DE2637099A1 - PROCESS FOR PRODUCING COMPOSITE ARRANGEMENTS WITH THIN-LAYER COMPONENTS AND COMPONENTS OBTAINED AFTER THEM - Google Patents

Description

TlEDTKE - BoHL.NG ■ Κ, ΝΝΕ - GROUP

Dipl.-Chem. Bühling Dipl.-Ing. Chins Dipl.-Ing. Group

λ £ ο 7 η Q Q Bavariaring 4, P.O. Box 20 24

^ 0 O / U σ α 8000 Munich 2

Tel .: (0 89) 53 96 53-56

Telex: 5 24 845 tipat

cable. Germaniapatent Munich

Aug 18, 1976 -

B 7588 / ICI case Q.28135

IMPERIAL CHEMICAL INDUSTRIES LIMITED London, United Kingdom

Process for the production of composite arrangements with Thin-film components and components obtained afterwards

The invention relates to a method for the production of composite arrangements Components that have components in the form of thin films.

Different classes of arrangements or components? in particular electrical, electrochemical or photochemical components, comprise a thin layer of a - usually insulating - organic material with a high degree of molecular orientation. Conventional Layers or films of material with a certain degree of orientation have been created, for example, by abrasive shaping made of single crystals, however, dislocations or defects and discontinuities usually occur in the crystal lattice before the desired low layer thickness is reached. Also, the dimensions of the resulting Layer limited by the size of the original crystal. Alternative techniques for making

^V 709809/1041

Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account 670-43-804

very thin layers make use of the deposition of Filming from the vapor phase; thermally grown oxide films have also been used.

The present invention now relates to a method of making a sheet or film of organic material with a high degree of molecular orientation on a substrate that is essentially the Formation of a very thin, preferably monomolecular layer of an organic material with a flat "de-localized" (without discrete spatial assignment) System of IL electrons on the surface of a suitable liquid and moving a substrate through the layer to deposit a film of the organic material includes on the substrate.

The organic material used according to the invention is one with a planar de-localized System of TC electrons that can be acyclic or cyclic can; such systems can be, for example, aromatic, non-aromatic or anti-aromatic systems and they can be carbocyclic, heterocyclic or organometallic. The applied organic material should be both have hydrophobic as well as hydrophilic properties, which expediently depend on the presence of suitable hydrophobic and / or hydrophilic groups in the molecule ("hydrophobic" denotes the ability to repel water, so that a water-soluble molecule ^ which carries such a hydrophobic group, to accumulate at the interface Air-water tends to decrease the surface tension of a solution in which it is dissolved. Under "Hydrophilic" is understood to mean the ability to attract water, which is due to the presence of electrical poles and dipoles in the group).

Typical hydrophobic groups include hydrocarbons

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hydrogen chains, which are usually linear alkyl radicals, but can be branched alkyls or linear polyacene chains or aromatic rings. Alkyl groups can contain heteroatom groups such as, for example, O, NH, S, SO ₂ . Typical hydrophilic groups include -COOH, OH, NHp, CN, SO H, NR ¹ y Sr _{>> 2} (with R ¹ = alkyl or aryl), PO ₄ and -SOCH ,.

It was previously believed that an organic molecule was responsible for the formation of a stable film on water contain hydrophobic hydrocarbon chains of considerable length, preferably more than 16 carbon atoms should. However, it has been found that the use of such materials is undesirable where the material is in a multi-layer arrangement is used, the semiconductor properties should show. So it was found for such an arrangement that it is for the case that the hydrophobic Group is formed by a hydrocarbon chain, it is desirable that the to be spread or deposited organic material does not have a hydrophobic chain longer than 10 carbon atoms (i.e. elongated Chain length) and preferably no hydrophobic group with more than 3 to 8 carbon atoms chain length; preferably any such chain will be linear.

A compound that has a plurality of both hydrophobic as well as hydrophilic groups can be used, but the hydrophobic / hydrophilic equation should be used. are maintained, for example in such a way that the connection is not in the carrier or support liquid dissolves or disperses (and so no surface film is formed) and otherwise in such a way that they does not become so predominantly hydrophobic that the film is unstable.

Usually the organic compound is therefore 709809/1041

have the following structure:

R - C - X,

where R is a hydrophobic group, X is a hydrophilic group and C is a cyclic or acyclic structure with a planar de-localized system of ^ -electrons means, although R or X in the case that C itself is pronounced hydrophobic or has hydrophilic properties, can be correspondingly absent. Preferably C is cyclic Structure and in addition to R and X it may have substituents such as H, halogen, quinoid oxygen, twofold bound sulfur, nitro, dimethylamine, acyl and oxyamino. One or more such substituents can or can act as metal ligands.

Alternative arrangements of the components can be: C-R-X or C-X-R.

When C is cyclic, it can have one or more rings, which can be carbo- or heterocyclic and may include metal atoms.

As examples of classes of organic compounds from which films are produced in the manner described the following should be mentioned. (In the formulas, R is preferably an n-alkyl chain of no more than 10, in particular 3 to 8 carbon atoms in length and η can be zero or an integer not more than 12 and preferably from 1 to 3).

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- 5 - Carbocyclic compounds

RO RSO,

(D

(2)

.N-NHR

- / ' Λ— N = N - /' vv OR

(4) (5)

R

NMe.

(Halide) "(6)

NMe,

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(7)

(8th)

(9)

RRR

(CH ₀ ) CO ₀ H zn ζ

(H)

(12)

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(13)

(15)

(17) SO ₃ Na

SO ₃ Na

SO ₃ Na

(16)

(CH

S, S

R R

C18)

(19)

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(20)

(22)

(21)

(CH) X λ η

(CH ₂ )

(24) (CH ₂ ) _n x

(CH ₂ ) η

(25)

O R Jl OH

(26

CN CN

(27)

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O (CH ₂ ) _n X

(28)

Heterocyclic compounds

(30)

ο (CH ₉ ;

(31)

(32)

(33)

(34)

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(36)

(37) (38)

R Ph.

R Pil

NMe

^(CH 2 »"
X

^{(C. H} 2> n

(39)

(40) (41)

(42)

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(43)

- 11 -

, N

(45)

N '

(46)

(49)

(52)

(47)

(48)

BF.

(50)

O>

ε, s

(53)

C54)

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(55)

(56)

BF,

(57)

(58)

(59) (60)

(64)

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(65)

NMe

(CH ₂ )

(66)

BF,

(67)

O (68)

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(69)

MeN,

(70)

Xj

NMe

C71) Me

N

\ BF,

Me

(72)

Transition metal complexes

(73)

N N

Vf

R R

C74) (75)

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(76)

^C 6 ^H 5

(77)

RCO "

OCOR

Cl

Cl

(78)

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SO ₉ NHR

(79)

SO ₂ NHR

(80)

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The exact location of the specified substituents may be unimportant and additional substituents may be included in the above molecules in accordance with ability of the resulting material are incorporated, a monomolecular layer on a suitable liquid and deposited in a suitably integral form on a substrate to achieve a Films with desired properties.

It has been found that Langmuir films can only be produced with great difficulty from mononuclear heterocyclic compounds can be formed and these are preferably avoided or left aside.

A preferred group of compounds for use in assemblies requiring electroluminescence or Show photoconductivity are the anthracenes (or other electroluminescent or photoconductive compounds such as pyrenes or perylenes), especially those that

in the 9-position with a hydrophobic linear alkyl with 3 to 8 carbon atoms are substituted, which more particularly has no more than 4 carbon atoms. The molecule expediently comprises a hydrophilic group in one of the 3, 4, 5, 6 or preferably 10 positions.

Preferably the molecule has only one of the hydrophilic and hydrophobic groups.

The deposited film of the organic material can be applied as it is, that is, in a monomolecular one Shape, however, is usually the increase in layer thickness through repeated application of layers of the same material may prove desirable to extend its applicability (typically 20 to 200 Layers for thin-film transistor arrangements and 1 to 10 layers for applications using the tunnel

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effects of warm electrons); or through interposition other materials; or modifying the material by forming a film with more than one Component.

This means that both monomolecular (e.g. for tunneling warm electrons) and multimolecular ones became (e.g. electroluminescent) organic films are used, the multimolecular films being passed through repeatedly of the substrate by a monomolecular layer of the organic material on a suitable Liquid, as described in more detail below, were formed.

Techniques for the formation of a monomolecular layer on a supporting substrate are from US Pat Langmuir trough technology known, however the procedure can be summarized as follows: As supportive or the carrier liquid is one which is usually inert to the organic material, i. e. it does not react adversely with the material under the conditions used in the process according to the invention of the layer or substrate (although it has been found desirable in certain circumstances to include Include fluid components, particularly ions, that interact with the film material or other components of the The liquid may be a solvent for the organic material, but it is preferably not, the important requirement being that the organic material adheres to the liquid soberf pool is enriched in such a way that it can be removed (or lifted off) as a layer or film. the Liquid can be organic or inorganic; The use of water is usually preferred, although the stability of the organic layer may be improved by the presence of inorganic ions.

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The formation of the monomolecular layer of the organic material on the surface of the carrier liquid is most conveniently carried out by applying an appropriate amount of a solution of the organic material in one volatile solvent on the surface of the liquid that normally does not apply to the carrier liquid is miscible. The technique of applying the organic material to the liquid sub-phase and compressing it are generally known to the person skilled in the art.

The transfer of the organic material to the substrate, which may be of any suitable material can be done by immersing the substrate in the carrier liquid and pulling it out again so that the film of the organic material adheres to the surfaces of the substrate. Precautions or means of maintenance The integrity of the layer on the liquid are necessary and can use a wiper or a sweeping agent or paddles, which are preferably controlled by a microbalance, the surface pressure of the Films constantly. This feature of maintaining constant pressure on the organic layer is important for producing an aligned deposit on the substrate.

The invention is ■ particularly suitable for "doping" either by incorporating the dopant as a foreign substance of suitable concentration in the film of the organic material on the carrier liquid or by deposition of the dopant as a separate one Layer or by "shooting in between" organic material (commonly referred to as host material will). An example of the application of such a technique could be the manufacture of an arrangement a device comprising alternating films of a photoconductor and sensitizer; age-

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nating p-type and η-type layers; as well as alternating Include semiconductor and insulator layers. Suitable dopants include dyes that add color to change the radiation emitted by the arrangement; for example, by the presence of about 1 ppm tetracene in the anthracene derivative changes the color from blue to yellow.

The invention is useful for making a variety of assemblies with different Purpose (see the applicant's patent application of the same in connection with the present application Days according to GB patent application 34263/75). Thus, according to one embodiment of the invention exploited the process for the production of electroluminescent devices, the anthracene derivatives or suitable semiconducting materials such as pyrene or perylene derivatives. Anthracene was previously used in electroluminescent devices in the form of crystals (see U.S. Patents 3,530,325 and 3,382,394 in which also the electroluminescence principle is specified).

According to this aspect of the invention, a method for producing a composite product is therefore provided in which a film of an organic material and preferably an anthracene, perylene or pyrene derivative, as described above, is deposited or deposited in contact with a suitable conductive material and subsequently with such a material is contacted or the organic material or preferably two surfaces of the organic material are contacted with two or more separate electrodes. The organic film formed can be of any suitable thickness, but preferably not exceeding 2 µm . Said arrangement can expediently be produced, for example, by forming a first layer

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a suitable electrode material by any suitable means; Formation of a multi-layer (approx to 500) film of a suitable anthracene derivative according to the Langmuir technique in contact with at least a surface of this layer; and applying a second electrode material to the surface of the so formed Films take place. Optionally, the anthracene film can be used after the application of the second electrode material are tempered. The first electrode material can, for example, be a suitable electron-injecting one Electrode material such as Al / AlpO. As the second Electrode material can be any defect electron injecting material such as Au, Pt, CuO / J, Se / Te etc. or mixtures thereof can be used. The application of organic hole injection materials is not excluded, such as bis (benzothiazolon) azine disulfonic acid.

Conveniently, the first electrode is on a base layer of adequate rigidity and insulating Properties for the intended use of the arrangement deposited.

Other uses of the process of the present invention include the formation of improved photoconductive materials and photo element systems in which the deposition of molecularly ordered material is an important factor in optimizing performance.

In yet another aspect of the invention a method of making improved insulated gate field effect transistors (IG-FET) such as e.g. thin-film transistors are provided.

A basic principle common to all types of unipolar transistors is the control of the current

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flow between a source and a sink electrode through a gate electrode. Cross sections of typical Transistor configurations are shown schematically in the attached Drawings shown (see also above registration) These are natural very much enlarged; many of the thin film components of transistors are of the order of magnitude only Thousands of a millimeter thick.

The problem of forming a relatively defect-free insulating layer can be avoided by removing the insulating layer deposited according to the Langmuir technique. Such films are used to form a multimolecular insulating Film component deposited of suitable thickness for the intended purpose. A cross section of one of these Arrangement is shown schematically in Figure 1 of the accompanying drawings. Typically the insulator film would Comprise 20 to 200 monomolecular layers.

The heat dissipation or dissipation in transistors can be reduced by the use of a polymer material of relative high thermal conductivity such as polyether sulfone are favored as an insulating substrate.

The application of the Langmuir technique for deposition of the semiconductor film in a transistor is also possible, although as in all cases where the technique is used, care must be taken that reagents or carrier liquids are used for the material that has already been deposited can be harmful, should be avoided.

Many deposited by the method of the invention Layers or films can act as both an insulator and an active component (depending on that a large charge mobility anisotropy exists parallel and perpendicular to the plane of the layer). A structural example for such an arrangement is shown schematically in

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2637039

Figure 2 shown. Materials with the required property can be selected from those listed above However, anthracene, perylene, pyrene, tetracene or naphthalene derivatives or organometallic compounds are used preferably applied.

Examples of materials suitable as source and drain electrodes are metals, alloys and metal oxides and salts such as Au, Al, In, Ag; High conductivity semiconductors such as Te and conductive organic materials such as bis (benzothiazolone) azine disulfonic acid. Similar materials can be used as gate electrode components can be applied.

The insulating substrate can be made from any of a wide range of materials such as mica, glass, Sapphire, split crystals, plastics with high thermal conductivity can be formed.

The material of the semiconducting layer can be any of a wide range of semiconductor materials include, to which CdS, Cd, Se, GaAs, Si, PbS, InAs, phthalocyanine, violanthrene, porphyrins and derivatives of Include anthracene, tetracene, naphthalene, pyrene and perylene.

The fabrication of thin-film arrangements and in particular of transistors, whose operability depends on the the exact spatial arrangement of their components depends on the accuracy with which the various Components can be deposited. To avoid unwanted capacitive effects, for example It is important that the gate electrode in a thin film transistor is "simultaneously" or aligned with the channel or the current path between the source and drain electrodes is deposited. The deposition of a component film according to the Langmuir technique at the desired

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Place with - if necessary - subsequent removal of the film from parts of the arrangement, for example by grinding or etching, offers a suitable method for bringing about an accurate localization of thin-film active or insulating components.

Other applications of the method according to the invention include the production of varactors, warm electron components, Warm electron transistors, Esaki M-I-M-I-M structures, Gunn effect oscillators and photodetectors. In the manufacture of varactors (components, whose reactance / capacitance can be changed in a controlled manner using a bias can) to the advantages of the deposition of film components, e.g. insulating layers, according to the Langmuir technique a high capacity (due to a thin insulating layer and a relatively large surface area), lower operating voltages due to the thin insulating layer as well as reproducibility of the characteristics of the component. Esaki M-I-M-I-M structures are layer structure arrangements with layer periods of the order of 50 to 100 A. With Gunn effect oscillators, a hot electron (0.3 eV) supplying contact is made on a single crystal preferred. This type of contact is best made using the tunnel injection principle through a thin film of insulator achieved.

A simple but effective photodetector with the structures shown in Figure 3 can be made using the Langmuir technique can be obtained. For example, a suitable photoconductor such as CdS can be placed between the gate electrode and deposited on the insulator; Light falling on the photoconductor makes it more conductive, what leads to an increase in the voltage drop across the isolator, which leads to a change in the conductance of the source-sink channel results. Alternatively, a photosensitive

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material such as a dye between the goal and the insulator (or in the insulator as a doping). Falling on the photosensitive material Light causes an injection of charge carriers into the dielectric under the influence of the gate voltage, where they affect the conduction of the source-sink current. Such arrangements are suitable for manufacture according to the method according to the invention; for example, one or both of insulators and semiconductors deposited as Langmuir film as described above will.

According to a further embodiment of the invention, a method for producing an electronic Component provided that a stage for the formation of a Langmuir film of an insulating or semiconducting organic material, in particular an organic material as described above, on a surface of an insulating, conductive or semiconducting material. (Under a Langmuir film is a film understood, which is obtained using the Lgngmuir trough technique).

The invention is described below on the basis of examples.

Examples 1 to 44 Manufacture of anthracene derivatives

Using the procedures of Sieglitz (Reports £ 6 (1925) 1619) and Stewart (Australian J. Chem. 1960 478), anthrone was converted to 9 ~ alkyl-10-hydroxymethylanthracene.

The conversion to the 10-bromomethyl derivative was as carried out as follows: 0.1 mol of the 1O-hydroxymethyl compound

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- 2 B -

manure was suspended in 500 ml of dry diethyl ether. Two drops of pyridine and then (dropwise) 0.05 mol of phosphorus tribromide in 50 ml of dry ether were added. The mixture was stirred for 2 hours at 20 ^° C., poured onto ice and extracted with dichloromethane to obtain the 10-bromomethyl compound.

A mixture of diethyl malonate (4.8 g), dry toluene (200 ml) and finely cut sodium (0.75 g) was ^{heated to 80 °} C. for 2 hours. 9-Alkyl-10-bromomethyl-anthrace, n (0.02 mol), dissolved in dry dioxane (200 ml), was added dropwise to the cooled solution with stirring and the mixture was stirred ^{at 20 ° C. overnight.} The mixture was diluted with 500 ml of 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 g) 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 evolved gradually The solution was diluted with petroleum ether for 30 minutes and cooled. 9-alkyl-anthranyl (10) propionic acid crystallized the end.

The following anthracenes were prepared in the manner described above:

R-.

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O CD OO CD CO

at
game
No. ^R l R ₂ Fp solvent
to the recrystalline
lize at
game
No. ^R l ^R 2 Fp solvent
to Umkri
install 1 C ₂ H ₅ H 50-52 Petroleum ether 17th ^C 6 ^H 13 CH ₂ CH ₂ CO ₂ H 164-6 Peircuether 2 C ₃ H ₇ H 55-59 Methanol 18th ^C 8 ^H 17 CH ₂ CH ₂ CO ₂ H 136-7 Il Il 3 ^C 4 ^H 9 H 4 8 Il 19th ^C 12 ^H 25 CH ₂ CH ₂ CO ₂ H 112-3 Methanol 4th ^C 6 ^H 13 H 67-8 Il 20th ^C 2 ^H 5 CHO 87-88 Ethanol 5 ^C 8 ^H 17 H 36-40 Il 21 ^C 3 ^H 7 CHO 94-5 Petroleum ether
-Toluene 6th ^C 12 ^H 25 H 40-45 Ethanol 22nd C ₄ H ₉ CHO 78 Petroleum ether 7th ^C 2 ^H 5 CH ₂ OH 193-7 Methanol 23 ^C 6 ^H 13 CHO 70 Il Il 8th C ₃ H ₇ CH ₂ OH 200 Il 24 ^C 8 ^H 17 CIIO 57-8 I · Il 9 C ₄ H ₉ CH ₂ OH 194-5 Il 25th ^C 12 ^H 25 CHO 80 Ethanol 10 ^C 6 ^H 13 CH ₂ OH 160-2 Il 26th ^C 2 ^H 5 CH ₂ Br 173-5 Petroleum ether
-Toluene 11 ^C 8 ^H 17 CH ₂ OH 153-4 Il 27 ^C 3 ^H 7 CH ₂ Br 145 Petroleum ether 12th ^C 12 ^H 25 CH ₂ OH 147-8 Il 28 C ₄ H ₉ CH ₂ Br 139 ■ ι H 13th ^C 18 ^H 37 CH ₂ OH 139-40 Cyclohexane 29 ^C 6 ^H 13 CH ₂ Br 139-40 Il Il 14th C ₂ H ₅ CH ₂ CH ₂ CO ₂ H 169 Petroleum ether 30th C ₈ H ₁₇ CH ₂ Br 105-7 Il Il 15th C ₃ H ₇ CH ₂ CH ₂ CO ₂ H 19 8-200 Il Il 31 ^C 12 ^H 25 CH ₂ Cl ^b 99-100 Il Il 16 C ₄ H ₉ CH ₂ CH ₂ CO ₂ H 127-8 ^a Il Il

Comments on the table:

a) This material crystallized in two forms with melting points 151-2 and 127-8 ⁰ C ⁰ C with identical spectroscopic properties. The latter material with a melting point of 127-128 ⁰ C is obtained after 4 or 5 recrystallizations from petroleum ether and this material was in all Langmuir trough experiments.

b) Prepared by the Stewart method (Australian J. Chem. 1960 478).

Other anthracene derivatives were prepared as described below.

Example 32 Production of 9-butyl-IO-carboxv-anthracene

9-Butyl-1O-anthraldehyde (6.6 g) was 4 hours Long brought to reflux conditions with silver oxide, the 50 tigern aqueous ethanol from silver nitrate (6.5 g) (150 ml) and sodium hydroxide (4 g) was. The mixture was diluted with 300 ml of water, filtered hot, then acidified and the product filtered off and recrystallized from toluene; Mp 176.

Example 33 Production of 9-butyl-anthranyl-r-acetic acid

A solution of 9-butyl-10-bromomethyl-anthracene (5.74 g) in dioxane (10 ml) was added for a few minutes long combined with potassium cyanide (1.4 g) in water (35 ml), diluted with water and filtered. The raw one

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- 29 - 263709 '$:.%

9-butyl-anthranyl-acetonitrile was used for 3 hours Potassium hydroxide (12.5 g) in ethoxyethanol (125 ml)

Brought to reflux conditions, cooled, acidified and the product filtered off and recrystallized from benzene; Mp 189 ° (2 g).

Example 54

Preparation of 9-butyl-10-thioimethyl-anthracene 9-butyl-10-bromomethyl-anthracene (0.05 mol) in dioxane (25 ml) was mixed with thiourea (0.38 g) in dioxane (25 ml) and water UO ml) refluxed and then evaporated to obtain the thiouronium salt. This salt was heated with a solution of sodium hydroxide (3g) in water (30ml) for 2 hours under nitrogen, diluted with water and extracted with chloroform. The extracts were dried and evaporated and the product (0.15 g) was recrystallized from acetic acid (mp 225-8 °).

ι Example 35

Manufacture of 9-Butvl-IO-methvlthiomethvl-anthracene

A mixture of 9-butyl-IO-bromomethyl-anthracene (1.6 g) and dimethyl sulfide (10 ml) in dimethylformamide (20 ml) was refluxed for 2 hours, cooled, poured into water and extracted with ether. The extracts were washed twice with water, dried and evaporated and the product was made from petroleum ether recrystallized; Mp 120-122 ° (0.8 g).

Example 56

Manufacture of (s-butyl-anthranylmethylJ-methylsulfoxide

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CH ₂ SOCH ₃

A solution of hydrogen peroxide (30 % \ 0.3 ml) was added dropwise with stirring to a solution of 9-butyl-10-methylthiomethyl-anthracene (0.72 g) in acetone (20 ml) and the solution was added overnight at room temperature left, diluted with water and the product filtered off and recrystallized from toluene petroleum ether; 167-8 °.

Example 37

Preparation of fe-butyl anthranylmethy j -methylsulf on a further oxidizing (3 hours reflux) of the above sulfoxides according to the same procedure (ELjOg afforded the sulfone, which was recrystallized from toluene, mp 200-202 ⁰ C.

Example 38 Production of Q-butyl-IO-aminomethyl-anthracene

9-Butyl-IO-bromomethyl-anthracene (7.2 g) in dioxane (100 ml) was added dropwise with stirring to a solution of ammonia with a density of O _f 88 g / cm ³ (40 ml) in dioxane (100 ml) ml) was added and the mixture was brought to reflux conditions for 3 hours, poured into dilute sodium hydroxide solution and extracted with ether, the extracts were dried and evaporated and the product was crystallized from dioxane-ethanol; mp 178 ° to 180 ° (3.7 g).

Example 39

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g-Butyl-IO-dimethylaminomethyl-anthracene

A solution of 9-butyl-IO-bromomethyl-anthracene (2 g) in dry dioxane (50 ml) was added dropwise to dimethylamine (5 ml) in dry dioxane (20 ml). The mixture was stirred for 2 hours, poured onto 10% aqueous sodium carbonate and extracted with ether in the usual manner. The product was crystallized from ethanol-water; Mp 73-5 ⁰ C

Example 40

Production 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 added with a solution of 9-butyl-10-anthraldehyde (5 * 1 g) in ethyl acetate (10 ml) treated. The mixture was stirred overnight, diluted with acetic acid (10 ml) and dissolved in water poured. Extraction with chloroform gave, after evaporation, a solid which was recrystallized from ethanol-water became; M.p. 75-77 ° (1.2 g).

Example 41

3- (9-butyl-10-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 recrystallized from petroleum ether; 170-175 °. Another recrystallization from acetic acid increased the mp to 185-186 ⁰ C.

Example 42

2- (9-Butyl-anthranyl-methyl) -1,3-propanediol 9-Butyl-IO-anthrylmethyl-malonic acid was by

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Reflux treatment with methanol containing a trace of sulfuric acid converted to its methyl ester. The ester (1.0 g) was dissolved in dry ether (30 ml), to a suspension of lithium aluminum hydride (0.5 g) in
dry ether (100 ml) added, refluxed for 3 hours, cooled and washed with water
and dilute sulfuric acid decomposed. After extraction with ether, the product was recrystallized from toluene; M.p. 147 °.

Example 43 Methyl 3- (9-butyl-10-anthracene) propionate

9-Butyl-IO-anthracene-propionic acid (2 g) was added to
Dissolved methanol, treated with 2 drops of concentrated sulfuric acid and brought the mixture to reflux conditions for 1 hour, cooled and diluted with water. The product was filtered off and recrystallized from ethanol to give needles with mp
from 98-100 ⁰ C.

Example 44

3- (9-butyl-10-anthracene) propanol

A lithium aluminum hydride reduction of methyl 3- (9-butyl-10-anthracene) propionate gave the required product, which was recrystallized from petroleum ether;
114-115 °.

Example 45

3- (1-ethyl-6-pyrenoyl) propionic acid

3-ethyl pyrene (10 g), nitrobenzene (80 ml) and succinic anhydride (5.22 g) were stirred together at 5 ° C, while powdered aluminum chloride (20 g) over 50 Was added over a period of minutes. The mixture was over

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Stirred overnight at room temperature, acidified with concentrated HCl and then subjected to steam distillation to separate off nitrobenzene. The aqueous mixture was extracted with chloroform and the extracts dried. Evaporation gave a solid which was recrystallized from acetic acid; Fp 136 to 147 ⁰ C.

Example 46

4- (6-ethylpyrene) butyric acid

The acid from Example 45 (2.7 g), diethylene glycol (18 ml), Sodium hydroxide (1.1 g) and hydrazine hydrate (2.8 ml) were refluxed for 1 hour, after which time Excess hydrazine and water were distilled off. The solution was heated to 220 ° C for 3 hours, cooled, acidified and extracted with chloroform. The ^ extracts were dried and evaporated to obtain of a brown solid with a mp of 1O5-12O ° C, the after recrystallization from acetic acid gave white crystals; Mp 125-127 ° C

Example 47 Methyl 4- (1-pvrenyl) butyrate

Pyrene butyric acid (5 g), methanol (250 ml) and sulfuric acid (0.5 ml) was refluxed for 3 hours, evaporated to a low mass and between Ether and water distributed. The ether layer was dried and evaporated and the resulting solid off Recrystallized hexane. Mp 52 ° C (4.0 g).

Example 48

4- (1-pyrenyl) butanol

The above ester (1.5 g), dry ether (200 ml)

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and lithium aluminum hydride (0.5 g) were added overnight Stirred at room temperature and carefully diluted with water. The ether layer was dried and evaporated and the product crystallizes from petroleum ether to give plate-shaped crystals; M.p. 76-78 °.

Example 49 4-pyrenyl butyric acid amide

4-pyrene-butyric acid (10 g) in dry toluene (100 ml) was stirred with thionyl chloride (3 ml) until all the solid had dissolved, followed by dryness The crude acid chloride was dissolved in dioxane (30 ml) and ammonia (3 ml) was added. The product was precipitated with water, filtered off and recrystallized from ethanol-water and then from isopropanol; M.p. 182-185 ° C

Example 50 Production of perylene butyric acid

Perylenoylpropionic acid was made by reacting perylene (7 g) with succinoyl chloride and aluminum chloride by the method of Zinke (reports £ 3 (1940) 1042) manufactured. To obtain a pure material it was necessary to stir the crude product with 2M aqueous Convert sodium hydroxide into its sodium salt. The insoluble sodium salt was then filtered off, some Washed times with chloroform to remove unreacted perylene and the resulting black solid was placed in a Soxhlet beaker and extracted with xylene until no more perylene was removed. Of the Solid was then acidified with HCl and extracted into chloroform. After drying, the solution gave on evaporation the required perylenoyl propionic acid in the form of a green solid; M.p. 180 ° C (0.6 g).

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The product was reduced using the Huang Minton method. A mixture of the above acid (0.6 g) and hydrazine (0.25 mL), Digol (4 ml) and sodium hydroxide (0.25 g) was heated to 200 ⁰ C for 4 hours. The product was isolated by acidification with dilute HCl and filtered off. The resulting brown solid was extracted with toluene in a Soxhlet. The toluene solution gave yellow crystals of perylene butyric acid on cooling; Mp 222-224 ° C.

Example 51

6- (N-acridonyl) hexanoic acid

A mixture of sodium hydride (1.2 g), methanol (4.7 ml) and dimethyl sulfoxide (45 ml) was heated ^{to 100 ° C. with acridone (3.5 g).} After all of the acridone had dissolved, methyl 6-bromohexanoate (3.6 g) in DMSO (17 ml) was added, the mixture stirred for 2 hours, diluted with water and extracted with methylene chloride. The extracts were dried and on evaporation gave an oily solid, methyl 6- [acridonyl (10)] hexanoate, which was crystallized from petroleum ether-toluene; Mp 106-108 ⁰ C (yield: 2.1 g; 36%).

The above ester was hydrolyzed by refluxing with sodium hydroxide (0.3 g) in methanol (30 ml) for 3 hours. After cooling, the solution was acidified and the product was filtered off. Recrystallization from petroleum ether-acetone a material was obtained having a melting point of 165-170 ⁰ C.

Example 52

(4-Octyl-naphthalene) -butyric acid

Octylnaphthalene (306 g), nitrobenzene (30 ml) and aluminum chloride (3.1 g) were ^{stirred at 0} ° C. and long-

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3d

succinic anhydride (1.3 g) was added together. The mixture was stirred overnight, then acidified and with Chloroform extracted. The extracts were dried and on evaporation gave the crude octylnaphthalenoyl propionic acid.

This solid was refluxed with hydrazine hydrate (2 ml), sodium hydroxide (1.7 g) and digol (50 ml) for 1 hour, after which the water was distilled off. After heating to 220 ^° C. for three hours, the solution was cooled, poured into dilute HCl and extracted with chloroform. The extracts were dried and evaporated and the product was recrystallized from petroleum ether; Mp 119-120 ⁰ C. ·

Example 53

4-butoxy-4 ^! -cyan-stüben

Butoxybenzaldehyde was prepared by treating p-hydroxybenzaldehyde (61 g) in ethanol (200 ml) with sodium hydroxide (20 g in 50 ml of water) and addition of butyl bromide (1 mol) in ethanol (100 ml). After two hours Under reflux treatment, the mixture was partitioned between ether and water and extracted with ether, etc. to obtain an oil which at bp 120-128 ° C beilTorr (40 g) was distilled.

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 (2.0 g) J added. After stirring overnight at room temperature, water (20 ml) was added and the product (7 g) was filtered off and recrystallized from ethanol; Mp 115 ⁰ C.

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Example 54

4-butoxy-4'-carboxy-stilbene

A mixture of the above cyano compound (1 g) with potassium hydroxide (1.2 g) and digol (50 ml) was heated in a distillation apparatus, removing any water and ammonia as it formed. After heating to 150 to 200 ^° C. for 30 minutes, the mixture was cooled, diluted with water and the product (the sodium salt of the acid required) was filtered off. The acid was released by heating with concentrated HCl in a methanol / water mixture (50:50) to 60 ^° C. for three hours and then filtered off. The solid was recrystallized from a large amount of ethanol; Mp 265-270 ⁰ C.

Example 55 Thin film transistor

A ΊΟ. / U thick film of cadmium sulfide was applied to a Surface of a carefully cleaned quartz disk as a substrate 2.5 cm in diameter and 2 mm thick by deposition from the vapor phase with heating of cadmium

o -5

sulfide formed at 1000 C in an evaporation chamber at 10 Torr pressure. The disk was kept at 200 ^° C. during the deposition.

Two indium / tin source and drain electrodes 500 pounds thick were deposited on the cadmium sulfide film, with the electrodes through a gap of 25 / u width were separated from each other.

The disc was then repeatedly placed in a trough with a sub-phase of ultrapure water with cadmium chloride (2.5 x 10 "* M) of pH 6.2 submerged on top of a monomolecular Layer of cadmium arachidate (applied to the subphase as a 1 mg / ml solution in chloroform) was distributed.

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The disk was immersed vertically with its flat surfaces at right angles to the surface of the subphase. The dipping speed was 3 »7 mm / min and the surface pressure on the film was 30 + 1 dynes / cm. Forty layers of cadmium arachidate were applied to the disc. After each dipping step, the disc was 1 minute air dried at 2O ⁰ C in length; after the completion of the immersion treatment, it was dried in the desiccator for 1 day.

Thereafter, a gold gate electrode (400 Å thick) was evaporated through a mask to form a disk-shaped zone 1 mm in diameter across the source / drain gap (but from these electrodes, of course separated by the cadmium arachidate film).

The resulting arrangement was tested using voltages up to 1 V, with characteristics of the pentode type were observed.

Example 56 Thin film transistor

An indium / tin contact was evaporated onto a surface of a substrate in the form of an n ⁺ indium phosphide crystal with an indium phosphide epitaxial layer grown on the other side. The crystal was purified by treatment with bromine in methanol and indium / tin source / drain electrodes were evaporated onto the surface having the indium phosphide epitaxial layer as before. The crystal then became as in example

described (but at pH 5.7) an immersion treatment to achieve a 20-layer cadmium arachidate film Subjected over the source / drain electrodes. A gold gate electrode was applied as before. The resulting Arrangement showed characteristics of the pen

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- 39 death type.

Example 57

Varactor

The procedure described in Example 56 was repeated up to and including the treatment with bromine in methanol. The substrate was subjected to an immersion treatment to obtain a 20-layer thick cadmium arachidate film, after which a gold gate electrode was applied.

By plotting the capacitance against the bias voltage (DC voltage), a curve was obtained that for MIS (Metal-insulator-semiconductor) arrangements is characteristic, with depletion effects and a weak inversion when applying negative bias.

Example 58

A glass substrate of 7.5 x 2.5 x 0.1 cm (microscope slide) was brushed in hot water for 2 hours in purified saturated chromic acid of 110 ⁰ C, to ultrasonic washing in ultra-pure water for 15 minutes, in 18 tigern Subjected "Decon-90" for 15 minutes, in ultrapure water for 15 minutes and in isopropanol for 15 minutes, and then stored in ultrapure water kept at pH 11-12 with NaOH for 12 hours. The slide was blown dry with an anti-static air dryer prior to use.

A substrate treated as above was subjected to a dipping treatment to coat the surface with a Langmuir pilm of cadmium arachidate of 3 layers thick to provide (this treatment offers a suitable method to make the surface of the glass suitable hydrophilic) what a diving treatment with a sub-

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phase of ultrapure water of pH 4.5 with 2.5 x 10 M barium chloride, on which a monomolecular layer of 9-butyl-IO-anthryl-propionic acid cadmium salt (applied as a 1 mg / ml solution in chloroform) was spread . Dipping took place at 19 "to 21 ^° C. at a speed of 3.7 mm / min and a surface pressure of 15 + 1 dyn / cm. 20 layers of the anthracene derivative were taken up by dipping.

Two gold electrodes, each 7 × 2 mm and 500 Å thick with a spacing of 25 μ were applied to the surface of the film thus obtained and electrical contact was made with the electrodes with the aid of silver paste.

The surface conductivity of the film was observed in the dark and under irradiation with white light. A photocurrent clearly above the dark current (approx. Factor 3) was observed, which was 1 V applied voltage was about 3 10 ~ 12a.

Example 59

On a surface of a cleaned as in Example 58 (but omitting the treatment with NaOH) A 500 Å thick aluminum layer was vapor-deposited onto a glass slide. The glass pane was then as in example 58 described subjected to an immersion treatment, only that the Langmuir film was treated with 9-butyl-10-anthryl-propionic acid Barium salt was formed. 467 layers were applied to the glass pane. A pattern of aluminum dots each 2.5 mm in diameter and 300 A thick was through vapor-deposited through a mask onto the anthracene film thus obtained.

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When a direct or alternating current of ^ OV (Au®, Al®) was applied, blue light was emitted. 4 and 5 show the Varactor bz ™. Photocurrent curves reported in Examples 59 and 58, respectively.

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Claims (16)

Claims Jv Method of making a film or a Layer of organic material with a high degree of molecular orientation on a substrate, characterized in that one very thin layer of an organic material with a planar de-localized system of / TC electrons on the Surface of a suitable liquid generated and the substrate moved through the layer in such a way that a film the organic material is deposited on a surface of the substrate. 2. The method according to claim 1, characterized in that the layer is a monomolecular layer. 3. The method according to claim 1 or 2, characterized in that the movement of the substrate through the layer is performed repeatedly so that a multilayer film arises on the substrate surface. 4. The method according to any one of the preceding claims, characterized in that the organic material is a possesses a cyclic structure with both hydrophilic and hydrophobic substituents. 5. The method according to any one of the preceding claims, characterized in that the hydrophobic group by a linear hydrocarbon chain is formed with a chain length of not more than 10 carbon atoms. 6. The method according to claim 5, characterized in that the hydrocarbon chain has a chain length of Has 3 to 8 carbon atoms. 7098 0 9/1041 7. The method according to any one of the preceding claims, characterized in that the film of the organic Material is formed by the deposition of up to 10 monomolecular layers on the substrate. 8. The method according to any one of claims 1 to 6, characterized in that the film of organic material is formed by depositing 20 to 200 monomolecular layers on the substrate. 9. The method according to any one of the preceding claims, characterized in that the organic material is a Anthracene, pyrene or perylene derivative is. 10. The method according to claim 9, characterized in that the organic material in a 9-position with a hydrophobic linear alkyl group with 3 to 8, preferably 3 or 4 carbon atoms substituted anthracene which has a hydrophilic group in the 10-position. 11. The method according to any one of the preceding claims, characterized in that the substrate is an electrode material includes. 12. The method according to claim 11, characterized in that the organic film is deposited on a substrate having a plurality of separate electrodes. 13. The method according to claim 11 or 12, characterized in that that the free surface of the film is contacted with a further electrode. 14. The method according to any one of the preceding claims, characterized in that the ab- 709809/104 different organic material comprises a dopant or a dopant. 15. The method according to any one of the preceding claims, characterized in that the deposition of the organic Material alternates with the deposition of a different organic or inorganic material. 16. Composite bodies, in particular electrical or electronic components, with at least one thin layer, obtained using the method according to any one of the preceding claims. 709809/1041