Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
• • 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
• • 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
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
  • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen 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
  • H10K85/60—Organic compounds having low molecular weight

Definitions

• the invention relates to a method for manufacturing an injection self-assembled monolayer (SAM) comprising molecules comprising a terminal thiol group on the surface of a metal support.
• SAM injection self-assembled monolayer
• the self-containing monolayers of molecules having a terminal thiol, grafted onto a metal support such as gold, silver, copper, nickel, platinum, palladium and aluminum, are used in the manufacture of organic electronic transistors to optimize the electronic transfer between the electrodes and the semiconductor material of the transistor. These are injection SAMs.
• Meirav Cohen-Atiya et al describe the adsorption of alkanethiols on different metal surfaces, such as gold, silver and mercury, by immersing the metal surface in a solution and adding the alkanethiols in this solution then that the metal surface is submerged.
• the metal surface is covered by up to 60%, which, on the contrary, means that 40% of the metal surface is not covered.
• holes i.e., empty surfaces, without grafted molecules, and other defects may exist in these monolayers deposited by liquid means.
• metal surfaces such as, for example, copper, chromium, aluminum and silver.
• This method was used for SAM training.
• a solution of octadecyltrichlorosilane (OTS) in anhydrous hexane is applied to the surface of poly (dimethylsiloxane) (PDMS) buffers.
• OTS octadecyltrichlorosilane
• the buffers are then dried by centrifugation.
• the "inked” pad is then contacted with the surface of the ITO substrate and a slight pressure is applied at 80 ° C, which facilitates the spontaneous formation of Si-O bonds and forms dense and very well localized SAMs.
• SAMs are regions terminated by methyl functionality.
• the molecules used to form the SAM are trichlorosilanes
• the substrate is made of ITO
• the applied pressure is called “light”
• the temperature used is 80 ° C.
• the improvement obtained in the performance of organic light emitting diodes (OLEDs) is said to be “subtle”, compared to OLEDs having no monoassembled layers.
• a pentacene-based thin film transistor was fabricated on the surface of a dielectric material by micro-contact printing.
• a 7-octenyltrichlorosilane (7-OTS) SAM was printed on a dielectric oxide material, A10 x , to modify the surface of the A10 x dielectric material or the pentacene / dielectric material interface.
• a polydimethylsiloxane (PDMS) buffer was selectively treated with a solution of 7-octenyltrichlorosilane (7-OTS) and the 7-OTS monolayer on the PDMS buffer was transferred to the prepared structure (A10 x ) using no specific pressure and at room temperature.
• PDMS polydimethylsiloxane
• the difference between the inverter comprising the SAM obtained from the microcontact formed 7-OTS and an inverter without such a monoassembled layer was that the voltage gain of the modified inverter with the 7-OTS molecules was lower than that of the inverter. of the unmodified inverter with the 7-OTS SAM and that the inverter with the 7-OTS SAM exhibited an effective transition voltage of between 0 and -5 volts while the 7-OTS SAM-free inverter exhibited a very marginal transition voltage close to 0 volts.
• the microswitched monoassembly technique was applied only for the formation of 7-octenyltrichlorosilane monoassembled layers and on dielectric materials such as A10 x or ITO.
• the bonds involved are bonds between a silane group and a metal oxide.
• the grafting can actually be done by a simple contact.
• the bonds to be created in the invention are bonds between a sulfur atom and a metal. In this case, a simple pressure is not enough for the grafting.
• the invention proposes to use a method of forming a self-assembled monolayer of molecules comprising a thiol group, on the surface of a metal substrate.
• the invention provides a method for manufacturing an injection self-assembled monolayer (SAM) comprising molecules with a thiol end group, on the surface of a metal-based support, characterized in that it comprises the steps following:
• step b) is carried out at a temperature above 90 ° C and below the melting temperature of the material constituting the buffer and at a pressure greater than or equal to 1000 N and less than or equal to 40 000 N, for between one and twenty minutes, inclusive.
• step b) is carried out at a temperature between 95 ° C and 115 ° C at a pressure of 1000 N for between five and ten minutes, inclusive.
• the SAM of step a) was obtained from at least one of the following molecules:
• CT - cysteamine
• PFBT pentafluorobenzenethiol
• the support it is preferably a metal chosen from gold, silver, copper, nickel, platinum, palladium and aluminum, or a metal oxide such as I ⁇ . (tin oxide and indium).
• the buffer is preferably made of silicone or poly (dimethylsiloxane).
• step b) the heating to the desired temperature can be obtained by a heating plate placed under the support.
• the heating in step b) can also be obtained by heating resistors inserted in the buffer.
• step b) when the method according to the invention, characterized in that the support is placed between the source and drain electrodes of an organic electronic circuit transistor, and the heating of step b) is advantageously obtained by passing a electrical current between these source and drain electrodes.
• step a The deposition of the SAM on the buffer, in step a), is advantageously carried out in a liquid route and the buffer and the SAM are dried, before carrying out step b).
• the method for manufacturing a self-assembled monolayer (injection SAM), constituted from molecules comprising a terminal thiol group, on the surface of a metal support, according to the invention, is done by transfer of the SAM onto the surface of the metal support by hot pressing a buffer on which the SAM has been deposited.
• injection SAM self-assembled monolayer
• the SAM was deposited on a raised area of the buffer.
• the grafting of the SAM on the surface of the support is done via the terminal thiol group of the molecules.
• the metal support is preferably selected from gold, silver, copper, nickel, platinum, palladium and aluminum. It is most preferably gold.
• the preferred terminal thiol group molecules used in the process of the invention are the following molecules: - 4- (methylsulfanyl) -thiophenol (MeSTP), which when forming a monoassembled layer is used to modify the work function, particularly gold, for an n-type semiconductor.
• the output work is 4.19 eV for the n-type semiconductor
• MeOTP 4-methoxythiophenol
• ATP 4-aminothiophenol
• DT - 1 -decanethiol
• cysteamine which is used to modify the output work, in particular gold, for an n-type semiconductor.
• the output work is then 4.68 eV
• PFDT perffuorodecanethiol
• PFOT perfluorooctanethiol
• PFBT pentafluorobenzenethiol
• the output of virgin gold is 4.75 eV.
• the method of the invention consists in using both a pressure and a heating during the transfer of the SAM on the surface of the support by printing by microcontact to improve the electrical performance, especially the injection between the metal, more particularly gold, silver, copper, nickel, platinum, palladium and aluminum (a thickness between nm and 100 nm, inclusive) and the organic semiconductor, for example pentacene, which is a p-type semiconductor or perylene diimide which is an n-type semiconductor.
• the step of transfer of the SAM by microcontact printing is carried out at a temperature greater than 90 ° C and below the melting temperature of the material constituting the buffer on the surface of which the SAM has been deposited. , and at a pressure greater than or equal to 1000 N and less than or equal to 40 000 N for between one and twenty minutes, inclusive.
• the SAM transfer step is preferably carried out at a temperature between 95 ° C and 115 ° C, inclusive, at a pressure of 1000 N, for between five and ten minutes, inclusive. .
• the heating during the transfer of the SAM can be carried out using a hot plate placed under the metal support.
• the heating can still be obtained, when the support is already in place between the source and drain electrodes of an organic electronic circuit transistor, by passing an electric current between these source and drain electrodes.
• a buffer for example silicone or poly (dimethylsiloxane) (PDMS), on which the SAM has been deposited.
• PDMS poly (dimethylsiloxane)
• the method of the invention may also include a step of depositing the desired SAM on a raised area of a buffer.
• This deposition can be carried out wet, in a manner known in the art.
• the pad covered with the SAM is then dried before transferring the SAM to the metal surface of the support.
• the sample and the silicone mold are then placed face to face and the mold is pressed onto the surface of the gold sample at 60 ° C. using a pressure of 1000 N for one minute.
• the sample is a gold electrode.
• This electrode was previously treated with an oxygen plasma. It can be, or mechanically treated or ozone under UV. This treatment serves to restore uniformity to the metal surface, before the implementation of the method of the invention.
• the electrode can also be brought to the desired surface by using a rinsing for a few minutes with a piranha solution (sulfuric acid + hydrogen peroxide), then with water, before undergoing a restructuring in water. sulfuric acid, which allows stripping of the surface.
• a piranha solution sulfuric acid + hydrogen peroxide
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of five minutes.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of fifteen minutes.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of five minutes and a printing temperature of 80 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of ten minutes and a printing temperature of 80 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of fifteen minutes and a printing temperature of 80 ° C.
• Example 2 The procedure is as in Example 1 but using a printing temperature of 100 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of five minutes and a printing temperature of 100 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of fifteen minutes and a printing temperature of 100 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of one minute and a printing temperature of 115 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of five minutes and a printing temperature of 115 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of ten minutes and a printing temperature of 115 ° C.
• the procedure is as in Examples 1, 2 and 3 respectively but using a printing time of fifteen minutes and a printing temperature of 115 ° C.
• the measurement of the contact angle of the water on the surface treated with the process according to the invention is used.
• the measurement of the drop angle gives access to the free energy of the surface.
• the surface energy of SAM-free virgin gold is 42 mN / cm 2 and the contact angle of water on virgin gold is 70 degrees.
• the electrical contact has also been tested.
• a test was also performed by not heating during microcontact printing.
• This test was carried out at a pressure of 10,000 N using a printing time of five minutes.
• Example 2 The procedure was as in Example 1 but using a printing temperature of 115 ° C.
• the SAM is well grafted and the electrical contact is good.
• CT - cysteamine
• the grafted molecule is PFBT and the sample on which the PFBT molecule has been grafted, by the process of the invention, was an ITO zone of a support.
• the sample was first pretreated with a 1% acetic acid solution.
• a solution of another acid or even a base may also be used.
• the PFBT was dispersed in ethanol and the resulting solution was dispersed on a silicone mold.
• the ethanol was then evaporated to leave on the mold only the molecule alone.
• the sample or, more exactly, the ITO zone of the sample and the silicone mold were then placed face to face and the mold was pressed onto the surface of the ITO zone at a temperature of 115 ° C. using a pressure of 35,000 N for 10 minutes.
• the sample obtained was tested as before.
• the droplet angle of the water was 95 °, which shows that grafting of PFBT to the ITO zone was performed.
• the process of the invention makes it possible to form a dense, compact and efficient monolayer for the production of organic transistors by microcontact printing.

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• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Mechanical Engineering (AREA)
• Thin Film Transistor (AREA)
• Fuel-Injection Apparatus (AREA)
• Micromachines (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Electrodes Of Semiconductors (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2011
  • 2011-02-04 FR FR1100349A patent/FR2971369B1/fr not_active Expired - Fee Related
• 2012
  • 2012-02-02 WO PCT/IB2012/050491 patent/WO2012104809A1/fr active Application Filing
  • 2012-02-02 KR KR1020137023344A patent/KR101946287B1/ko active IP Right Grant
  • 2012-02-02 US US13/983,159 patent/US9459526B2/en active Active
  • 2012-02-02 JP JP2013552311A patent/JP6018584B2/ja not_active Expired - Fee Related
  • 2012-02-02 EP EP12704322.2A patent/EP2671268A1/de not_active Withdrawn

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