CN1764551A - Shift method and the donor element of thermo-sensitive material to substrate - Google Patents

Shift method and the donor element of thermo-sensitive material to substrate Download PDF

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Publication number
CN1764551A
CN1764551A CNA2004800083329A CN200480008332A CN1764551A CN 1764551 A CN1764551 A CN 1764551A CN A2004800083329 A CNA2004800083329 A CN A2004800083329A CN 200480008332 A CN200480008332 A CN 200480008332A CN 1764551 A CN1764551 A CN 1764551A
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layer
substrate
donor element
recipient
fragility
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Chinese (zh)
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G·B·芬切尔
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
    • B41M5/38214—Structural details, e.g. multilayer systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/18—Deposition of organic active material using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/30—Thermal donors, e.g. thermal ribbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • 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

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Thin Film Transistor (AREA)
  • Electroluminescent Light Sources (AREA)
  • Formation Of Insulating Films (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

Disclose the method that forms patterned semiconductor-dielectric substance by by the use of thermal means on substrate, but comprised heating thermal imaging donor element, donor element comprises that substrate and semi-conducting material are in conjunction with dielectric transfer layer.With the required pattern that will on recipient, form just as the exposure alms giver, thereby the exposed portion of semiconductor and dielectric material layer is shifted simultaneously, forms the required pattern of semiconductor and dielectric substance on recipient.Semi-conducting material can be patterned the formation thin film transistor (TFT).Method also can be used for forming the pattern of light emitting polymer or little molecule and electric charge injection layer to form the active display of photosensitive organic used for electronic device.Also disclose and be used for the method donor element.The method that forms thin film transistor (TFT) and the used donor element of method is also disclosed.

Description

Shift method and the donor element of thermo-sensitive material to substrate
Invention field
The present invention relates to shift the method for fragility or thermo-sensitive material by thermal imaging method.The present invention+also relate to sandwich construction that is used to carry out this method.These methods comprise that the heat transfer by induced with laser is imaged on the pattern that forms light emitting polymer or semiconductor-dielectric material on the substrate.The present invention relates to form the method for film organic transistor (TFT) and polymer light-emitting display (PLED) by this by the use of thermal means.
The invention technical background
Made thin film transistor (TFT), organic semiconducting materials such as pentacene, poly-inferior thienyl ethenylidene (polythieneylenevinylene), thiophene oligomers, benzothiophene dimer and polyacetylene in conjunction with organic semiconducting materials.Organic material also can be used for forming transistorized other element, as the conductive layer that forms grid, source electrode and drain electrode with form dielectric insulating barrier.
The all or part of comparable conventional transistor of being made by organic material of transistor is cheaply made with being easy to.Although also do not reach and silicon transistor components identical density, the low cost of organic transistor means that they can be used for not requiring high density and the uneconomic application of conventional transistor.For example, organic transistor can be used for cheapness or one-time item, as electronic paper, placard and books, smart card, toy, utensil be used for the electronic bar code of product sign.Organic transistor also can be flexible, and this is favourable in some applications.For example, the flexible transistor array can be used for LCD (LCD), kneetop computer and the TV of flexible electrophoretic display, PLED and computer.Although the saving of manufacturing cost is that significantly the further reduction of organic transistor manufacturing cost is favourable.
Can organic material be applied on the transistorized part by spin coating, casting, printing or other method.Some organic materials also can apply by physical gas-phase deposite method.The electroactive polymer presoma also can be applied in and change into polymer, and is general by heating.Use mask that direct pattern can be provided in deposition process.If use photoresist in deposition process, then post-depositional wet chemical etching is essential, and this may cause organic semi-conductor seriously to be demoted.Although the manufacturing technology that needs than silicon-based transistor easily and cheap, that this method remains is complicated, slow, lack enough decomposing force, expose device in harmful heat and chemical process, and more expensive than essential.
Make the potentiality that organic transistor provides further cost to reduce by printing technology fully.People's such as F.Garnier " All Polymer Field-Effect Transistor Realized byPrinting Techniques ", Science, 265 volumes, on September 16th, 1994, the 1684-1686 page or leaf discloses by seeing through mask deposition electrically conductive graphite based polyalcohol printing ink formation grid, source electrode and drain electrode and has formed transistor.With α, ω-two (hexyl) six thiophen semiconductors materials deposit in source electrode and the drain electrode by flash distillation.
People's such as Z.Bao " High-Performance Plastic Transistors Fabricated byPrinting Techniques ", Chem.Mater.1997,9,1299-1201 discloses the transistorized production of high-performance, and wherein primary element is printed directly on the plastic supporting base that scribbles tin indium oxide (ITO).Use mask to form the printed patterns of transistor unit.
Ink jet printing also is used to apply organic semiconducting materials.Referring to US6087196, EP0880303A1, WO99/66483 and WO99/43031.Although help manufacture process, to use for some, serigraphy and ink jet printing can not provide enough decomposing force.In addition, also be difficult to control the glacing flatness and the uniformity of final film in the ink jet printing process.
Thermal transfer method is well-known in using as color proof.This thermal transfer method comprises that for example dye sublimation, dyestuff shift, fusion is shifted and ablator shifts and generally uses the imaging heat of laser instrument induced material to shift.These methods are described among UK2083726, US4942141, US5019549, US4948776, US5156938, US5171650 and the US4643917.
The thermal transfer method of induced with laser generally uses donor element, comprises the material layer (" transfer layer ") and the recipient element that will be transferred, and comprises the surface that is used to accept material for transfer.The substrate of donor element or recipient element is transparent, or the both is transparent.Make donor element and recipient element closely near or contact with each other, and optionally be exposed to laser emission, utilize infrared laser usually.Expose portion at transfer layer produces heat, and these parts of transfer layer are transferred on the surface of recipient element.If the material of transfer layer can not absorb the laser emission of incident, then donor element must comprise the zone of heating near transfer layer.Ejection (ejection) layer of the polymeric material of can vaporizing also can be provided between zone of heating and alms giver's carrier, and it resolves into gaseous molecular when being heated.The expose portion that promotes transfer layer that is decomposed into of ejection layer provides additional force to the recipient element.
In a kind of digital thermal transfer method of induced with laser, only expose and take place once, thereby the transfer of material from donor element to the recipient element can be once by accumulation 1 pixel at the little selection area that installs.Computer control helps the transfer of high-speed and high definition.Perhaps, in similar approach, the whole device of radiation, but and use mask optionally to expose the required part (US5937272) of thermal imaging layer.
The thermal transfer method of induced with laser is generally than above-mentioned coating, deposition with become the pattern method fast and cheap, and allows high definition ground formation characteristic pattern.Although project of printing provides at a high speed in printing machine, large tracts of land printing and high definition, the by the use of thermal means of induced with laser has the attendant advantages that does not need follow-up printed layers solvent compatibility, thereby has enlarged the scope that can use material.But, also do not have to realize direct heat printing to the ultrathin film of the semiconductor of the responsive fragility of disturbance (for example big thermograde, humidity, pressure or mechanical stress) or luminous organic material.The trial of thermal transfer material such as pentacene, copper fluoride phthalocyanine or luminous organic material causes the severely degrade and/or the part evaporation of material usually.
The thermal transfer method that needs a kind of thermal transfer method, especially induced with laser can be used for making organic transistor and the used organic semiconducting materials of other organic electronic device forms with manufacturing luminescent device such as used the applying with pattern of luminescent material of display.
Summary of the invention
Method of the present invention provides a kind of method of using thermal imaging method to shift fragility or thermo-sensitive material.Method of the present invention comprises:
A. form donor element, this donor element comprises:
I. substrate; With
Ii. the transfer layer and the protective layer between substrate and fragility or heat-sensitive layer that comprise fragility or thermo-sensitive material;
B. the transfer layer of placing donor element contacts with the recipient element; With
C. the selection zone that exposes donor element to laser emission to shift the sandwich construction that the part transfer layer forms patterning to the recipient element.
But the present invention also provides the thermal imaging donor element, comprising:
A. substrate;
B. zone of heating;
C. protective layer; With
D. fragility or heat-sensitive layer.
Method of the present invention and donor element are used to make thin film transistor (TFT) and polymer light-emitting display.
The accompanying drawing summary
Fig. 1 is the transistorized side view of thermal imaging.
Fig. 2 is top contact thin film transistor (TFT) and the transistorized side view of end contact membrane.
Fig. 3 is the side view of polymer LED (PLED).
Fig. 4 is the figure of printed transistor IV characteristic.
Fig. 5 is the scintigram of printed transistor.
Detailed Description Of The Invention
Term used herein " organic electronic device " refers to that wherein any element such as semiconductor, conduction or light-sensitive element all are the electronic device of organic material.
The term " vicinity " that also uses herein must not refer to that a layer directly is next to another layer. Can think to provide one or more intermediate layers in the middle of the layer located adjacent one another.
Method of the present invention provides by thermal imaging and has shifted temperature-sensitive or fragile material to the method for recipient element from donor element. This method is particularly useful for making organic electronic device such as TFT and PLED. Fragility or thermo-sensitive material are incorporated in the transfer layer of donor element, and are not subjected to produce in the thermal transfer method impact of heat owing to protective layer. The example of interested especially fragility or thermo-sensitive material is organic or inorganic semiconductor, light emitting polymer and little molecule emitter, but method also can be used for shifting firmer material. Protective layer can be included in the structure electronic device also useful material. Dielectric and charge injection material are respectively preferred protective layers during TFT and PLED make. Method of the present invention also can be used for shifting simultaneously one or more electroactive layers, and the process simplification and the registration fidelity that cause making in the multilayer electronic device architecture are improved.
In one embodiment of the present invention, disclose the thermal imaging method of the pattern of a kind of formation semi-conducting material (for example p-or n-type organic or inorganic semiconductor) and dielectric material, wherein material is transferred to simultaneously on the recipient that forms pattern or do not form pattern and is formed sandwich construction. Sandwich construction can be used for electronic device, includes organic electronic device. For example, semiconductor layer and dielectric layer can be transferred to by method heat of the present invention and before be deposited on the source electrode and drain electrode of accepting on the substrate, then can form " end contact membrane transistor " by the print gates layer on the semiconductor layer that shifts and dielectric layer top. In the preferred embodiment of this method, donor element comprises flexible substrate, scribbles zone of heating and the semiconductor layer on the dielectric layer top of dielectric layer. When this alms giver of thermal imaging, semiconductor layer is directly transferred in source electrode (112) and the drain electrode (114), electrolyte (118) and semiconductor layer (16) are transferred simultaneously, with identical pattern and do not destroy semiconductor-dielectric interface. Can shift other dielectric layer to cover any irregularity part of the first dielectric layer by thermal imaging or other technology. Can grid layer (120) be printed onto on the dielectric layer by thermal imaging or conventional method, to finish the transistorized manufacturing (seeing Fig. 2) of end contact structures.
Perhaps, in " top contact " structure, grid will be printed on the recipient, then print dielectric by thermal imaging or other printing process at grid. Next depositing semiconductor layers applies source electrode and drain electrode on the semiconductor layer top at last, shifts or other printing process by heat.
Except semiconductor-dielectric layer, method of the present invention can be a plurality of dielectric layers and forms pattern, as long as the pattern of each layer is identical in a plurality of layer. For electric insulation, can apply continuous dielectric layer.
Also can use negative imaging pattern to form pattern for one or more layers simultaneously. In negative imaging pattern, remove the zone of required pattern outside by laser ablation or alternate manner to form the layer (for example semiconductor layer, dielectric layer or dielectric+semiconductor layer) of patterning. Then but the layer of registration lamination pattern is to other element of the source electrode that prints and drain electrode or required electronic device. This negative formation method also can be combined with the formation electronic device with method of the present invention.
Can negative be imaged on the upper dielectric that forms patterning of alms giver and organic semiconductor layer manufacturing in conjunction with the organic semi-conductor thin film transistor (TFT) by utilizing. Then utilize the dielectric and the organic semiconductor layer that are laminated to source electrode and the upper deposit patterned of drain electrode, then deposit grid.
In different transistor arrangements, the pattern of dielectric substance can shift by heat and directly transfer on the grid layer. After the transfer that is printed on dielectric layer of source electrode and drain electrode. Then then the organic semiconducting materials that utilizes method of the present invention to shift to have protective layer deposits grid on source electrode and drain electrode layer.
In another embodiment of the present invention, the thermal transfer method of the pattern of formation light emitting polymer (or little molecule emitter) and charge injection material is disclosed, wherein polymer and charge injection material are transferred on the recipient element simultaneously. In this method, donor element comprises the charge injection material layer of substrate, adjacent substrate and the light emitting polymer of adjacent charge implanted layer (or little molecule emitter) layer. Donor element also can comprise zone of heating between substrate and electric charge injection layer, and comprises optional ejection layer between substrate and zone of heating. In this method; electric charge injection layer is as protective layer; the responsive light emitting polymer (or little molecule emitter) of protection can directly not be exposed to the heat that laser beam produces, and allows organic luminescence polymer and little molecule emitter directly not to shift with degrading. This method has also been eliminated tediously long lamination step, if set up illuminator/charge injection pattern by negative imaging, then it is essential. This method of the present invention makes manufacturing low cost, polychrome, active display become possibility. In this embodiment, the use of light emitting polymer is preferred.
In order to form the required pattern of semi-conducting material and dielectric material according to the preferred embodiments of the invention at recipient, but provide the donor element (10) of thermal imaging. Donor element comprises substrate (12), optional ejection layer (14), zone of heating (18) and comprises dielectric layer (16) and the transfer layer of semiconductor layer (15), as shown in Figure 1. Fig. 1 also shows the recipient element (20) of the adhesive layer (24) that comprises base member (22) and choose wantonly. The expose portion of transfer layer (17) is transferred on the recipient element.
Substrate (12) is for being applicable to the material of electronic device. Substrate (12) is preferably flexible and transparent, and to be conducive to exposing donor element (10) by laser emission, this further describes hereinafter. Suitable transparent membrane comprises polyester (most preferably PETG), polyether sulfone, polyvinyl chloride, polyimides, poly-(vinyl alcohol-be total to-acetal), polyethylene and cellulose esters, such as cellulose acetate.
Suitable dielectric comprises polycarboxylated styrene, polyvinylpyridine, polyvinylphenol, glass resin, fluorinated copolymers and methacrylic acid copolymer.
Suitable organic semiconducting materials comprises pentacene, six thiophene, aphthacene, poly-inferior thienyl ethenylidene, thiophene oligomers, benzothiophene dimer and polyacetylene.Suitable inorganic semiconductor material comprises ZnO 2, CdS and non-crystalline silicon.
The ejection layer also can be provided between substrate and zone of heating.Ejection layer (14) comprises having low decomposition temperature preferably less than about 275 ℃ material.The ejection layer is preferably nonmetallic.Suitable material comprises NC Nitroncellulose, polyvinyl chloride, chliorinated polyvinyl chloride, polymethyl methacrylate and polymethacrylate copolymer.The ejection layer typically is about 1 micron thickness.
Ejection layer (14) also can comprise the radiation absorbing dye that is dissolved in the low decomposition temperature adhesive.Absorbing dye absorbs the radiation in the exposure Laser emission bands of a spectrum.Typically, the radiation in the exposure Laser emission infra-red range, absorbing dye is an infrared absorbing dye.Suitable infrared absorbing dye is TIC-5c (2-[2-[2-chloro-3[[1,3-dihydro-1,3,3-trimethyl-2H-indoles-2-subunit] ethylidene]-1-cyclopentene-1-yl] vinyl]-1,3,3-trimethyl-3-H-indoles, with salt (1: 1), the CAS#128433-68-1 of trifluoromethayl sulfonic acid), can be from E.I.DuPont de Nemours, Inc. (Wilmington DE) obtains.The substituted dyes that absorbs at 830nm comprises ADS 830 (2-[2-[2-chloro-3-[2-[1,3-dihydro-1,1-dimethyl-3-(4-sulfo group butyl)-2H-benzo [e] indoles-2-subunit] ethylidene]-1-cyclohexene-1-yl] vinyl]-1,1-dimethyl-3-(4-sulfo group butyl)-1H-benzo [e] indoles, inner salt, free acid, CAS#162411-28-1); And SQS ((4-[[3-[[2,6-two (1, the 1-dimethyl ethyl)-and 4H-thiapyran-4-subunit] methyl]-2-hydroxyl-4-oxo-2-cyclobutane-1-subunit] methyl]-2,6-two (1, the 1-dimethyl ethyl)-and thiapyran, hydroxide, inner salt, CAS#88878-49-3 also can be from E.I.DuPont de Nemours, Inc. (Wilmington DE) obtains.Laser can be with other wavelength bands of a spectrum emission, so select to absorb the dyestuff of radiation in those specific wavelength bands of a spectrum.
Dielectric layer also can comprise the dyestuff of a small amount of absorption laser emission such as the dyestuff of listing above.
Can comprise also in the ejection layer (14) that foaming agent is to increase the propulsive force that produces in the ejection layer.Suitable foaming agent comprises: diazoparaffins (diazo alkyls); Diazol; Nitrine (N 3) compound; Ammonium salt; Can be decomposed to form the oxide of oxygen; Carbonate and peroxide.For example, can use diazonium compound such as 4-diazo-N, N '-diethylaniline borofluoride.Also can use the mixture of foaming agent.
Zone of heating (18) is preferably the thin metal layer that can absorb incident radiation.The preferred Ni of metal, Al, V or Cr, thickness make layer show the absorption maximum (25-35%) of incoming laser beam.The Ni layer of preferred 30-150 .
The transfer layer of semiconductor (15) and electrolyte (16) material can comprise by evaporation or be dissolved into the organic semiconducting materials that deposits on the suitable dielectric.The suitable dielectric layer of organic transistor comprises having high dielectric constant materials.The electric capacity of dielectric layer is generally at least 10 -8F/cm 2In addition, the semiconductor that dielectric layer is necessary for evaporation provides suitable interface, so that their crystallite size and corresponding field-effect mobility are big.
Recipient element (20) comprises substrate (22) and optional adhesive phase (24).Substrate (22) is the sheet material of dimensionally stable.Suitable sheet material comprises the transparent membrane of PETG, polyether sulfone, polyimides, poly-(vinyl alcohol-be total to-acetal), polyethylene or cellulose esters such as cellulose acetate.The recipient substrate also can be opaque material, as is filled with the PETG of Chinese white such as titanium dioxide; Ivory; Or synthetic paper, as Tyvek Spunbond polyolefin.
The adhesive phase (24) of recipient element (20) can be any low Tg polymer.The suitable bonding material comprises Merlon; Polyurethane; Polyester; Polyvinyl chloride; Styrene/acrylonitrile copolymer; Poly-(caprolactone); The copolymer of vinylacetate and ethene and/or vinyl chloride; (methyl) Voncoat R 3310 (as butyl methacrylate) and copolymer; With their mixture.Also can use contact adhesive.
In the method for the invention, make the donor element (10) of Fig. 1 contact formation assembly (30) with recipient element (20).The outer surface of transfer layer (17) contacts with adhesive coating (24), if present.If adhesive coating (24) does not exist, then the outer surface of transfer layer (17) contacts recipient substrate (22).
Can use vacuum and/or pressure that donor element (10) and recipient element (20) are secured together formation assembly (30).In one embodiment, can donor element (10) and recipient element (20) be secured together by the layer at the peripheral place of fuser assembly.In another embodiment, available belt is held together donor element (10) and recipient element (20), is bonded on the imaging device then.Also can use pin/matched moulds system.In yet another embodiment, donor element can be laminated on the recipient element.If donor element (10) and recipient element (20) are flexible, then assembly (30) can be installed on the roller easily to help laser imaging.
Assembly (30) optionally is exposed to laser emission (R), the required pattern (see figure 1) of exposing patterns for forming on substrate.Laser emission or laser beam (R) are focused on the interface portion between dielectric layer (16) and the zone of heating (18).The neighbouring part of the exposed portion heating ejection layer (14) of dielectric layer (16) causes the decomposition and the evaporation of ejection layer (14), and the exposed portion that advances transfer layer (17) is to recipient.Required transfer layer (17) part of electrolyte (16) and semi-conducting material (15) therefore is transferred on the recipient element (20), stays unwanted patterns of material on substrate (12).
After the exposure, separately donor element (10) and recipient element (20) stay unwanted dielectric (16) and semiconductor (15) layer segment on substrate (12), stay the imaging moiety of transfer layer (17) on recipient element (20).Can further process the sandwich construction that obtains then and form required organic electronic device.For example, can use method of the present invention to make the OTFT of organic semiconducting materials.
Preferably apply radiation, as shown in Figure 1 by substrate element (12).About 600mJ/cm can be up to 2The laser flow under provide laser emission, preferably about 75-440mJ/cm 2Can use various types of laser instrument exposure transfer layers (17).Laser instrument is preferably launched in infrared, near-infrared or visibility region.Especially advantageously the diode laser of launching in the 750-870nm zone, reason are that their small size, low cost, stability, reliability, intensity and modulation is convenient.The diode laser of launching in the 780-850nm scope is most preferred.This laser instrument can (San Jose CA) obtains from Spectra Diode Laboratories.Also can use the laser instrument of other type and emitted laser device in other wavelength bands of a spectrum.
By the protective layer that directly is exposed to the heat that produces in the transfer process is provided, method of the present invention also can be used as the thermal imaging method that shifts the material layer that is as thin as about 100 -150 .Also transferable thicker layer (promptly greater than 150 ).
Fig. 2 has shown the side view of going up the end contact structure of the film polymer transistor of making (104) at substrate (100).Transistor (104) comprising: source electrode (112) on substrate (100) and drain electrode (114); Organic semiconducting materials (116) in source electrode (112) separately and drain electrode (114); Dielectric substance on organic semiconducting materials (18) layer forms insulating barrier; With the conductive material layer on insulating barrier (118), form gate electrode (120).
Fig. 2 has also shown the TFT (102) of top contact (bottom-gate) structure.This TFT comprises: the gate electrode (120) on substrate (100); The layer of the dielectric substance on grid layer (118); Source electrode on dielectric (112) and drain electrode (114); Semiconductor layer (116) in source electrode (112) and drain electrode (114); With other dielectric layer as encapsulated layer (119, not shown) at this.In top contact TFT structure (102), after forming required gate pattern (120), apply dielectric layer (118) by thermal imaging or alternative method, then depositing semiconductor layers (116).On the top of organic semiconducting materials (116) pattern, apply one group of source electrode (112) and drain electrode (114).In source electrode (112) and drain electrode (114), apply encapsulated layer (119).In top contact structure, second dielectric layer (encapsulated layer (119)) is as the barrier layer, and helps the transfer of semiconductor layer and degradation not.If gate electrode (118), source electrode (112) and drain electrode (114) are connected on the electromotive force, then when gate electrode (118) when being opened, electric current will flow to drain electrode (114) by organic semiconducting materials (116) from source electrode (112).
If produce by thermal imaging, then the gap between source electrode (112) and the drain electrode (114) can be as small as a pixel (5 microns).The thickness of source electrode (112) and drain electrode (114) can be about 100 to about 10000 .The thickness of dielectric layer (118) can be about 100 to about 15000 .If by the thermal evaporation deposition, the thickness of semiconductor layer (116) can be about 50 to about 2000 , if from solution-cast, then is up to 10000 .In end contact TFT, in source electrode (112) and drain electrode (114), apply organic semiconductor and pattern of dielectric material.
Can use method of the present invention to make the polymer light-emitting display.Fig. 3 has shown the side view of PLED.Flexible substrate (200) scribbles ITO, and it constitutes the positive pole (201) of display.Apply electric charge injection layer (202) and light emitting polymer (203) atop.
Embodiment
Non-limiting example has illustrated the method for thin electrolyte of the transfer of this paper requirement and description and semiconductor layer.Following amount provides with wt%.The CREO unit comprises that 81.2cm is long, the roller of girth 91cm.CREO 3244 Spectrum Trendsetter Exposure Unit (can be from Creo-Scitex, Inc., Vancouver, Canada obtains) and comprising the outer diode laser of 20 tile reds, it launches the laser beam of 830nm when 1 microsecond pulse width.Cut apart the array that laser beam forms 240 5 microns overlapping * 2 microns hot spots by light valve.GMA is a glycidyl methacrylate; MMA is a methyl methacrylate; BA is a butyl acrylate; With MMA be methacrylic acid.
Embodiment 1
Use four donor elements to print the TFT of the end contact structure of describing in the following examples by thermal imaging.Each of donor element comprises the thick Mylar of 4 mils (0.0363mm) Substrate, the 400D optical clarity can be from E.I.DuPont de Nemours, and (Wilmington DE) obtains Inc., is coated with extremely about 40% light transmittance of 100 nickel by electron beam deposition.
According to the polyaniline (PANI) of the process of describing among the US5863465 by the emulsion polymerization prepared use.Use dinonylnaphthalene sulfonic acid (DNNSA) as adulterant.Doped P ANI is called as PANI-DNNSA hereinafter.The adding of control DNNSA makes the sulphur atom molal quantity of acid equal the molal quantity of nitrogen-atoms in the PANI skeleton.This confirms by elementary analysis behind washing, separation and the dry PANI-DNNSA that obtains.Utilize following processes to use the audio frequency Dukane ultrasonoscope that has horn probe that CNT is dispersed among the PANI-DNNSA.Hybrid laser CNT in 2 ounces of bottles, 59mg, (CNI, Houston is TX) with 19.03g dimethylbenzene.With the horn probe dispersed mixture that is immersed in certain depth in the mixture 10 minutes, thereby observe stable mixing eddy current.In nanotube/xylene mixture, add PANI-DNNSA (5.9g, in dimethylbenzene, 32.9% solid).The mixture that obtains disperseed 5 minutes again, and twice in vibration bottle is so that wash CNT from bottle wall upper punch therebetween.Use a #10Meyer rod that DNNSA-PANI/SWNT solution is coated on the electron beam deposition Ni layer to 1.2 micron thickness.Dry rear film comprises the NT of 3wt% and the polyaniline of 97wt%.The DNNSA-PANI/SWNT donor element is used for print gates and source electrode and drain electrode.
By being coated with on the Mylar  film of Ni the donor element that coating polyvinyl pyrelene to 1.1 micron thickness prepares dielectric-semiconductor layer.(Sigma-Aldrich, Milwaukee WI) are evaporated on dielectric-semiconductor layer with pentacene to use Kurt Lesker evaporimeter then.Pentacene thin film is 6 " * 6 " the zone at room temperature be evaporated with the speed of 0.3 .The thickness of pentacene layer is 250 , and this uses quartz crystal to record.By following printing 3 " * 3 " base plate.
DNNSA-PANI/SWNT donor element and recipient element are loaded on the CREO3244 spectrum Trendsetter Exposure Unit.The recipient element is the 4 mil Mylar  films that scribble 1.4 micron films, and 1.4 micron films are obtained by GMA 2%/MMA51%/BA 40%/MMA 3% latex (solid of 33wt%), and glass transition temperature is 39 ℃.
Printing source electrode and drain electrode layer under 3.45 watts laser flow, roller speed remains on 100RPM.Laser beam is focused between nickel dam and the DNNSA-PANI/SWNT at the interface.Nickel absorbs the laser beam of incident, makes at its organic matter at the interface and partly decomposes, and gaseous decomposition product advances the exposed portion of DNNSA-PANI/SWNT conductive layer to the recipient element.After the formation of source electrode and drain electrode is finished, semiconductor-dielectric alms giver is loaded on 3244 Trendsetter that replace the DNNSA-PANI/SWNT donor element.Semiconductor-dielectric donor element is exposed under 7 watts.After removing the donor element different, keep being registrated to pixel level with reorientation.Because the glass transition point of coating is low on the recipient element, so it is for the transfer of semiconductor surface and to be attached on the recipient element be enough to glue.
At last, use DNNSA-PANI/SWNT donor element print gates on the dielectric layer top of shifting of before in the printing of source electrode and drain electrode, describing.Grid layer is 3.6 watts of exposures down.
The IV characteristic of a printed transistor is shown in Fig. 4, and grid voltage is from 0 to 100V, and Vsd is in same scope.The scintigram of printed transistor also is shown in Fig. 5.

Claims (28)

1. method comprises:
A. form donor element, this donor element comprises:
I. substrate; With
Ii. transfer layer, wherein transfer layer comprises fragility or thermo-sensitive material, and the protective layer between substrate and fragility or heat-sensitive layer;
B. the transfer layer of placing donor element contacts with the recipient element; With
C. the selection zone that exposes donor element forms sandwich construction just as, patterning to laser emission to the recipient element to shift the part transfer layer.
2. the process of claim 1 wherein that donor element also comprises the ejection layer between transfer layer and substrate.
3. the method for claim 2 wherein sprays layer and comprises that decomposition temperature is lower than 275 ℃ organic material.
4. the method for claim 3 wherein sprays layer and is selected from NC Nitroncellulose, polyvinyl chloride, chliorinated polyvinyl chloride, polymethyl methacrylate and polymethyl methacrylate copolymer.
5. the method for claim 2 wherein sprays layer and also comprises the radiation absorbing dye.
6. the method for claim 5, wherein the radiation absorbing dye is an infrared absorbing dye.
7. the method for claim 6, wherein infrared absorbing dye is selected from 2-[2-[2-chloro-3-[(1,3-dihydro-1,3,3-trimethyl-2H-indoles-2-subunit) ethylidene]-1-cyclopentene-1-yl] vinyl]-1,3,3-trimethyl-3-H-indoles, with the salt (1: 1) of trifluoromethayl sulfonic acid; 2-[2-[2-chloro-3-[[1,3-dihydro-1,1-dimethyl-3-(4-sulfo group butyl)-2H-benzo [e] indoles-2-subunit] ethylidene]-1-cyclohexene-1-yl] vinyl]-1,1-dimethyl-3-(4-sulfo group butyl)-1H-benzo [e] indoles, inner salt, free acid; And 4-[[3-[[2, two (1, the 1-the dimethyl ethyl)-4H-thiapyran-4-subunits of 6-] methyl]-2-hydroxyl-4-oxo-2-cyclobutane-1-subunit] methyl]-2, two (1, the 1-the dimethyl ethyl)-thiapyrans of 6-, inner salt.
8. the process of claim 1 wherein that the substrate of donor element is a fexible film.
9. the method for claim 8, wherein fexible film comprises the polymer that is selected from polyester, polyether sulfone, polyvinyl chloride, polyimides, poly-(vinyl alcohol-altogether-acetal), polyethylene and cellulose esters.
10. the process of claim 1 wherein that fragility or thermo-sensitive material include dynamo-electric activated material.
11. the method for claim 10, wherein organic electric activating material comprise luminescence polymer material or luminous little molecule, protective layer comprises electric charge injection layer, and the recipient element comprises substrate and anode layer.
12. the method for claim 11, wherein anode layer comprises indium tin oxide target.
13. the polymer LED of making according to the method for claim 12.
14. the fragility of the process of claim 1 wherein or thermo-sensitive material comprise organic or inorganic semiconductor, protective layer comprises dielectric substance.
15. the method for claim 14, wherein organic semiconductor is selected from pentacene, six thiophene, aphthacene, poly-inferior thienyl ethenylidene, thiophene oligomers, benzothiophene dimer and polyacetylene.
16. the method for claim 14, wherein dielectric substance is selected from polycarboxylated styrene, polyvinylphenol, polyvinylpyridine, glass resin, fluorinated copolymers and methacrylic acid copolymer.
17. the method for claim 14, wherein the recipient element comprises the conductive layer of substrate and patterning.
18. the method for claim 17, wherein the substrate of recipient element comprises mineral-filled polyester, ivory or spunbond polyolefin.
19. the method for claim 14, wherein the recipient element also comprises adhesive phase.
20. the method for claim 19, wherein adhesive phase comprises and is selected from Merlon; Polyurethane; Polyester; Polyvinyl chloride; Styrene/acrylonitrile copolymer; Poly-(caprolactone); At least a copolymer in vinylacetate and ethene and the vinyl chloride; (methyl) Voncoat R 3310; (methyl) acrylate copolymer; With their polymer of mixture.
21. the method for claim 14, wherein donor element also comprises the ejection layer between transfer layer and substrate.
22. the method for claim 14, wherein donor element also comprises zone of heating between substrate and transfer layer.
23. the method for claim 22, wherein zone of heating comprises the thin layer of Ni, Al or Cr.
24. the method for claim 17, wherein the conductive layer of patterning comprises transistorized source electrode and drain electrode.
25. the method for claim 24, wherein the conductive layer of patterning also comprises interior connection.
26. but the donor element of a thermal imaging comprises:
A. substrate;
B. zone of heating;
C. protective layer; With
D. fragility or heat-sensitive layer.
But 27. the thermal imaging donor element of claim 26, wherein:
Substrate is a fexible film, and fexible film comprises the polymer that is selected from polyester, polyether sulfone, polyvinyl chloride, polyimides, poly-(vinyl alcohol-be total to-acetal), polyethylene and cellulose esters;
Zone of heating comprises the thin layer of Ni, Al or Cr;
Protective layer comprises dielectric substance or electric charge injection material; With
Fragility or heat-sensitive layer comprise organic semiconductor or light emitting polymer or luminous little molecule.
28. the donor element of claim 27 wherein deposits fragility or heat-sensitive layer by evaporation or from solution-cast at protective layer.
CNA2004800083329A 2003-03-27 2004-03-25 Shift method and the donor element of thermo-sensitive material to substrate Pending CN1764551A (en)

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