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GB1572182A - Method of coating - Google Patents

Method of coating Download PDF

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Publication number
GB1572182A
GB1572182A GB34264/75A GB3426475A GB1572182A GB 1572182 A GB1572182 A GB 1572182A GB 34264/75 A GB34264/75 A GB 34264/75A GB 3426475 A GB3426475 A GB 3426475A GB 1572182 A GB1572182 A GB 1572182A
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GB
United Kingdom
Prior art keywords
film
organic material
substrate
anthracene
water
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.)
Expired
Application number
GB34264/75A
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to GB34264/75A priority Critical patent/GB1572182A/en
Priority to FR7625129A priority patent/FR2321770A1/en
Priority to JP9855476A priority patent/JPS5235579A/en
Priority to DE2637099A priority patent/DE2637099C2/en
Priority to NL7609164A priority patent/NL7609164A/en
Publication of GB1572182A publication Critical patent/GB1572182A/en
Expired legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/20—Processes for applying liquids or other fluent materials performed by dipping substances to be applied floating on a fluid
    • B05D1/202—Langmuir Blodgett films (LB films)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/38—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings polycyclic
    • C07C57/40—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings polycyclic containing condensed ring systems
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    • C07C59/40—Unsaturated compounds
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    • C07C59/48—Unsaturated compounds containing hydroxy or O-metal groups containing six-membered aromatic rings
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    • C07C59/40—Unsaturated compounds
    • C07C59/76—Unsaturated compounds containing keto groups
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    • C07C63/33—Polycyclic acids
    • C07C63/337—Polycyclic acids with carboxyl groups bound to condensed ring systems
    • C07C63/42—Polycyclic acids with carboxyl groups bound to condensed ring systems containing three or more condensed rings
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    • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • C07C65/28—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups having unsaturation outside the aromatic rings
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
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    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
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  • Spectroscopy & Molecular Physics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Electromagnetism (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Thin Film Transistor (AREA)
  • Led Devices (AREA)
  • Light Receiving Elements (AREA)

Description

(54) METHOD OF COATING (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London SWIP 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted'to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a method for the preparation of composite devices comprising thin film components.
Several classes of devices, particularly electrical, electrochemical or photochemical devices, comprise a thin layer of an organic material, usually insulating, having a high degree of molecular orientation. Conventionally sheets or films of material retaining a degree of orientation have been prepared, for example, by abrasion-shaping from a single crystal, but dislocations and discontinuities in the crystal lattice usually occur before the desired thinness is attained. Also, the dimensions of the resulting sheet are limited by the size of the original crystal.
Alternative techniques for the preparation of very thin layers have employed deposition of films from vapour; thermally grown oxide films have also been used.
The present invention provides a method of preparing an electrical, electrochemical or photochemical device comprising a film of organic material, said film having a high degree of molecular orientation, upon a substrate, the method comprising forming a mono-molecular layer of an organic material having a planar delocalised system of 7r-electrons upon the surface of a suitable liquid and repeatedly passing a substrate through the layer so that a film comprising a plurality of monomolecular layers of the organic material is formed upon the substrate.
The organic material employed according to the invention is one having a planar delocalised system of 7t-electrons which may be acyclic or cyclic; such systems may be for example aromatic, non-aromatic or anti-aromatic systems, and they may be homocyclic, heterocyclic or organo-metallic. The organic material employed must have both hydrophobic and hydrophilic properties, conveniently resulting from the presence in the molecule of suitable hydrophobic and/or hydrophilic groupings (by 'hydrophobic' we mean the property of repelling water, so that a water-soluble molecule carrying such a hydrophobic group tends to become concentrated at an air-water interface thereby reducing the surface tension of a solution in which it is dissolved. By 'hydrophilic' we mean the property of attracting water, owing to the presence in the group of electric poles and dipoles).
Typical hydrophobic groups include hydrocarbon chains which usually are linear alkyl groups but which may be branched alkyl or linear polyacene chains or aromatic rings. Alkyl groups may contain heteroatomic groundings, e.g. 0 NH, S SO2. Typical hydrophilic groups include + + -COOH, OH, NH2, CN, SO3H, NR'3, SR'2 (where R' is alkyl or aryl), PO4 and -SOCH3.
It has previously been considered that for the production of a stable film, an organic molecule on water should contain a hydrophobic hydrocarbon chain of considerable length - preferably greater than 16 carbon atoms. However we have found that the use of such materials is undesirable for example where the material is employed in a multilayer device required to display semiconductor properties.
Thus, for such a device we have found that where the hydrophobic group is a hydrocarbon chain it is desirable that the organic material to be laid down does not comprise a hydrophobic chain more than 10 carbon atoms in length (i.e. straight chain length) and preferably comprises no hydrophobic group greater than from 3 to 8 carbon atoms in chain length; preferably any such chain will be linear.
A compound comprising a plurality of both hydrophobic and hydrophilic groups may be employed, but the "hydrophobic/hydrophilic balance" must be retained, for example so that the compound does not dissolve or disperse in the support liquid and also so that it does not become so overwhelmingly hydrophobic that the film is unstable.
Usually, therefore, the organic compound will have the structure: R-C-X where R is a hydrophobic group, X is a hydrophilic group and C is a cyclic or acyclic structure having a planar delocalised system of R-electrons, although where C itself has marked hydrophobic or hydrophilic properties R or X as appropriate may be absent. Preferably C is a cyclic structure, and it may comprise substituents in addition to R and X, for example H, halogen, quinonoid oxygen, doubly bound sulphur, nitro, dimethylamino, acyl and oxyamino. One or more of such substituents may function as metal ligands.
Alternative arrangements of constituents may be C - R - X or C - X - R.
Where C is cyclic it may comprise one or more rings, which may be homo- or heterocyclic, and which may include metal atoms.
As examples of classes of organic compound which we can form into films in the described manner we would mention the following. (In the formulae R is preferably a normal alkyl chain of length not greater than 10, more preferably 3-8, carbon atoms and n may be O or an integer not greater than 12 and preferably 1 to 3.) Homocyclic compounds
5
5
Transition Metal Complexes
The precise location of the substituents indicated may not be important, and additional substituents may be incorporated into the above molecules, consistent with the resulting material being capable of forming a monomolecular layer upon a suitable liquid and of being deposited in a suitably integral form upon a substrate to give a film having desired properties.
Mononuclear heterocyclic compounds, we have found, can be formed into Langmuir films only with great difficulty and are preferably avoided.
For use in devices which display electroluminescence or photoconductivity a preferred group of compounds are the anthracenes, (or other electroluminescent or photoconducting compounds, such as pyrenes, perylenes) particularly those substituted on the 9 position by a linear-alkyl hydrophobic group having from 3 to 8 carbon atoms and particularly preferably having not more than 4 carbon atoms.
The molecule conveniently comprises a hydrophilic group located in one of positions 3, 4, 5, 6 or preferably 10.
Preferably the molecule comprises only one each of the hydrophilic and hydrophobic groups.
The multimolecular film of organic material is obtained by repeated applications of layers of the same material (typically 20200 for thin film transistor devices); or by, say, interlaying with other materials; or to modify it by forming a film comprising more than one component.
Techniques for the formation of a monomolecular film on a supporting substrate are known from Langmuir Trough technology but the process may be summarised as follows. The supporting liquid is one which is usually inert to the organic material, that is, it does not react (although we have found it desirable in some circumstances to include in the liquid components, particularly ions, which react with the film material or other component of the product) adversely with the material of the layer or of the substrate under the conditions employed in the process of the invention. It may be a solvent for the organic material, but preferably is not, the important requirements being that the organic material concentrates at the liquid surface so that it may be removed as a film. The liquid may be organic or inorganic; usually we prefer to use water, although the presence of inorganic ions may improve the stability of the organic layer.
Formation of the monomolecular layer of the organic material on the surface of the supporting liquid is most conveniently effected by applying to the surface of the liquid an appropriate volume of a solution of the organic material in a volatile solvent which is normally immiscible with the supporting liquid. The technique of applying the organic material to the liquid subphase and of compressing it are well-known in the art.
Transfer of the organic material to the substrate, which can be of any appropriate material, is effected by dipping the substrate into the supporting liquid and withdrawing it again, so that the film of organic material adheres to the surfaces of the substrate. Provision of means for maintaining the integrity of the layer on the liquid is necessary and this can comprise a sweep or paddle, preferably responsive to a microbalance which constantly measures the surface pressure of the film. This feature of maintaining constant pressure upon the organic layer is important for the production of an aligned deposit upon the support.
The invention lends itself particularly to 'doping', either by incorporating the dopant as an 'impurity' at a suitable concentration in the film of organic material on the supporting liquid, or by deposition of the dopant as a separate layer, or by interleaving with the organic material (usually referred to as the host material). An example of the application of such a technique could be the preparation of a device comprising alternate films of a photoconductor and sensitiser; alternate p-type and n-type layers; and alternate semiconductor and insulator layers. Suitable dopants include colourants intended to alter the colour of the radiation emitted by the device, for example the presence of about 1 part per million by weight of tetracene in the anthracene derivative will change the colour from blue to yellow.
The method of the invention may be employed in the preparation of different devices. Thus, we have employed the method in preparing electroluminescent devices comprising anthracene derivatives or other suitable semiconducting materials e.g. pyrene and perylene derivatives. Anthracene has previously been employed in electroluminescent devices in the form of crystals (see US Patent No.
3,530,325 and US Patent No. 3,382,394 in which the electroluminescent principle is also referred to).
According to the present invention we provide a method of preparing a composite product comprising depositing a film of an organic material, preferably an anthracene, perylene or pyrene derivative as described above, the organic material being deposited upon a substrate which is a suitable conducting material.
The organic film formed may be of any convenient thickness but preferably does not exceed 2 r,Lm. Preparation of the said device may be effected conveniently for example forming by any suitable means a first layer of a suitable electrode material, forming in contact with at least one surface of this layer, by the Langmuir technique, a multimolecular (ca. 20500) film of, say, a suitable anthracene derivative, and to, the surface of the said film so produced, applying a second electrode material. Optionally the anthracene film may be annealed after application of the second electrode material. The first electrode material may be for example a suitable electron-injecting electrode material, e.g. Al203 on Al metal.
As the second electrode material may be used any positive-hole injecting material e.g. Au, Pt, CuO/I, Se/Te etc, or mixtures thereof. The use of organic positive hole injecting materials is not excluded e.g. a bisbenzothiazolone azine disulphonic acid.
Conveniently the first electrode will be deposited upon a base sheet of appropriate rigidity and insulating properties for the intended purpose of the device.
Further applications of the method of the invention include the production of improved photoconductive and photovoltaic systems, in which deposition of molecularly ordered material is an important factor in optimising performance.
According to yet a further aspect, the invention provides a method of preparing improved insulated gate field effect transistors, e.g. thin film transistors.
The basic principle common to all types of unipolar transistors is the control by a gate electrode of current flow between a source and a drain electrode.
Sections of typical transistor figurations are shown .diagrammatically in the attached drawings. The diagrams are, of course, very greatly magnified; many of the thin-film components of transistors are of the order of only thousandths of a millimetre in thickness.
The problem of forming an insulator film relatively free from imperfections may be obviated by depositing the film of insulator using the Langmuir technique.
Such films are deposited to form a multimolecular insulating film component of appropriate thickness for the intended purpose. A section of such a device is shown diagrammatically in Figure 1 in the drawings. Typically the insulator film would comprise 20 to 200 monomolecular layers.
Heat dissipation in transistors may be encouraged by the use, as an insulating substrate, of a polymeric material of relatively high thermal conductivity, for example polyether sulphone.
The use of the Langmuir technique for the deposition of the semiconductor film in a transistor is also feasible, although, as in all cases in which the technique is applied, it will be appreciated that reactants or support liquids deleterious to already deposited material will be avoided.
Many films laid down by the method of the invention may function as both the insulator and as an active component (dependent upon there being a large anisotropy of mobility for charge movement parallel and perpendicular to the plane of the layer). An exemplary structure for such a device is shown diagrammatically in Figure 2. Materials having the required property may be selected from those listed earlier, but preferably will be an anthracene, perylene, pyrene, tetracene or naphthalene derivative or an organometallic compound.
Examples of materials suitable as source and drain electrodes are metals, alloys and metal oxides and salts, e.g. Au, Al, In, Ag; high conductivity semiconductors, e.g. Te, and conducting organic materials e.g. a bis benzothiazolone azine disulphonic acid. Similar materials may be used as gate electrodes components.
The insulating substrate may be of any of a wide range of materials, e.g. mica, glass, sapphire, cleared crystals, high thermal conductivity plastics.
The material of the semiconducting film may comprise any of a wide range of semiconductor materials, including CdS, Cd, Se, GaAs, Si, PbS, InAs, phthalocyanine, violanthrene, porphyrins and derivatives of anthracene, of tetracene, of naphthalene, of pyrene and of perylene.
The fabrication of thin layer devices, and particularly the fabrication of transistors which rely for their operability upon the accurate spacing of their components, depends upon the accuracy with which the various components may be deposited. For example, to avoid undesirable capacitative effects it is important that in a thin film transistor the gate electrode is laid down in register with the channel between the source and drain electrodes. The deposition of a component film by the Langmuir technique in the desired location, followed where necessary by removal of the film from parts of the device, for example by abrasion or etching, provides a convenient method of effecting accurate location of thin active or insulating components.
Other applications of the method of the invention include the production of varactors, hot electron devices, hot electron transistors, Esaki M-I-M-I-M structures, Gunn-Effect oscillators and photodetectors. Thus, in the production of varactors (devices whose reactance/capacitance can be varied in a controlled manner using a bias voltage) the advantages of depositing film components e.g. insulating films, by Langmuir technique include higher capacitance due to a thin insulating film and relatively large area, lower operating voltages due to the thin insulating film and reproducibility of the characteristic of the device. Esaki M-I-M-I-M structures are layered structured deviceswith layer periods of the order of 50100 A. In Gunn-Effect Oscillators, a contact supplying hot electrons (0.3 eV) to a single crystal is preferred. This type of contact is best achieved using the nrincinle of tunnel-iniection through a thin insulator film.
A photodetector of simple but effective design, having the structures shown in Figure 3, may be obtained using the Langmuir technique. For example a suitable photoconductor, e.g. CdS, may be deposited between the gate electrode and the insulator; light falling on the photoconductor renders it more conducting resulting in an increased voltage drop across the insulator which produces a change in conductance of the source-chain channel. Alternatively, a photosensitive material, e.g. a dye may be incorporated between the gate and insulator (or in the insulator as a dopant). Light falling on the photosensitive material causes charge carriers to be injected into the dielectric under the influence of the gate voltage where they affect the source-chain current conductance. Such devices lend themselves to preparation by the method of the invention; for example one or both insulator and semi-conductor may be deposited as a Langmuir film as described above.
In a further embodiment of the invention, therefore, there is provided a method of preparing an electronic device which comprises the step of forming upon a surface of an insulating, a conducting or a semiconducting material a multimolecular Langmuir film of an insulating or semiconducting organic material, particularly an organic material as hereinbefore described. (By Langmuir film is meant a film obtained using Langmuir Trough techniques).
The invention is illustrated by the following Examples.
EXAMPLES 1 "4.
Preparation of anthracene derivatives Anthrone was converted to 9-alkyl-l0-hydroxy-methyl anthracene using the methods of Sieglitz (Berichte 1923, 56, 1619) and of Stewart. (Australian J. Chem.
1960, 478).
Conversion to the l0-bromomethyl derivative was as follows:-- 0.1 mole of the 10-hydroxymethyl compound was suspended in 500 ml of dry diethyl ether. 2 Drops of pyridine were added followed (dropwise) by 0.05 mole of phosphorus tribromide in 50 ml of dry ether. The mixture was stirred for 2 hours at 200 C, poured onto ice and extracted with dichloromethane to give the 10-bromomethyl compound.
A mixture of diethyl malonate (4.8 cm), dry toluene (200 ml) and finely cut sodium (0.75 gm) was heated to 800C for 2 hours. 9-alkyl- l0-bromomethyl anthracene (0.02 mole) dissolved in dry dioxan (200 ml) was added dropwise with stirring to the cooled solution and stirred overnight at 200 C. The mixture was diluted with 500 ml water and the toluene layer removed, washed twice with water, dried and evaporated to give the crude malonate ester. This was refluxed in ethanol (100 ml) and sodium hydroxide (5 gm) in water (20 ml) for 30 minutes, cooled, acidified and diluted with water to give the solid malonic acid.
The acid was suspended in tetrahydronaphthalene and heated. Carbon dioxide was evolved and after 30 minutes the solution was diluted with petroleum ether and cooled. 9-alkyl-l0-anthracene propionic acid crystallised out.
By the routes described above the following anthracenes were prepared:
Ex. Recrystallisation Ex. Recrystallisation No. R1 R2 mp solvent No. R1 R2 mp solvent 1 C2H5 H 50-52 pet ether 17 C6H13 CH2CH2CO2H 164-6 pet ether 2 C3H7 H 55-59 methanol 18 C8H17 CH2CH2CO2H 136-7 " " 3 C4H9 H 48 " 19 C12H25 CH2CH2CO2H 112-3 methanol 4 C6H13 H 67-8 " 20 C2H5 CHO 87-88 ethanol 5 C8H17 H 36-40 " 21 C3H7 CHO 94-5 pet ether/toluene 6 C12H25 H 40-45 ethanol 22 C4H9 CHO 78 pet ether 7 C2H5 CH2OH 193-7 methanol 23 C6H13 CHO 70 " " 8 C3H7 CH2OH 200 " 24 C6H17 CHO 57-8 " " 9 C4H9 CH2OH 194-5 " 25 C12H25 CHO 80 ethanol 10 C6H13 CH2OH 160-2 " 26 C2H5 CH2Bv 173-5 pet/ether/toluene 11 C8H17 CH2OH 153-4 " 27 C3H7 CH2Bv 145 pet ether 12 C12H25 CH2OH 147-8 " 28 C4H9 CH2Bv 139 " " 13 C18H37 CH2OH 139-40 cyclohexane 29 C6H13 CH2Bv 139-40 " " 14 C2H5 CH2CH2CO2H 169 pet ether 30 C8H17 CH2Bv 105-7 " " 15 C3H7 CH2CH2CO2H 198-200 " " 31 C12H25 CH2Clb 99-100 " " 16 C4H9 CH2CH2CO2H 127-8 a " " Notes for Table: a This material crystallises in two forms. mp 151-2 and mp 127-80C having identical spectroscopic properties. The latter material mp 1278 is only obtained after 4 or 5 recrystallisations from petroleum ether, and this was the material used in all Langmuir Trough experiments. b Prepared by the method of Stewart (Australian J. Chem. 1960, 478).
Other anthracene derivatives were prepared as described below.
EXAMPLE 32.
Preparation of 9-Butyl-1 0-carboxy anthracene 9-Butyl-l0-anthraldehyde (6.6 g) was refluxed for 4 hours with silver oxide, prepared from silver nitrate (6.5 g), 50% aqueous ethanol (150 ml) and sodium hydroxide (4 g). The mixture was diluted with water (300 ml), filtered hot then acidified, and the product was filtered off and recrystallised from toluene, mp 176 .
EXAMPLE 33.
Preparation of 9-butyl-10-anthryl-acetic acid A solution of 9-butyl-10-bromomethyl anthracene (5.74 g) in dioxan (10 ml) was named with potassium cyanide (1.4 g) in water (35 ml) for a few minutes, diluted with water and filtered. The crude 9-butyl-l0-anthryl-acetonitrile was refluxed for 3 hours with potassium hydroxide (12.5 g) in ethoxyethanol (125 ml), cooled, acidified and the product was filtered off and recrystallised from benzene, mp 189 (2 g).
EXAMPLE 34.
Preparation of 9-butyl-1 O4hiolmethyl anthracenes 9-Alkyl-lO-bromomethyl anthracene (0.05 mole) in dioxan (25 ml) and water (10 ml), then evaporated to give the thiouronium salt. This salt was heated with a solution of sodium hydroxide (3 g) in water (30 ml) under nitrogen for 2 hours, diluted with water and extracted with chloroform. The extracts were dried and evaporated and the product (0.15 g) was recrystallised from acetic acid (mp 2258 ).
EXAMPLE 35.
Preparation of 9-butyl-10-methylthiomethyl anthracene A mixture of 9-butyl-lO-bromomethyl anthracene (1.6 g) and dimethyl sulphide (10 ml) in dimethyl formamide (20 ml) was refluxed for 2 hours, cooled, poured into water and extracted with ether. The extracts were washed twice with water, dried and evapored and the product was recrystallised from petroleum ether, mp 120-122 (0.8 g).
EXAMPLE 36.
Preparation of 9-butyl-1 0-anthrylmethyl sulphoxide
A solution of hydrogen peroxide (30%, 0.3 ml) was added dropwise with stirring to a solution of 9-butyl-l0-methylthiomethyl anthracene (0.72 g) in acetone (20 ml) and the solution was left overnight at room temperature, diluted with water and the product was filtered off and recrystallised from toluene-pet ether mp 1678 .
EXAMPLE 37.
Preparation of 9-butyl-10-anthrylmethyl sulphone Further oxidation (reflux 3 hours) of the above sulphoxide by the same method (H202-acetone) gave the sulphone which was recrystallised from toluene mp 200202 C.
EXAMPLE 38.
Preparation of 9-butyl-10-aminomethyl anthracene 9-butyl-10-bromomethyl anthracene (7.2 g) in dioxan (100 ml) was added dropwise with stirring to a solution of 880 ammonia (40 ml) in dioxan (100 ml) and the mixture was refluxed for 3 hours, poured into dilute sodium hydroxide and extracted with ether. The extracts were dried and evaporated and the product was crystallised from dioxan-ethanol, mp 178180 (3.7 g).
EXAMPLE 39.
9-butyl-10-dimethylaminomethyl anthracene A solution of 9-butyl-10-bromomethyl anthracene (2 g) in dry dioxan (50 ml) was added dropwise to dimethylamine (5 ml) in dry dioxan (20 ml). The mixture was stirred for 2 hours, poured on to 10% aqueous sodium carbonate and extracted with ether in the normal way. The product was crystallised from ethanol-water, mp 73--5"C.
EXAMPLE 40.
Preparation of ethyl-3-(9-butyl-10-anthryl)-2-propenoate A suspension of "powdered" sodium (0.6 g) in ethyl acetate (10 ml) and ethanol (2 drops) was treated with a solution of 9-butyl-l0-anthraldehyde (5.1 g) in ethyl acetate (10 ml). The mixture was stirred overnight, diluted with acetic acid (10 ml) and poured into water. Extraction with chloroform gave, after evaporation, a solid which was recrystallised from ethanol-water, mp 7577 (1.2 g).
EXAMPLE 41.
3-(9-butyl-l0-anthryl)-2-propenoic acid The above ester was refluxed with alcoholic NaOH for 1 hour, cooled and acidified. The product was filtered off, dried and recrystallised from petroleum ether mp 170175. A further recrystallisation from acetic acid raised the mp to 185-186 C.
EXAMPLE 42.
2-09-butyl-10-anthrylmethyl)-1 3-propanediol 9-butyl-10-anthrylmethyl malonic acid was converted to its methyl ester by refluxing with methanol containing a trace of sulphuric acid. The ester (1.0 g) was dissolved in dry ether (30 ml), added to a suspension of lithium aluminium hydride (0.5 g) in dry ether (100 ml) refluxed for 3 hours, cooled and decomposed with water and dilute sulphuric acid. After ether extraction the product was recrystallised from toluene, mp 147 .
EXAMPLE 43.
Methyl-3X9-butyl-10-anthracene) propionate 9-butyl-10-anthracene propionic acid (2 g) was dissolved in methanol, 2 drops concentrated sulphuric acid were added and the mixture was refluxed for 1 hour, cooled and diluted with water. The product was filtered off and recrystallised from ethanol giving needles mp 98-100 C.
EXAMPLE 44.
3-f9-butyl-10-anthracene) propanol Lithium aluminium hydride reduction of methyl 3-(9-butyl-l0-anthracene) propionate gave the required product which was recrystallised from petroleum ether mp 114-1150.
EXAMPLE 45.
3-01-Ethyl-6-pyrenoyl) propionic acid 3 Ethylpyrene (10 g), nitrobenzene (80 ml) and succinic anhydride (5.22 g) were stirred together at 5 C while powdered aluminium chloride (20 g) was added over 50 minutes. The mixture was stirred overnight at room temperature, acidified with concentrated HCI then steam distilled to remove nitrobenzene. The aqueous mixture was extracted with chloroform and the extracts were dried and evaporated yielding a solid which was recrystallised from acetic acid, mp 136-147 C.
EXAMPLE 46.
4-66-Ethylpyrene)butyric acid The acid from Example 45 (2.7 g), digol (18 ml) sodium hydroxide (1.1 g) and hydrazine hydrate (2.8 ml) was refluxed for 1 hour then the excess hydrazine and water were distilled off. The solution was heated at 2200 for 3 hours, cooled, acidified and extracted with chloroform. The extracts were dried and evaporated yielding a brown solid mp 105--1200C which on recrystallisation from acetic acid gave white crystals mp 125-70C.
EXAMPLE 47.
Methyl4-(l-pyrenyl) butyrate Pyranebutyric acid (5 g), methanol (250 ml) and sulphuric acid (0.5 ml) were heated under reflux for 3 hours, evaporated to small bulk and partitioned between ether and water. The ether layer was dried and evaporated and the resultant solid was recrystallised from hexane mp 52"C (4.0 g).
EXAMPLE 48.
4(1-Pyrenyl) butanol The above ester (1.5 g), dry ether (200 ml) and lithium aluminium hydride (0.5 g) were stirred overnight at room temperature and diluted carefully with water. The ether layer was dried and evaporated and the product crystallised from petroleum ether, giving plates mp 7678 .
EXAMPLE 49.
4-Pyrenebutyric acid amide 4-Pyrenebutyric acid (10 g) in dry toluene (100 ml) was stirred with thionyl chloride (3 ml) until all the solid was dissolved, then evaporated to dryness. The crude acid chloride was dissolved in dioxan (30 ml) and ammonia (3 ml) was added.
The product was precipitated with water, filtered off and recrystallised from ethanol-water, then isopropanol, mp 182--185"C.
EXAMPLE 50.
Preparation of perylene-butyric acid Perylenoyl propionic acid was prepared by reaction of perylene (7 g) with succinoyl chloride and aluminium chloride according to the method of Zinke (Berichte 1940, 73, 1042). In order to obtain a pure material it was necessary to convert the crude product to its sodium salt by stirring with 2M aqueous sodium hydroxide. The insoluble sodium salt was then filtered, washed several times with chloroform to remove unreacted perylene, and the resultant black solid was placed in a Soxhlet thimble and extracted with xylene until no more perylene was removed. The solid was then acidified with HC1 and extracted into chloroform.
After drying, the solution on evaporation yielded the required perylenoyl propionic acid as a green solid mp 1800C (0.6 g).
The product was reduced using the Huang Minton procedure. A mixture of the above acid (0.6 g) hydrazine (0.25 ml), digol (4 ml) and sodium hydroxide (0.25 g) were heated to 2000 for 4 hours. The product was isolated by acidification with dilute HC1 and filtration. The resultant brown solid was Soxhlet extracted with toluene, the toluene solution yielding yellow crystals of perylenebutyric acid, mp 222224 on cooling.
EXAMPLE 51.
6-(N-Acridonyl)-hexanoic acid A mixture of sodium hydride (1.2 g) methanol (4.7 ml) and dimethyl sulphoxide (45 ml) was heated to 1000 with acridone (3.5 g). When all the acridone had dissolved, methyl 6-bromohexanoate (3.6 g) in DMSO (17 ml) was added, the mixture was stirred for 2 hours, diluted with water and extracted with methylene chloride. The extracts were dried and evaporated giving an oily solid, methyl-64N- acrydonyl)-hexanoate, which was crystallised from petroleum ether-toluene, mo 106--8"C yield 2.lug (36%).
The above ester was hydrolysed by refluxing for 3 hours with sodium hydroxide (0.3 g) in methanol (30 ml). After cooling the solution was acidified and the product filtered off. Recrystallisation from petroleum ether-acetone gave material mp 165170 .
EXAMPLE 52.
(4-Octyl naphthalene) butyric acid Octylnaphthalene (3.06 g), nitrobenzene (30 ml) and aluminium chloride (3.1 g) were stirred at OOC, succinic anhydride (1.3 g) was added slowly and the mixture was stirred overnight, acidified and extracted with chloroform. The extracts were dried and evaporated yielding the crude octylnaphthalenoyl propionic acid.
This solid was refluxed with hydrazine hydrate (2 ml) sodium hydroxide (1.7 g) and digol (50 ml) for I hour, then the water was distilled off. After heating at 2200 for 3 hours, the solution was cooled, poured into dilute HCI and extracted with chloroform. The extracts were dried and evaporated and the product was recrystallised from petroleum ether, mp 119--120"C.
EXAMPLE 53.
4-Butoxy4 '-cyanostilbene Butoxybenzaldehyde was prepared by treating p-hydroxbenzaldehyde (61 g) in ethanol (200 ml) with sodium hydroxide (20 g in 50 ml water) and adding the butyl bromide (1 mole) in ethanol (100 ml). After refluxing 2 hours, the mixture was partitioned between ether and water and ether extracted etc. giving an oil which was distilled bp 120--128"C at I mm (40 g).
A solution of 4-cyanobenzyl-triphenyl phosphonium bromide (18.4 g) in warm ethanol (250 ml) was treated with a solution of 4-butoxybenzaldehyde (71 g) in ethanol (50 ml) and a solution of sodium ethoxide in ethanol (from sodium hydride (20g)) was added dropwise with stirring. After stirring overnight at room temperature, water (20 ml) was added and the product (7 g) was filtered off and recrystallised from ethanol mp 115".
EXAMPLE 54.
4-Butoxy4'-carboxy stilbene A mixture of the above cyano compound (1 g) potassium hydroxide (1.2 g) and digol (50 ml) was heated in a distillation apparatus, removing any water and ammonia as it was formed. After 30 minutes at 150220 , the mixture was cooled, diluted with water and the product (the sodium salt of the required acid) was filtered off. The acid was liberated by heating with concentrated HC1 in a 5050 methanol water mixture at 600 for 3 hours, then filtering. The solid was recrystallised from a large quantity of ethanol mp 265270 .
EXAMPLE 55.
Thin film transistor A film of cadmium sulphide 10,u thick was formed upon one surface of a thoroughly cleaned quartz disc substrate 2.5 cm diameter and 2 mm thick by deposition from vapour produced by heating cadmium sulphide to 1000C in an evaporating chamber at 10--5 mm pressure. During deposition the disc was held at 200"C.
Two indium/tin source and drain electrodes, 500 A thick, were deposited upon the cadmium sulphide film, the electrodes being separated by a gap 25y wide.
The disc was then dipped repeatedly into a trough containing a sub-phase of ultrapure water containing cadmium chloride (2.5x 10-4M) at pH 6.2 and carrying a monomolecular film of cadmium arachidate applied to the subphase in a 1 mg/ml solution in chloroform. The disc was immersed vertically, its planar surfaces being at right angles to the surface of the subphase. Dipping speed was 3.7 mm/min and the surface pressure on the film was 30i 1 dyne/cm. 40 layers of cadmium arachidate were applied to the disc. After each immersion the disc was air dried at 200C for 1 minute; after completion of dipping it was dried in a desiccator for one day.
A gold gate electrode (400 A thick) was then applied by evaporation, through a mask, to form a disc 1 mm diameter across the source/drain gap (and separated from these electrodes, of course, by the cadmium arachidate film).
The resulting device was tested using voltages up to one volt, pentode type characteristics being observed.
EXAMPLE 56.
Thin film transistor To one surface of a substrate in the form of an n+ indium phosphide crystal, having on the other surface an epitaxially grown indium phosphide layer, was applied an indium/tin contact by evaporation. The crystal was cleaned by treatment with bromine in methanol and on to the surface carrying the epitaxially grown indium phosphide were evaporated source/chain indium/tin electrodes as before.
The crystal was then dipped as described in Example 55 (but at pH 5.7) to give a cadmium arachidate film 20 layers thick over the source/drain electrodes. A gold gate electrode was applied as before. The resulting device displayed pentode type characteristics.
EXAMPLE 57.
Varactor The process described in Example 56 was repeated, up to and including treatment with bromine in methanol. The substrate was dipped to give a cadmium arachidate film 20 layers thick, after which a gold gate electrode was applied.
The curve shown in Figure 4 was obtained by plotting capacitance against DC bias voltage. This is a characteristic MIS curve showing depletion and weak inversion upon application of negative bias.
EXAMPLE 58.
A glass substrate 3" x 1" x 1 mm (chance microscope slip) was brushed in hot water, cleaned in saturated chromosulphuric acid at 1100 for 2 hours, ultrasonically rinsed in ultra pure water for 15 minutes, in 18% "Decon-90" (RTM) for 15 minutes, in ultra pure water for 15 minutes and in isopropanol for 15 minutes, and then placed in ultra pure water maintained at pH 11-12 with NaOH for 12 hours.
Before use the slip was blown dry using an antistatic air dryer.
A substrate treated as above was dipped to provide the surface with Langmuir film of cadmium arachidate 3 layers thick (this provides a convenient method of rendering the surface of the glass suitably hydrophilic), followed by dipping into a subphase consisting of ultra pure water at pH 4.5 containing a 2.5 x 10-4M barium chloride and carrying a monomolecular layer of the cadmium salt of 9-butyl-l0anthryl propionic acid (applied as a 1 mg/ml solution in chloroform). Dipping was effected at 19--210C, at a rate of 3.7 mm/min and a surface pressure of 15+ 1 dynes/cm. 20 Layers of the anthracene derivative were picked up.by dipping.
Two gold electrodes, each 7 x 2 mm and 500 A thick and 25 ,u apart were applied to the surface of the film so obtained and electrical contact with the electrodes made via silver paste.
The surface conductivity of the film was observed in the dark and during irradiation with white light. The current/voltage curve shown in Figure 5 was obtained.
EXAMPLE 59.
One surface of a glass slip, cleaned as in Example 58 but omitting the treatment with NaOH, was coated by evaporation with a 500A thick layer of aluminium. The slip was dipped as described in Example 58 except that the Langmuir film was the barium salt of 9-butyl-lO-anthryl propionic acid. 467 Layers were applied to the slip. A pattern of aluminium dots, each 2.5 mm in diameter and 300 A thick, was deposited from vapour through a mask onto the anthracene film so obtained.
Application of a current of 40 v, Dc or Ac (Au+, Al-) produced an emission of blue light.
Attention is drawn to co-pending application 34263/75 (Serial No. 1,572,181) in which is claimed an electronic, electrical, electrochemical or photochemical device comprising a substrate in association with a thin film of organic material, which film is prepared by a process which comprises forming a monomolecular layer of the organic material upon the surface of a suitable supporting liquid and repeatedly passing the substrate through the layer so that a film comprising a plurality of monomolecular layers of the organic material is deposited upon the surface of the substrate.

Claims (13)

WHAT WE CLAIM IS:
1. A method of preparing an electrical, electrochemical or photochemical device comprising a sheet or film of organic material, said sheet or film having a high degree of molecular orientation, upon a substrate, the method comprising forming a monomolecular layer of an organic material having a planar delocalised system of 7r-electrons upon the surface of a suitable liquid and repeatedly passing a substrate through the layer so that a film comprising a plurality of monomolecular layers of the organic material is formed upon a surface of the substrate.
2. A method according to claim 1 in which the organic material is a cyclic structure having both hydrophilic and hydrophobic substituent groupings.
3. A method according to claim 1 or 2 in which the hydrophobic grouping is a linear hydrocarbon chain of chain length not greater than 10 carbon atoms.
4. A method according to claim 3 in which the hydrocarbon chain is of chain length 3 to 8 carbon atoms.
5. A method according to any one of claims I to 6 in which the film of organic material is formed by depositing between 20 and 200 monomolecular layers upon the substrate.
6. A method according to any one of the preceding claims in which the organic material is a semiconducting material which is an anthracene, pyrene or perylene derivative and is deposited upon a conducting substrate.
7. A method according to claim 6 in which the organic material is anthracene substituted in the 9 position by a linear alkyl hydrophobic group having from 3 to 8, preferably 3 or 4, carbon atoms and in'position 10 by a hydrophilic group.
8. A method according to any one of the preceding claims in which the substrate comprises an electrode material.
9. A method according to claim 8, in which the organic film is deposited upon a substrate comprising a plurality of separate electrodes.
10. A method according to claim 8 or claim 9 in which the free surface of the film is contacted with a further electrode.
I I. A method according to any one of the preceding claims in which the organic material deposited upon the substrate comprises a dopant.
12. A method according to any one of the preceding claims in which deposition of the organic material is alternated with deposition of a different organic or inorganic material.
13. A method as claimed in claim 1 and substantially as hereinbefore described.
GB34264/75A 1975-08-18 1975-08-18 Method of coating Expired GB1572182A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB34264/75A GB1572182A (en) 1975-08-18 1975-08-18 Method of coating
FR7625129A FR2321770A1 (en) 1975-08-18 1976-08-18 PROCESS FOR PREPARING COMPOSITE DEVICES CONTAINING THIN FILMS WITH A HIGH DEGREE OF MOLECULAR ORIENTATION
JP9855476A JPS5235579A (en) 1975-08-18 1976-08-18 Method of making thin film having high molecular orientation*
DE2637099A DE2637099C2 (en) 1975-08-18 1976-08-18 Process for the production of a film or a layer of organic material with a high degree of molecular orientation on a substrate and the use thereof
NL7609164A NL7609164A (en) 1975-08-18 1976-08-18 PROCESS FOR THE MANUFACTURE OF A SHEET OR FILM OF ORGANIC MATERIAL AND SHEET OR FILM MADE BY THIS PROCESS.

Applications Claiming Priority (1)

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JP (1) JPS5235579A (en)
DE (1) DE2637099C2 (en)
FR (1) FR2321770A1 (en)
GB (1) GB1572182A (en)
NL (1) NL7609164A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076060A2 (en) * 1981-09-25 1983-04-06 Imperial Chemical Industries Plc Method of applying thin films to substrates
US4618509A (en) * 1981-03-23 1986-10-21 University Of Delaware Arrays of stacked metal coordination compounds
WO2009095909A2 (en) * 2008-01-28 2009-08-06 Yeda Research And Development Company Ltd. Solar cells
WO2012146456A1 (en) * 2011-04-27 2012-11-01 Siemens Aktiengesellschaft Component having an oriented organic semiconductor

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59120508U (en) * 1983-02-02 1984-08-14 株式会社呉英製作所 Drilling/cutting machine for civil engineering and construction
FR2564231B1 (en) * 1984-05-10 1986-09-05 Commissariat Energie Atomique ELECTRICALLY CONDUCTIVE FILMS COMPRISING AT LEAST ONE MONOMOLECULAR LAYER OF AN ORGANIC COMPLEX WITH LOAD TRANSFER AND THEIR MANUFACTURING METHOD
US4939556A (en) * 1986-07-10 1990-07-03 Canon Kabushiki Kaisha Conductor device
EP0450862B1 (en) * 1990-03-27 1999-06-30 Kabushiki Kaisha Toshiba Organic thin film element
DE19937262A1 (en) * 1999-08-06 2001-03-01 Siemens Ag Arrangement with transistor function

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3621321A (en) * 1969-10-28 1971-11-16 Canadian Patents Dev Electroluminescent device with light emitting aromatic, hydrocarbon material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4618509A (en) * 1981-03-23 1986-10-21 University Of Delaware Arrays of stacked metal coordination compounds
EP0076060A2 (en) * 1981-09-25 1983-04-06 Imperial Chemical Industries Plc Method of applying thin films to substrates
EP0076060B1 (en) * 1981-09-25 1986-12-17 Imperial Chemical Industries Plc Method of applying thin films to substrates
WO2009095909A2 (en) * 2008-01-28 2009-08-06 Yeda Research And Development Company Ltd. Solar cells
WO2009095909A3 (en) * 2008-01-28 2009-09-24 Yeda Research And Development Company Ltd. Solar cells
WO2012146456A1 (en) * 2011-04-27 2012-11-01 Siemens Aktiengesellschaft Component having an oriented organic semiconductor
US9159959B2 (en) 2011-04-27 2015-10-13 Siemens Aktiengesellschaft Component having an oriented organic semiconductor

Also Published As

Publication number Publication date
JPS5235579A (en) 1977-03-18
FR2321770B1 (en) 1982-08-13
DE2637099C2 (en) 1986-01-30
FR2321770A1 (en) 1977-03-18
NL7609164A (en) 1977-02-22
DE2637099A1 (en) 1977-03-03

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