metal 70 layer protrudes from the underlying NiCr adhesion later 62.
Subsequently, an organic semiconductor material (not shown in Figure 6) is deposited over the source and drain electrodes 66, 68 to fill a channel 70 between the source and drain electrodes 66, 68. The metal closest to the channel 70 for the source electrode 66 is NiCr and the metal closest to the channel 70 for the drain electrode 68 is the further metal 70. The metal closest to the channel 70 dominates the electrical characteristics of the electrode.
With reference to Figures 7a and 7b, we describe a method of forming an asymmetric source and drain electrode 72 of the type described with reference to Figure 6 using an offset source according to an embodiment of the present invention.
Referring to Figure 7a, a glass substrate 64 is exposed to a first NiCr metal source 74 using known line of sight evaporation deposition techniques. A shutter 76 is provided to regulate exposure time and a mask 78 is provided to pattern the NiCr metal upon the glass substrate 64. Following evaporation of the NiCr metal the substrate 64 is therefore provided with a patterned NiCr adhesion layer 62.
Subsequently and with reference to Figure 7b, the glass substrate 64 is exposed to a further metal source 80 such as Au. The location of the source of the further metal 80 is offset from that of the NiCr metal source 74 and so the Au is deposited over the patterned NiCr adhesion layer 62 in an offset manner also as a patterned layer 70 in order to provide an asymmetric source and drain electrode 66, 68 arrangement 72 as described in Figure 6.
With reference to Figures 8a and 8b, we describe a method of forming an asymmetric source and drain electrode of the type described with reference to Figure 6 using an offset mask according to an embodiment of the present invention. Referring to Figure 8a, a glass substrate 64 is exposed to a first NiCr metal source 74 using known line of sight evaporation deposition techniques. A shutter 76 is provided to regulate exposure time and a mask 78 is provided to pattern the NiCr metal upon the glass substrate 64. Following evaporation of the NiCr metal the substrate 64 is provided with a patterned NiCr adhesion layer
62.
Subsequently and with reference to Figure 8b, the position of the mask 78 is offset by a small amount and the glass substrate 64 is exposed to a further metal source 80 such as gold, Au. The location of the further metal source 80 is fixed in the same position as the NiCr metal source 74. This change of metal source without change of relative position can be achieved through use of a carousel arrangement. The Au is deposited over the patterned NiCr adhesion layer 62 in an offset manner also as a patterned layer 70 in order to provide an asymmetric source and drain electrode 66, 68 arrangement 72 as described in Figure 6.
In a further embodiment of the present invention, in addition to providing asymmetric electrodes to promote the injection and extraction of charge in an organic thin film transistor, asymmetric electrodes can be used to control organic semiconductor material crystal growth by controlling the extent of nucleation on the surfaces of the source and drain electrodes and particularly along the channel edge.
Asymmetry in the crystal growth and domain size at source and drain electrodes can improve crystal growth across a channel and eliminate grain boundaries caused when crystals grow from each side of the channel and meet towards the middle of the channel. A grain boundary represents an amorphous rather than ordered portion of a crystal and can present a barrier to the mobility of charge through the crystal. The asymmetry in crystal growth can be introduced by differences in physical shape, patterning and surface chemistry between source and drain electrodes in addition to differences in material composition as described above. The asymmetry in nucleation so that the nucleation of crystals is preferred at one of the source and drain electrodes and so that nucleation is promoted at one electrode and suppressed at the other electrode can also introduced by differences in physical shape, patterning and surface chemistry between source and drain electrodes in addition to differences in material composition as described above. This asymmetry in nucleation can cause crystal formation to commence at one electrode, for example the source electrode and progress across the channel to the other electrode, the drain electrode.
Thus Figure 9a is a schematic diagram of a patterned asymmetric source and drain electrode according to an embodiment of the present invention where the asymmetry between electrodes arises from a difference in the patterning of the electrodes. A gold, Au source electrode 90 and gold, Au drain electrode 92 are provided having a channel 70 therebetween.
The source electrode 90 is patterned with a structure that promotes nucleation and growth of organic semiconductor crystals. The drain electrode 92 has a linear edge. In this case and as illustrated in Figure 9a, both electrodes can be IB
fabricated from the same material and can be deposited in a single masked evaporation process or patterned photolithographically via a lift-off procedure. Such patterns can be sawtooth, castellations, concave or convex semidiscs or other suitable shapes.
Referring to Figure 9b, the source electrode 90 comprises an edge sawtooth pattern and the drain electrode 92 is provided with a complementary sawtooth pattern. By providing one electrode with peaks and the other electrode with corresponding troughs encourages the crystallisation in a direction from one electrode to the other. Such a crystallisation growth can result in a material without grain boundaries which form when crystallisation proceeds from both electrodes at the same time. Since grain boundaries act as barriers to charge transport and can also act as charge trap sites, both of which can reduce overall charge mobility, such a reduce in the formation of grain boundaries is beneficial to the overall performance of the device.
As seen in Figures 9a and 9b the use of a physically patterned electrode structure provides a larger effective width for the transistor, for a given linear width on a device. The larger effective width can allow a use of organic semiconductor materials with lower intrinsic mobility.
In a further embodiment of the present invention, the chemical property or surface energy of the source and drain electrodes can be altered and optimised to promote organic semiconductor crystallisation nucleation and increase the efficiency of charge injection and extraction. Application of a surface treatment to one or both of the source and drain electrodes can be by made by depositing a self-assembled monolayer (SAM) over the source and/or drain electrodes. SAM molecules with polar end groups can be used to provide local wetting and nucleate crystallisation. SAM molecules with hydrophobic end groups (e.g. fluorinated molecules) can be used to provide an anti-wetting "background" that promotes movement of organic semiconductor molecules to the wetting regions.
Such SAM molecules can be deposited using ink jet printing. A particularly preferred SAM molecule comprises F4TCNQ.
OTFTs according to embodiments of the present invention have a wide range of possible applications. One such application is to drive pixels in an optical device, preferably an organic optical device. Examples of such optical devices include photoresponsive devices, in particular photodetectors, and light- emissive devices, in particular organic light emitting devices. OTFTs are particularly suited for use with active matrix organic light emitting devices, e.g. for use in display applications.
Figure 10 shows a pixel comprising an organic thin film transistor 100 and an adjacent organic light emitting device 102 fabricated on a common substrate 104. The OTFT 100 comprises gate electrode 106, dielectric layer 108, source and drain electrodes 110 and 112 respectively, and OSC layer 114. The OLED 102 comprises anode 116, cathode 118 and an electroluminescent layer 120 provided between the anode 116 and cathode 118. Further layers may be located between the anode 116 and cathode 118, such as charge transporting, charge injecting or charge blocking layers. In the embodiment of Figure 10, the layer of cathode material 118 extends across both the OTFT 100 and the OLED 102, and an insulating layer 122 is provided to electrically isolate the cathode layer 118 from the OSC layer 122. The active areas of the OTFT 100 and the OLED 102 are defined by a common bank material formed by depositing a layer of photoresist 124 on substrate 104 and patterning it to define OTFT 100 and OLED 102 areas on the substrate.
In Figure 10, the drain electrode 112 is directly connected to the anode 116 of the organic light emitting device 102 for switching the organic light emitting device 102 between emitting and non-emitting states.
In an alternative arrangement illustrated in Figure 11 , an organic thin film transistor 200 may be fabricated in a stacked relationship to an organic light emitting device 202. In such an embodiment, the organic thin film transistor 202 is built up as described above in either a top or bottom gate configuration. As with the embodiment of Figure 10, the active areas of the OTFT 200 and OLED
202 are defined by a patterned layer of photoresist 124, however in this stacked arrangement, there are two separate bank layers 124 - one for the OLED 202 and one for the OTFT 200. A planarisation layer 204 (also known as a passivation layer) is deposited over the OTFT 200. Exemplary passivation layers 204 include BCBs and parylenes. The organic light emitting device 202 is fabricated over the passivation layer 204 and the anode 116 of the organic light emitting device 202 is electrically connected to the drain electrode 112 of the OFTF 200 by a conductive via 206 passing through passivation layer 204 and bank layer 124. It will be appreciated that pixel circuits comprising an OTFT and an optically active area (e.g. light emitting or light sensing area) may comprise further elements. In particular, the OLED pixel circuits of Figures 10 and 11 will typically comprise least one further transistor in addition to the driving transistor shown, and at least one capacitor. It will be appreciated that the organic light emitting devices described herein may be top or bottom-emitting devices. That is, the devices may emit light through either the anode or cathode side of the device. In a transparent device, both the anode and cathode are transparent. It will be appreciated that a transparent cathode device need not have a transparent anode (unless, of course, a fully transparent device is desired), and so the transparent anode used for bottom-emitting devices may be replaced or supplemented with a layer of reflective material such as a layer of aluminium.
Transparent cathodes are particularly advantageous for active matrix devices because emission through a transparent anode in such devices may be at least partially blocked by OTFT drive circuitry located underneath the emissive pixels as can be seen from the embodiment illustrated in Figure 11.
Thicknesses of the gate electrode, source and drain electrodes may be in the region of 5 - 200nm, although typically 50nm as measured by Atomic Force Microscopy (AFM), for example.
Other layers may be included in the device architecture. For example, in addition to providing a self assembled monolayer (SAM) on the gate, source or drain electrodes one may be provided on the, substrate, insulating layer and organic semiconductor material to promote crystallity, reduce contact resistance, repair surface characteristics and promote adhesion where required. In particular, the dielectric surface in the channel region may be provided with a monolayer comprising a binding region and an organic region to improve device performance, e.g. by improving the organic semiconductor's morphology (in particular polymer alignment and crystallinity) and covering charge traps, in particular for a high k dielectric surface. Exemplary materials for such a monolayer include chloro- or alkoxy-silanes with long alkyl chains, eg octadecyltrichlorosilane.
No doubt many other effective alternatives will occur to the skilled person. It will be understood that the invention is not limited to the described embodiments and encompasses modifications apparent to those skilled in the art lying within the spirit and scope of the claims appended hereto.

Claims

Claims
1. An organic thin film transistor comprising source and drain electrodes, an organic semiconductor disposed in a channel region between the source
5 and drain electrodes, a gate electrode and a dielectric disposed between source and drain electrodes and gate electrode, wherein the source electrode and the drain electrode comprise at least one different physical and/or material property from each other.
2. An organic thin film transistor as claimed in claim 1 , wherein the at least o one different physical and/or material property is a physical structure.
3. An organic thin film transistor as claimed in claim 2, wherein the physical structure comprises patterned surface features.
4. An organic thin film transistor as claimed in claim 3, wherein the patterned surface features are raised surface features and/or
5 indentations.
5. An organic thin film transistor as claimed in claim 4, wherein the raised surface features and/or indentations are selected from a sawtooth profile, castellations and concave or convex profiles.
6. An organic thin film transistor as claimed in claim 5, wherein the source o electrode comprises a patterned surface feature along an edge adjacent the channel region and the drain electrode comprises a patterned surface feature along an edge adjacent the channel region offset from the patterned surface feature of the source electrode such that raised surface features of one electrode are paired with indented surface features of the other electrode.
5 7. An organic thin film transistor as claimed in any one of claims 2 to 6, wherein the different physical structures are formed by stamping or photolithography.
8. An organic thin film transistor as claimed in any preceding claim, wherein the different physical property includes a different surface area of
D electrode.
9. An organic thin film transistor as claimed in any preceding claim, wherein the different physical property includes a different shape of electrode.
10. An organic thin film transistor as claimed in any preceding claim, wherein the different physical property includes a different surface treatment of
5 electrode.
11. An organic thin film transistor as claimed in claim 10, wherein the surface treatment comprises an addition of a self-assembled monolayer.
12. An organic thin film transistor as claimed in any one of the preceding claims, wherein at least one different physical and/or material property is o a different material composition of the source and drain electrodes.
13. An organic thin film transistor as claimed in claim 12, wherein the different material composition provides a different workfunction of source and drain electrodes.
14. An organic thin film transistor as claimed in claim 13, wherein the source 5 electrode has a workfunction greater than or equal to the workfunction of the organic semiconductor and the drain electrode has a workfunction lower than the organic semiconductor.
15. An organic thin film transistor as claimed in any one of the preceding claims, wherein at least one of the source and drain electrodes is a
) conducting organic material.
16. An organic thin film transistor as claimed in claim 15, wherein the conducting organic material comprises a polymer.
17. An organic thin film transistor as claimed in claim 16, wherein the polymer comprises poly(ethylene dioxythiophene).
5 18. An organic thin film transistor as claimed in any of claims 15 to 17, wherein the conducting organic material is deposited by any one of inkjet printing, spin coating or stamp printing.
19. An organic thin film transistor as claimed in any one of claims 12 to 14, wherein the different material composition of the source and drain D electrodes comprises oxidised portions of the source and drain electrodes.
20. An organic thin film transistor as claimed in claim 19, wherein the oxidised portions comprise an oxygen compound.
21. An organic thin film transistor as claimed in claim 20, wherein the oxidised portions comprises oxides of Mo, MoCr, W or V.
22. An organic thin film transistor as claimed in claim 21 , wherein the oxidised portions comprise MoCr-oxide, MOO3, WO3 or V2O5.
23. An organic thin film transistor as claimed in any one of claims 12 to 22, wherein the source and drain electrodes comprise a bilayer of at least two overlapping layers and wherein an upper layer of the bilayer is positionally offset from a lower layer.
24. An organic thin film transistor as claimed in claim 23, wherein an upper layer of the source electrode bilayer overlaps and is adjacent the channel region of the transistor and the lower layer of the drain electrode bilayer is adjacent the channel region of the transistor.
25. An organic thin film transistor as claimed in claim 23, wherein an upper layer of the drain electrode bilayer overlaps and is adjacent the channel region of the transistor and the lower layer of the source electrode bilayer is adjacent the channel region of the transistor.
26. An organic thin film transistor comprising source and drain electrodes, an organic semiconductor disposed in a channel region between the source and drain electrodes, a gate electrode and a dielectric disposed between source and drain electrodes and gate electrode, wherein one or both of the source electrode and the drain electrode are patterned to provide an increased effective channel width contact area at the interface between the organic semiconductor and patterned electrode.
27. An organic thin film transistor as claimed in any preceding claim, wherein the organic thin film transistor is a bottom-gate organic thin film transistor.
28. An organic thin film transistor as claimed in any preceding claim, wherein the organic thin film transistor is a top-gate organic thin film transistor.
29. A method of fabricating an organic thin film transistor comprising source and drain electrodes with a channel region therebetween, a gate electrode, a dielectric layer disposed between the source and drain electrodes and the gate electrode, and an organic semiconductor disposed in the channel region between the source and drain electrodes, the method comprising providing a source and drain electrode that have at least one different physical and/or material property from each other.
30. A method as claimed in claim 29, wherein providing a source and drain electrode that have a different physical property to each other comprises changing the physical structure of at least one electrode.
31. A method as claimed in claim 30, wherein changing the physical structure of at least one electrode comprises surface patterning the electrode.
32. A method as claimed in claim 29, wherein providing a source and drain electrode that have at least one different physical and/or material property from each other includes providing the source electrode with a different surface treatment than the drain electrode.
5 33. A method as claimed in claim 32, wherein the surface treatment includes seeding a surface of the source and/or drain electrodes with a crystallisation region and whereby the organic semiconductor material crystallises at the crystallisation region.
34. A method as claimed in claim 29, wherein providing a source and drain o electrode that have a different material property to each other comprises depositing a source electrode with a different workfunction to the drain electrode.
35. An asymmetric organic thin film transistor substantially as hereinbefore described and/or with reference to Figures 4 to 11 of the accompanying
5 drawings.
36. A method of fabricating an asymmetric organic thin film transistor substantially as hereinbefore described and/or with reference to Figures 4 to 11 of the accompanying drawings.
PCT/GB2009/000668 2008-03-19 2009-03-12 Organic thin film transistor Ceased WO2009115772A1 (en)

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US12/933,675 US8829494B2 (en) 2008-03-19 2009-03-12 Organic thin film transistor
KR1020107023283A KR101509420B1 (en) 2008-03-19 2009-03-12 Organic thin film transistor
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CN102017211A (en) 2011-04-13

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