EP0228429A1 - Agrégat pélliculaire ayant des propriétés de conductibilité électrique - Google Patents

Agrégat pélliculaire ayant des propriétés de conductibilité électrique

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Publication number
EP0228429A1
EP0228429A1 EP86904183A EP86904183A EP0228429A1 EP 0228429 A1 EP0228429 A1 EP 0228429A1 EP 86904183 A EP86904183 A EP 86904183A EP 86904183 A EP86904183 A EP 86904183A EP 0228429 A1 EP0228429 A1 EP 0228429A1
Authority
EP
European Patent Office
Prior art keywords
groups
group
zone
polarizable
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP86904183A
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German (de)
English (en)
Inventor
Paavo Kinnunen
Jorma Virtanen
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K & V LICENCING OY
Original Assignee
K & V Licencing Oy
Ksv-Chemicals Oy
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Publication of EP0228429A1 publication Critical patent/EP0228429A1/fr
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • 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
    • H10K85/30—Coordination compounds
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • H10K85/701—Langmuir Blodgett films
    • 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
    • H10K85/731—Liquid crystalline materials
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni

Definitions

  • the object of this invention is a film aggregate having electricity conducting properties, which film aggregate comprises a substantially inert substrate or support surface and carried by or on this surface, one or several film layers, each layer being comprised of an organic material which is tailor-made to give specific electrical properties to the film.
  • the invention concerns also new chemical compounds and intermediates which are useful for making the film layer.
  • the film aggregate according to the invention may be used in a variety of different electronic, electric, electrochemical or photochemical applications, such as in microcircuits, photocells, sensors, microphones, miniature lasers, semiconductor lasers, etc.
  • From the GB-patent specifications 1 572 181 and 1 572 182 are known film aggregates comprising several monomolecular layers of an organic material, especially a fatty acid derivative, on top of a substrate, the molecule comprising a hydrophilic part, a hydrophobic part and between these a cyclic or an acyclic group, which forms a planar cyclic ⁇ -electron system.
  • the conducting area in these film aggregates is formed by one single zone in each layer.
  • the conductive properties of these film aggregates are however not satisfying.
  • the present invention thus concerns a novel type of film aggregate which more specifically comprises, carried by or on a substantially inert substrate surface, one or several monomolecular film layers of a surface active compound, the conductive properties of which aggregate can be selectively modified as desired, even so as to be superconducting at a temperature of use of -40 to + 80°C.
  • Each film layer has a thickness of only one molecule, which generally means a layer thickness of 15 to 40 ⁇ .
  • the molecules forming the film layer are liquid crystals, i.e. they exhibit the optical and electrical properties of crystals but the mechanical properties of a liquid. They have a strong organizational tendency, wherefore the co-operative degree of orientation of the molecules in the film layer is very high.
  • Each monomolecular film layer is of sandwich-type construction comprising several individual zones which are parallel to each other and to the substrate surface, each zone corresponding to a specific part or portion of the organic molecule forming the film layer.
  • the film layer is characterized in that it, on the one hand, comprises a so called charge-transfer (CT) zone containing groups capable of forming charge-transfer complexes (electron gas forming) and, on the other hand, a polarizable zone containing polarizable groups interacting electrically with and being located at a distance from the charge-transfer zone and separated therefrom by an electrically neutral, spacertype zone.
  • CT charge-transfer
  • polarizable zone containing polarizable groups interacting electrically with and being located at a distance from the charge-transfer zone and separated therefrom by an electrically neutral, spacertype zone.
  • the basic unit from which a single film layer is built comprises, on a molecular level, basically a derivative of a fatty acid, fatty alcohol or a fatty amine, preferably constituting a side chain of a larger structural entity such as of a phosphoglycerol or a phosphothreitol.
  • both of the hydroxy groups in the glycerol moiety or all three hydroxy groups of the threitol, respectively, are etherified, esterified or amidified by the said basic fatty compound.
  • the said basic fatty compound (acid, alcohol, amine) is a substantially aliphatic, long-chained hydrocarbon contain ing covalently bound in the chain the above mentioned charge-transfer groups and/or polarizable groups.
  • a monomolecular film aggregate of afore mentioned type is shown in the appended Figure 1 in cross-section.
  • a single film layer in the embodiment shown is formed from individual parallel zones, which in the figure have been given the reference numerals 2 to 7.
  • each zone corresponds to a specific part in the molecule from which the film is built.
  • all the zones 2 to 7 in the film layer are formed from their respective counterparts in one and the same organic molecule, starting from the support surface 1 to the opposite end of the molecule, which in the embodiment shown is the hydrophilic part 7 of the molecule.
  • a single molecule extends only through the zones 3 to 7, in which case the support surface has to be precoated with a compound corresponding to the zone 2, as will be explained in more detail below.
  • the individual zones in the film layer are thus formed by cooperatively acting parts of different molecules or side chains "packed” side by side in a mutually parallel manner, and extending generally perpendicularly to the substrate surface, the said co-operative parts of different molecules/side chains being positioned at substantially the same distance from the support surface or the opposite end of the molecule, respectively.
  • the numeral 1 denotes the support surface of the film aggregate, which support surface is made from a substantially inert material, such as silicon, glass, a suitable plastic or metal, and which may be coated with one or several film layers. The coating of the support surface takes place in a manner known and will be discussed in more detail below.
  • the reference numeral 2 Adjacent the support surface 1 one of the so-called spacerzones has been given the reference numeral 2, which as regards its electrical properties is substantially inert and which advantageously is formed by an aliphatic or substantially aliphatic straight or branched hydrocarbon group, the length of which may vary considerably and which can have from 1 to 20, but preferably 4 to 16 carbon atoms.
  • This hydrocarbon group may also as a chain member contain a heteroatom, such as oxygen, nitrogen or sulphur, provided that the presence of such a heteroatom does not substantially affect the relatively inert nature of the said group.
  • the spacer-zone 2 corresponds to the hydrophobic end of the basic fatty unit and in a preferred embodiment is formed by the outer ends of the fatty side chains of the phospholipid molecule.
  • the spacer-zone 2 may also be formed from a substantially aliphatic hydrocarbon used for precoating the substrate surface.
  • the part of the molecule forming this zone may also exhibit polymerizing properties, for example in the form of double or triple bonds, which may form crosslinks, such as polyacetylene structures with the corresponding parts in the side chains of the same or of an adjacent molecule.
  • this part of the molecule may contain groups, which facilitate the binding of the molecule to the support surface, for example photoactivated diazo groups bonded to an aromatic (benzene) group.
  • Adjacent the zone 2 of the film layer follows, in a direction away from the support surface, the conductive area of the film, which as a whole is formed by a polarizable zone 3 (or 5), a charge-transfer zone 5 (or 3) and a spacer zone 4 separating these. This area may extend over a distance of from 5 to 30 ⁇ .
  • the mutual position of the polarizable and charge-transfer zones respectively is not critical, provided that the film layer does contain these two zones and that they are separated by a spacer-type zone.
  • the spacer-zone 4 corresponds to the above defined zone 2, and the substantially aliphatic groups contained therein may also be polymerizable (e.g. over triple bonds) with corresponding groups in adjacent chains.
  • the conducting properties of the film are believed to result from interaction between the zones 3 and 5, which involves direct electron transfer between the zones, or the polarizable zone may form a kind of a buffer zone to the charge-transfer zone. Irrespective of the reason for the good properties, the result from the standpoint of electrical conductivity is optimal and studies have shown that it is possible to obtain even superconducting properties at high temperature (300°F).
  • the electrical properties of the films can be modified or regulated at two levels: firstly, by suitably choosing the groups to be used in the conducting area, the films may be "tailored" according to intended use, and secondly, the electrical properties of the finished film may, in addition, be subsequently modified, e.g. by means of light or an external electrical field.
  • the outermost film zone is formed by a hydrophilic group, e.g. the phosphoryl group of the phospholipid molecule.
  • a hydrophilic group e.g. the phosphoryl group of the phospholipid molecule.
  • other polar groups may be employed, such as present in sulfo- and arsenolipids.
  • the groups contained in the hydrophilic zone may be modified to exhibit polymerizing properties, for example in the form of double bonds.
  • a typical alcohol ester exhibiting polymerizing properties is also serine, which together with adjacent similar groups forms a polyamide structure.
  • Groups or pairs of groups forming part of the molecule and suitable for use in the charge-transfer zone of the film layer are known in the art and according to the invention any pair of charge-transfer groups may be used, provided it possible to bind the same covalently to the substantially aliphatic hydrocarbon chain.
  • the compounds (or groups) capable of forming charge-transfer complexes can generally be characterized as containing conjugated cyclic systems ( ⁇ - electrons), such as in aromatic rings, for example bridged or fused aryl groups containing generally from 1 to 6 rings, e.g. phenyl, naphtyl, anthryl, phenanthryl, or more complex aromatic systems, such as pyrene, perylene, triphenylene, which groups optionally may be substituted in order to enhance either their donor or their acceptor properties, respectively.
  • Suitable substituents thus are e.g. alkyl (preferably 1-3 C), alkoxy (preferably 1-3 C), cyano, hydroxy, oxo, amino, substituted amino (e.g.
  • An aromatic ring may contain a substituent in any of the free (available) positions, i.e. generally not more than 4 substituents in a ring.
  • the cyclic systems may also contain usually not more than 4, and generally only up to two heteroatoms, such as oxygen, nitrogen, sulphur, and/or selenium as an integral part of the ring, such as in carbazole, phenothiazine, pyrazine, acridine, thianthrene, oxanthrene, tetrathiofulvalene, tetraselenofulvalene, etc., and metal atoms.
  • certain compounds which do not belong to the above mentioned general classes that is for example A-vitamin disclosed below, the chain of which may form the spacer group.
  • the quinone type groups and of these quite specifically the pair benzoquinone-hydroquinone, as well as the hydroquinone forms of anthracene and phenanthrene.
  • An applicable pair is also tetracyanobenzene as the acceptor and tetramet hylbenzene as the donor.
  • CT-pairs are tetracyanoquinodimethane (TCNQ) and the oxygen of the ester and ether bonds of the diacyl- and dialkylphospholipids.
  • TCNQ tetracyanoquinodimethane
  • pyrene is capable of forming a charge-transfer type system with another pyrene group.
  • polarizable moieties can be parinaric acid, vitamin A, and diphenyltetradiene, -hexatriene and so on.
  • suitable groups for the purposes of the invention comprise the aromatic hydrocarbon groups which also may contain heteroatoms as long as these do not substantially influence the general nature of the compounds. Of these may be again especially mentioned the pyrene and perylene group.
  • the different zones correspond to molecular parts belonging to the same molecule, possibly excluding the first spacer-zone, i.e. molecule extending from the support surface or conducting area, respectively, to the outermost zone of the film layer.
  • the first spacer-zone i.e. molecule extending from the support surface or conducting area, respectively.
  • a typical compound to be used in the layer is a phosphoglycerol derivative, both substantially aliphatic ether, amide or ester side chains of which contain, possibly at a distance (1 to 20 C- atoms) from the outer end of the side chain, covalently bound a polarizable group, for example a pyrene group, and at a distance therefrom (1 to 20 C-atoms) in one of the aliphatic side chains of the glycerol the one member of a charge-transfer complex pair, for example a benzoquinone group, and in the other side chain the corresponding hydroquinone group.
  • the positions of the polarizable and the charge-transfer groups in the side chains may be reversed whereby the charge-transfer zone in the described embodiment will be closer to the support surface.
  • the support surface may, prior to coating the same, be treated in order to modify its surface properties, for example as described in the international application PCT/FI85/00102.
  • a pretreated surface may, as was mentioned earlier, be further coated with a monomolecular layer forming the first spacer zone.
  • a compound used for precoating with e.g. a covalently bound member of a charge-transfer pair, or alternatively, a polarizable group, which then will form part of the conducting area (3 to 5) of the film layer.
  • the outermost substantially aliphatic hydrocarbon moiety in the fatty chain for example in a fatty side chain of the phosphoglycerol and possibly, in addition, the second member of the charge-transfer complex pair or one or both of the polarizable groups, respectively, will be absent in the film forming compound to be applied onto the pretreated support surface.
  • Essential is that in the film layer formed, irrespective of the method of preparation, the different zones will be uniform both to their structure and to their properties.
  • the fatty acids, alcohols or amines which, when part of the film layer, form the respective zones necessary for obtaining the desired electrical properties in the finished film, and which contain covalently bound a polarizable group and/or a group constituting one member of charge-transfer pair, in a substantially aliphatic hydrocarbon chain may be characterized by the general formulas
  • zig-zag-symbols mean substantially aliphatic, straight or branched hydrocarbyl groups containing about 1 to 20 C-atoms, preferably from 4 to 16 C-atoms, and which may contain heteroatoms (oxygen, nitrogen, sulphur) provided these do not substantially affect the substantially aliphatic nature of the hydrocarbyl group
  • A means one member of a charge-transfer pair and B means a polarizable group, the integers n, m and q mean 0 or 1,
  • compounds for forming the film layer are preferably used phosphoglycerols wherein both hydroxy groups have been substituted with a compound having either the formula (la) or the formula (lb), or a threitol derivative, wherein at least two of the hydroxy groups have been substituted with either a compound of the formula (la) or with a compound of the formula (lb), thus forming an ester-, ether or amide bond with the compound (la) or (lb) respectively.
  • substituted compounds are new and thus also form an object of the present invention.
  • the phosphoglycerols of the invention may be schematically presented in the following manner.
  • n, m and q have the meanings given in connection with the formu las la and lb
  • a and A' mean groups forming a chargetransfer complex
  • B and B' which may be the same or different, mean a polarizable group
  • n', m' and q' have the meaning of 0 or 1
  • X is hydrogen, or it is the residue of an alcohol, especially a lower alkanol, amino lower alkanol, serine, choline, 1- or 3-glycerol forming an ester with the phosphoric acid group, with the provision that n+m, and n'+m' are irrespective of each other 1 or 2, and q and q' are irrespective of each other 0 or 1.
  • the compounds of the formula (Ila) and (lib) thus contain in their fatty side chains either 1, 2 or 3 spacer groups, and one or two active groups, i.e. either both a chargetransfer group as well as a polarizable group, or only one of these groups.
  • a third spacer zone can be provided by precoating the substrate surface with a corresponding substantially aliphatic hydrocarbon as mentioned earlier.
  • the compound described above for precoating the substrate may carry the corresponding absent group as well in order to obtain a usable film.
  • such a group may also be provided in the side chain of a differently substituted phospholipid which is used as a mixture with the first mentioned, or in certain instances, in a corresponding fatty acid, alcohol or amine of the formula (la) or (lb), respectively, used as such together with the first mentioned phospholipid.
  • substantially aliphatic means that in the formulas I and II the spacer group may contain also nonaliphatic groups, but that it remains substantially alip hatic in character.
  • the spacer groups may contain double or triple bonds capable of polymerizing, and in the terminal spacer groups additionally groups which bind covalently to the support surface, as mentioned above.
  • the compounds according to the invention form for example the following sub classes.
  • the compounds (Ila) and (lIb) according to the invention are substantially aliphatic dialkyl-, diacyl-, diamide-, alkyl-amide-, acyl-amide- or alkyl-acyl-phosphoglycerols, containing either about 3 to 60 substantially aliphatic carbon atoms in a side chain thereof (corresponding to three spacer groups), or about 2 to 40 such carbon atoms (corresponding to two spacer groups).
  • Each side chain contains one charge-transfer group (A or A'), as well as a polarizable group (B or B'). If only two spacer groups are present in the chain the support surface can be precoated with a substantially aliphatic hydrocarbon compound corresponding to the hydrophobic outer end, i.e. a spacer group.
  • each side chain contains at least one active group. If in the compound (Ila) a polarizable group B or B' or in the compound (lib) a charge-transfer group A or A' is missing in a side chain, the support surface can be precoated with a compound substituted with a polarizable group B or B or a required charge- transfer group A' or A respectively, and containing from 1 to 20 carbon atoms in a substantially aliphatic chain.
  • a required polarizable or charge-transfer group can also be provided using a mixture of appropritely susbtituted phospholipids.
  • the threitolphospholipids may be used in connection with precoated substrates providing required spacer an optionally polarizable or charge-transfer groups. Similary, for the film formation a mixture of suitably substituted glycerophospholipids and/or threitolphospholipids may be used, for example in order to provide the necessary CT-members, as well as a mode wherein a glycero- or threitolphospholipid is used under carefully controlled conditions together with a free fatty acid, alcohol or amine of the formula (la) or (lb) containing the necessary active groups.
  • the afore mentioned compounds may be prepared with processes known as such.
  • glycerol or D-mannitol may be prepared, for example, by introducing into a glycerol or D-mannitol, or into threitol, the acyl, amide and/or alkyl side chains which are to be included in the final compound and which carry the desired charge-transfer and/or polarizable groups (M. Kates, Methods in Membrane Biology, Vol. 8, 1977, Plenum Publ.Corp. p. 219-290). Thereafter e.g. the substituted D-mannitol is split and reduced to the corresponding glycerol. The substituted glycerol may thereafter be esterified in its free position in order to introduce the desired phosphoryl group or a derivative thereof.
  • phosphoryl-glycerol group may be introduced by reacting a 1,2-diacyl-glycerol with phosphorous oxychloride in the presence of triethylamine.
  • the product obtained is thereafter reacted with 1-trityl-snglycerol in the presence of triethylamine and the hydroxy groups of the phosphoryl-glycerol groups are liberated.
  • p. 40-74 are disclosed processes for the preparation of phosphoryl-ethanolamine and -choline.
  • the film aggregate according to the invention may be prepared in a conventional manner for example applying Langmuir-Blodgett-coating techniques.
  • This technique is based on letting the film forming, surface active compound, for instance a phospho- or sulpholipid, orient itself at the interface between two phases, for example the interface between a liquid (water, glycerol, etc) and a gas, such as air, argon, etc., whereby the hydrophilic part of the molecule orients itself towards the liquid, and the hydrophobic part, that is the lipophilic part, orients itself in a direction away from the liquid.
  • the desired compound or mixture of compounds is dissolved in a suitable organic solvent or solvent mixture, e.g.
  • the solvent evaporates rapidly.
  • the film is transferred as a monomolecular layer onto the support surface, the lipophilic part towards the support surface if the body is transported through the film in a direction from the air to water, and the hydrophilic part towards the support surface if the body is transported through the film in the opposite direction, i.e. from the water to air.
  • the fatty acids, alcohols, amines and their derivatives are often very poorly soluble in the solvents used for the manufacture of Langmuir films at liquid-gas interfaces.
  • the compounds thu ⁇ formed are easily dissolved e.g. into chloroform, whereby they may be easily spread as monomolecular layers with controlled compression onto a water surface, which is a requisite for making Langmuir-Blodgett films on solid substrate surfaces.
  • the film aggregates obtained according to the invention may be used a such or they may be polymerized, for example using light or heat, or alternatively they may in a suitable manner be bonded to the support surface, either the layer as a whole or only sections thereof, depending on the intended use.
  • Non-polymerized or non-bonded film areas may thereafter be removed in a suitable manner, for example by dissolution, whereby a conducting film of desired configuration can be obtained.
  • One suitable area of use is e.g. in microlitography, drawing microcircuits into the film with a laser or electron beam in order to promote polymerisation and/or bonding to the surface, and thereafter removing the untreated areas.
  • the conductivity of the compounds according to the invention in the film aggregates is best measured using a so called four point measurement system, according to which onto the silicon, glass etc substrate surface is e.g. vacuum deposited metallic conducting electrodes, e.g. of gold.
  • the films may be layered directly onto the substrate surface or the surface can be rendered hydrophobic by alkylation or by using the method disclosed in the Applicants' international application PCT/FI85/00102.
  • a monomolecular layer may then be formed from one type of molecule.
  • Optimal with regard to conductivity is, however, a structure which is comprised of one type of phospholipid derivative, wherein, instead of using a mixture of two different acids, these two acids are interconnected over a common glycerol structure.
  • the voltage is applied between the furthermost electrodes and the conductivity of the film aggregate is measured as a current between the centerm ⁇ st electrodes.
  • the frequency dependancy of the current is dependant of the composition of the film.
  • the energy belts and conditions (states) of the film may optically be measured based on the absorption of electromagnetic radiation in the UV and visible area, as well as in IR frequencies.
  • the transmission measurement carried out in the optical and UV area usually requires the use of quartz as the substrate. In some cases additional information is received from fluorescence emission and excitation spectra and the relationship to time of the former allowing for the evaluation of the formation of exitons and their diffusion in the film, as well as the influence on these processes by an external field.
  • 1-hexadecyl-2,5-dimethylbenzene 70 g was dissolved into 120 ml of 1,2-dichlorobenzene.
  • the methylesterchloride of hexanoic diacid was added in 100 ml of 1,2-dichloroethane and while stirring on an ice bath 42.3 g of aluminium chloride was added in small portions. The mixture was stirred on the ice bath for 1.5 hours and at room temperature for 1.5 hours.
  • the reaction mixture was poured into a mixture of 250 ml of ice and 110 ml of 0.5 M hydrochloric acid.
  • the mixture was extracted with 400 ml of dichloromethane, and washed with water, 160 ml of saturated sodium bicarbonate solution and with water.
  • the ester obtained from the previous step was dissolved while heating into diethylene glycol (50 ml) containing 1.2 g of potassium hydroxide. The mixture was heated for one hour on a water bath. The reaction mixture was poured into a mixture containing 50 g of ice and 12 ml of concentrated hydrochloric acid. 160 ml of ether was added. The ether layer was washed to neutral and dried over sodium sulfate. Crystallization from 60 ml of ethanol afforded 5.8 g of crystals with a m.p. of 73-75°C. This acid was used for preparing the phospholipid.
  • the mixture was dried on sodium sulfate and evaportaed to dryness and purified chromatographically.
  • Silica was used in an amount of 3 kg and the eluent was petrolether/ ethylacetate 19:1. 350 g of an oily product was obtained and was used a such in the next step.
  • the dichloromethane solution was washed three times with 400 ml of 1:3-mixture of methanol and water and dried on sodium sulfate. The solution was evaporated to dryness and crystallized from 950 ml methanol. 169 g of a pure product was obtained which according to NMR had the correct structure.
  • This product was used for the preparation of phospholipids and also for the preparation of quinonehexanoic acid derivatives.
  • This product was transformed to its acid chloride using oxalyl chloride and was bonded to further active groups using a Friedel-Crafts reaction.
  • the acid chloride from the previous step (18 g) was dissolved into 60 ml of 1,2-dichloroethane. 12.0 g of pyrene and in ice, 23.7 g aluminium chloride. The mixture was stirred in ice for 0.5 hours and 2 hours at room temperature. It was poured into a mixture containing 180 g of ice and 90 ml of 2M hydrochloric acid, 120 ml of dichloromethane was added and washed with water, 0.5M sodium hydroxide and 0.5M hydrochloric acid and water. The mixture was fractionated on a silica column using as the eluent a 9:1-mixture of toluene/ethyl acetate. After crystallizing from the eluent in the refrigerator 14.8 g of the desired product was obtained.
  • the product from the previous step (8.4 g) was reduced using the Wolf-Kishner method, whereby 3.6 g of a product with a m.p. of 118-118.5°C was obtained.
  • 1-pyrenyl-dodecanyl-3-triphenylmethyl-sn-glycerol (6.0 g; prepared by reacting pyrenyldodecanol mesylate with isopropylidene glycerol and hydrolyzing the isopropylidene protection and protecting the liberated primary hydroxy group with a triphenylmethyl group), decylquinone hexanoic acid (3.7 g) and dimethylaminopyridine (210 mg) was dissolved into 50 ml of dichloromethane. 2.1 g of dicyclohexylcarbodi-imide was added. The mixture was allowed to react for 4 hours at room temperature and 50 ml of hexane was added.
  • the product from the previous step (7.9 g) was dissolved into toluene and added to a 150 g boric acid/silica column and eluted with with 500 ml of toluene and toluene/ethyl acetate 95:5 and 90:10.
  • the product was crystallized from ethanol, whereby 3.7 g of a pure product (m.p. 80-1°C) was obtained which was used for the preparation of phospholipids by introducing a phosphoryl group in a known manner.

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Abstract

Un agrégat pelliculaire conducteur d'électricité comprend une surface de support sensiblement inerte qui porte une ou plusieurs couches pelliculaires monomoléculaires formées par un agent tensio-actif du type à cristaux liquides ayant des propriétés électriques modifiables. La couche pelliculaire a une structure de type intercalaire ayant au moins les zones suivantes: - une zone d'écartement (3) contenant des groupes hydrocarbyles aliphatiques et sensiblement inerte pour ce qui est de ses caractéristiques électriques, - une zone conductrice (3 - 5) composée d'une part d'une zone de transfert de charge (3 ou 5) et d'autre part d'une zone polarisable (5 et 3), une zone d'écartement (4) étant agencée entre ces deux zones, - une zone d'écartement (6) correspondant à la zone (2) ci-dessus, - une zone hydrophile (7). Des glycérophospholipides et des thréitolphospholipides novateurs sont utilisés pour former ces pellicules. Ils contiennent dans leurs chaînes latérales d'acides gras au moins un groupe polarisable et un groupe de transfert de charge. L'invention concerne également les acides gras, les alcools et les amines utilisés pour former les chaînes latérales des lipides et portant un groupe polarisable et un groupe de transfert de charge.
EP86904183A 1985-06-28 1986-06-27 Agrégat pélliculaire ayant des propriétés de conductibilité électrique Ceased EP0228429A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI852574 1985-06-28
FI852574A FI852574A0 (fi) 1985-06-28 1985-06-28 Filmstruktur samt nya foereningar foer anvaendning i detsamma.

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EP0228429A1 true EP0228429A1 (fr) 1987-07-15

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EP86904183A Ceased EP0228429A1 (fr) 1985-06-28 1986-06-27 Agrégat pélliculaire ayant des propriétés de conductibilité électrique

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EP (1) EP0228429A1 (fr)
JP (1) JPS62503202A (fr)
AU (1) AU6134586A (fr)
BR (1) BR8606785A (fr)
DK (1) DK95887D0 (fr)
FI (1) FI852574A0 (fr)
HU (1) HUT46820A (fr)
WO (1) WO1987000343A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI77679C (fi) * 1987-02-23 1989-04-10 K & V Licencing Oy Filmaggregat och foerfarande foer dess framstaellning.
FI871320A (fi) * 1987-03-25 1988-09-26 K & V Licencing Oy Nya langmuir-blodgettmembranstrukturer.
US5441610A (en) * 1992-02-28 1995-08-15 Renlund; Gary M. Oxygen supply and removal method and apparatus
DE4343412A1 (de) * 1993-12-18 1995-06-22 Basf Ag Elektrolumineszierende Anordnungen
US6531591B1 (en) 1999-07-07 2003-03-11 Exiqon A/S Synthesis of stable quinone and photoreactive ketone phosphoramidite reagents for solid phase synthesis of photoreactive-oligomer conjugates
FR2966466B1 (fr) * 2010-10-21 2013-07-12 Rhodia Operations Accepteurs quinones pour application photovoltaique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60120361A (ja) * 1983-12-05 1985-06-27 Canon Inc 感光体
FR2564231B1 (fr) * 1984-05-10 1986-09-05 Commissariat Energie Atomique Films conducteurs de l'electricite comprenant au moins une couche monomoleculaire d'un complexe organique a transfert de charge et leur procede de fabrication
FR2564004B1 (fr) * 1984-05-10 1993-04-09 Commissariat Energie Atomique Procede de fabrication d'un film mince comportant au moins une couche monomoleculaire de molecules non amphiphiles

Non-Patent Citations (1)

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Title
See references of WO8700343A1 *

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DK95887A (da) 1987-02-25
JPS62503202A (ja) 1987-12-17
HUT46820A (en) 1988-11-28
BR8606785A (pt) 1987-10-13
WO1987000343A1 (fr) 1987-01-15
AU6134586A (en) 1987-01-30
DK95887D0 (da) 1987-02-25
FI852574A0 (fi) 1985-06-28

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