DE2637099C2 - 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 - Google Patents

Description

The invention relates to a method for producing a film or a layer made of organic material having a high degree of molecular orientation on a substrate as well as the use of the film or the Layer made by this process in connection with the substrate as electrical or electronic Composite body for building elements.

Different groups of known electrical, electrochemical, photochemical or electronic Composite bodies or components contain a very thin layer of one - generally insulating - organic material with a high degree of molecular orientation. Common layers For example, from a material with a certain degree of molecular orientation have been made by Abrasions made from a single crystal, however, generally undesirable occurrences in the crystal lattice Dislocations and defects before the desired small layer thickness has been achieved. Furthermore are the dimensions of the layer obtained by the size of the single crystal used as the starting material limited. Alternative methods of producing very thin layers are the vapor deposition method as well (ζ, B. for oxide films) thermal growth.

From US-PS 36 21 321 it is known that electronic composite bodies such. B. Rectifiers can contain a thin layer of anthracene or naphthalene.
The invention relates to a method for producing a film or a layer of organic material with a high degree of molecular orientation on a substrate, in which a very thin layer of organic material with a planar delocalized electron system is produced on the surface of a suitable liquid and moving the substrate through the layer such that a film of the organic material is deposited on a surface of the substrate.

I ;.; The very thin layer of organic material created on the surface of the liquid is pre-

V ;: preferably a monomolecular layer.

% The organic material with a delocalized jr-EIektronensystem, a material having a cyclic or

fe; be with acyclic structure. The plane delocalized π-electron system can be an aromatic, non-aromatic

i; "table or anti-aromatic as well as a carbocyclic, heterocyclic or organometallic ^ -electro-

\ 'r _r n system. The organic material should have both hydrophobic and hydrophilic properties,

ύ- suitably obtained by making the molecule of the material hydrophobic and / or hydrophilic

■; Substitucnten has a molecule that is water-soluble and has a hydrophobic substituent. tends

| y to accumulate at the water / air interface, reducing the surface tension of a solution in which it

is; solved hl, is reduced.

ΨΙ Typical hydrophobic substituents include hydrocarbon groups which are suitably linear

Ä are alkyl groups, but are branched alkyl groups or linear polyacene groups or aromatic groups

yl can be. AlkyJgruppen can be heteroatom groups such. B. O, NH, S or SO ₂ contain. Too typical

I 'include hydrophilic substituents

j | - COOH, OH, NHj, CN, SO ₃ H, NR ₃ , SRJ (R '= alkyl or aryl group), PO ₄ and - SOCH ₃ .

Ki It was previously believed that the molecules of an organic material were responsible for the formation of a stable

fj films on water a hydrophobic hydrocarbon group with a considerable chain length of preferred

gf should contain more than 16 carbon atoms. However, it was found that the application

?! such materials is undesirable when the material is applied in a composite laminated body which

j | · should show semiconductor properties. It was found for such a composite body that for the case

jt that the hydrophobic substituent is a hydrocarbon group, it is desirable that the or

p organic material to be deposited does not have any hydrophobic substituents with a linear chain length of

I have more than 10 carbon atoms and preferably no hydrophobic substituents with a chain length of

I contains more than 3 to 8 carbon atoms; such a hydrocarbon group is preferably linear.

§ An organic material that has more than one hydrophobic and more than one hydrophilic substituent

Ii can be used, but the balance between hydrophobic and hydrophilic

Behavior z. B. maintained in such a way that the organic material does not dissolve or disperse in the carrier liquid (with the result that no surface film is formed) and otherwise in such a way that the organic material does not become so predominantly hydrophobic that the film is unstable.
The organic material therefore generally has the following structure:

R- / 7-X

where R denotes a hydrophobic substituent, X denotes a hydrophilic substituent and / 7 denotes a cyclic or acyclic structure with a planar delocalized ^ -electron system, although R or X in the case that 77 itself has pronounced hydrophobic or hydrophilic properties, may be absent accordingly. Preferably / 7 is a cyclic structure, and / 7 may in addition to R and X substituents such as e.g. B. have a halogen atom, a quinoid oxygen atom, a doubly bonded sulfur atom or a nitro, dimethylamino, acyl or oxyamino group. One or more such substituents can act as a metal ligand.
Alternative structures of the organic material can be:

f Π-RX or Π-XR

If / 7 is a cyclic structure, it can have one or more than one ring that is carbo- or hetero-

ψ can be cyclic and include metal atoms.

gi Examples of groups of organic materials from which films can be made by the process according to the invention

|| or layers that can be produced are the following: (In the formulas, R is preferably an n-alkyl- so

ΪΛ group with a chain length of not more than 10, in particular from 3 to 8 carbon atoms, and η can

be zero or an integer not exceeding 12 and preferably from 1 to 3.)

Carbocyclic Materials

$. R RO RSO ₂

(CH ₂ J _n X

(D (2)

N-NHR

(4) (5)

NMe,

NMe ₂

(6)

(CHJ _n X

(7)

(CHj) _n X

(8th)

HO NHCOCH ₃

SO ₃ H

RRR

ROR

SO ₃ Na

(14)

S-N-S

O NH ₂

SO ₃ Na

SO ₃ Na

R S-S

R R

(CH ₂ ) "X

(19)

(CH ₂ ) "X

(20)

(CHJ _n X

(23)

(CHj) "X

(24)

(25)

- (CHj) _n X

OH

(26)

O (CH ₂ ) "X

(28)

30 Heterocyclic Materials

(29)

(31) (CHj) _n X

(37)

(CH ₂ ) ,, X

(38)

(CH,), X

NMe

R Ph

R Ph

(42)

(44)

SR

(48)

-R

(49)

(50)

15th 20th 25th 30th 35

HO ₃ S

R SFf

SO ₃ H

(53)

(52)

(55)

40 45 50 55

(56)

OO

R BF?

65

(59)

ν; bf?

(57)

00

(60)

(61)

26th 37 099 ι R. J ti / \ BFf \ / CH 3 (63)

(64)

(65)

N-N.

(68)

(67)

(69)

BFf

(70)

(71)

Me

a / N = N

N-N

Me

Me

BFf

(72)

(73)

Transition metal complexes

lsi

Ni Tj

Tf

RR

(74)

Ni NH HN

I I

R R

(75)

C ₆ H ₅

(78)

ROCO

OCOR

(77)

O SO ₂ NHR

(79)

SO ₂ NHR

(80)

j, 'The exact position of the specified substituents may be unimportant, and additional substituents

· '- can be incorporated into the molecules given above, provided that the obtained

> 1 organic material is present on a suitable liquid (hereinafter also referred to as carrier liquid

te) to form a monomolecular layer and in a suitable integral form on a sub-

f strat to be deposited and thereby to form a film with desired properties. s

It has been found that Langmuir films made from mononuclear heterocyclic materials only have large

^, Difficulty can be formed, and these materials are preferably not used.
P A preferred group of organic materials for use in making a film or

a layer for composite bodies that show electroluminescence or photoconductivity are the anthracene

i * derivatives (or other electrolutninescent or photoconductive compounds such as pyrenes or perylenes), and

/ in particular those that are in the 9-position with a hydrophobic linear alkyl group that is 3 to 8 and above

4 'preferably contains no more than 4 carbon atoms, are substituted. The molecule of the anthracene derivative

; ■ has a suitable fabric in one of the positions 3, 4, 5, 6 and 10 and preferably in the 10 position

p hydrophilic substituents.

Sj The molecule of the organic material preferably has only one hydrophilic and one hydrophobic

Yl substituents.

jk The deposited film of the organic material can be used as such, that is, as a mono-

H: molecular layer, but is generally an increase in film thickness by repetitive deposition

ff monomolecular layers of the same material for expanding the applicability of the obtained

I composite body is advantageous (typically 20 to 200 monoJecular layers for thin-film transistor

I Composite body and 1 to 10 monomolecular layers for applications using the tunnel effect

I from hot electrons). Furthermore, layers made of other materials (organic or inorganic) lg can be layered in between, or the organic material can be modified so that a film is made of

more than one component is produced.

This means that both monomolecular layers (e.g. for tunneling hot electrons) and (e.g. electroluminescent) composite films composed of several or a large number of monomolecular layers wherein the composite films are made by repeatedly passing the substrate through a monomolecular layer of the organic material that is on the surface of a suitable liquid was generated, is moved through.

Process for the production of a monomolecular layer of organic material on a substrate are known as the Langmuir trough process and can be summarized as follows: As a carrier liquid a liquid which is generally inert to the organic material is used, i. H. among the at Process according to the invention applied does not adversely affect the material of the layer or conditions of the substrate reacts into the liquid, although it has been found desirable in certain circumstances Constituents, in particular ions, to include those with the organic material of the layer or other components of the composite body react. The liquid can door the organic matter Solvent, but this is not preferred. An important requirement is that the organic Material accumulates on the surface of the liquid in such a way that it is removed as a layer or film (or can be withdrawn). The liquid can be organic or inorganic; in general, the Use of water as the carrier liquid is preferred, although the stability of the layer consists of the organic Material can possibly be improved by the presence of inorganic ions.

The monomolecular layer made of the organic material is on the surface of the carrier liquid

II suitably produced by applying a suitable amount of a solution of the organic to this surface H material in a volatile solvent that is generally associated with the carrier liquid (also called liquid

fe subphase) is not miscible, is applied. The process of applying the organic

ß material on the carrier liquid and its compression are known.

p | The organic material is transferred to the substrate, which can consist of any suitable material.

<: '/ by dipping the substrate into the carrier liquid and then pulling it out again, so that the film

p made of the organic material adheres to the surface of the substrate. Maintaining facilities

! $ the integrity of the layer on the liquid are necessary and can be obtained from a wiper or pad-

Il del consist, which is preferably controlled by a microbalance, the surface pressure of the layer

| i: s constantly measures. Maintaining a constant pressure on the layer of organic material is essential

isf important for the deposition with a high degree of molecular orientation on the substrate.
it; The inventive method is particularly suitable for the production of films or layers that

| i contain a dopant, either by incorporating the dopant as a foreign substance

ψ of suitable concentration in the layer of the organic material that is generated on the carrier liquid

pj. is, or by deposition of the dopant as a separate layer or by alternating

; |, Deposition of layers from the dopant and layers from the organic material (that in the

pt is generally referred to as host material). An example of the application of such a procedure is

SS the production of a composite body, the alternating films of a photoconductor and a sensitizer

H tor; contains alternating layers of p-type and η-type or alternating semiconductor and insulator layers.

ί ^; Suitable dopants include dyes that change the color of radiation emitted by the composite; for example, the presence of about 1 ppm tetracene in the anthracene

i, derivative the color changed from blue to yellow.

p The film or the layer which was produced by the method according to the invention can be used in conjunction

; with the substrate as an electrical or electronic composite door with a large number of components

;. various purposes (see DE-OS 26 37 206) can be used. So there is an execution

\ i form of the use according to the invention in the use of electroluminescent composite bodies which

Layers of an anthracene derivative or a suitable semiconducting material such as e.g. B. a pyrene or perylene derivative. Anthracene used to be used in electroluminescent devices in the form of crystals applied (see US-PSS 35 30 325 and 33 82 394, in which also on the electroluminescence principle Is referred to).

According to one embodiment of the use according to the invention, a composite body is used, too its manufacture a film of an organic material and preferably an anthracene, perylene or Pyrene derivative as described above in contact with a suitable conductive material as substrate deposited or deposited on a substrate and subsequently in contact with a conductive material is brought or the layer of the organic material or preferably two surfaces of the ίο Layer of the organic material with two or more than two separate electrodes in contact to be brought. The formed film of the organic material may have any suitable thickness, such as but preferably does not exceed 2 µm. The said composite body can suitably, for. B. by applying a first layer of a suitable first electrode material through a suitable one Measure; Deposition of a composite film comprising about 20 to 500 monomolecular layers of e.g. B. a contains suitable anthracene derivative, according to the Langmuir process in contact with at least one upper i

surface of the first layer and applying a second electrode material on the surface of the so 'manufacturer ·

produced composite film. Optionally, after the application of the second electrode material are annealed. The first electrode material can, for example, be a suitable one Electron injecting electrode material such as e.g. B. AI / AliO. As the second electrode material a hole-injecting material such as. B. Au, Pt, CuO / J or Se / Te or mixtures thereof are used will. The use of organic hole injecting materials such as B. of bis (benzothiazolone) azine disulfonic acid is possible.

The first electrode material is expediently on a carrier layer with an appropriate steepness and suitable insulating properties door applied to the intended use of the composite body.

Other composites used in the present invention include photoconductive composites and photo element systems, in which the deposition of layers of organic material with a high degree of molecular orientation is an important factor in optimizing performance.

Further composite bodies which are used according to the invention are composite bodies for field effect transistors with an insulated gate (IG-FET) such as e.g. B. thin film transistors. _f

An all types of unipolar transistors common basic principle in the control of the Stromflus- _'t

ses between a source and a drain electrode through a gate electrode. Cross-sections of typical transistor configurations are shown schematically in the accompanying figures (see also DE-OS 26 37 206), it being noted that many thin-film components of transistors are only a few micrometers thick in terms of magnitude. '■

Difficulties encountered in forming a relatively defect-free insulator film can be avoided by depositing the insulating film by the Langmuir method. Langmuir monomolecular layers are used to form a composite film serving as an insulator film having a suitable thickness for the intended purpose. A cross section of such a composite body is shown schematically in Fi g. 1 shown. Typically, the insulator film would contain 20 to 200 monomolecular layers.

The heat dissipation or dissipation in transistors can be achieved through the use of a polymer material with relatively high thermal conductivity, such as polyethersulfone, is favored as an insulating substrate will.

The application of the Langmuir process to the deposition of a semiconductor film in a transistor is also possible, although, as in all cases in which this procedure is used, care must be taken to that reagents or carrier liquids, which can be harmful to already deposited material, to be avoided are.

Many of the layers or films deposited by the process according to the invention can be both Insulator and act as an active component (which is due to the fact that a large charge mobile-5ö anisotropy exists parallel and perpendicular to the plane of the layer). A structural example of one Composite body is shown schematically in FIG. Organic materials with the required properties can be selected from those listed above, but anthracene, perylene, Pyrene, tetracene or naphthalene derivatives or organometallic materials are preferred.

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

The insulating substrate can be made of various materials such as. B. mica, glass, sapphire, split crystals or plastics with high thermal conductivity.

M) Examples of the material of the semiconductor are various semiconductor materials including CdS, Cd, Se, GaAs, Si, PbS, InAs, phthalocyanine, violanthrene, porphyrins and derivatives of anthracene, tetracene, naphthalene, pyrene and perylene. '.

The successful production of thin-film composite bodies or components and in particular of Transistors, the operability of which is based on the precise spatial arrangement of their components, depends on the accuracy with which the various components can be deposited. For example To avoid unwanted capacitive effects, it is important that the gate electrode is Thin film transistor with precise alignment according to the channel between the source and drain electrodes is deposited. The deposition of a component film by the Langmuir method at the r

Γ * 12

desired location with - if necessary - subsequent removal of the film from parts of the composite body, for example by grinding or etching, offers a suitable method for achieving an accurate Localization of active or insulating thin-film components.

The use according to the invention also includes the use of composite bodies for varactors, Hot electron components, hot electron transistors, Esaki-M-I-M-I-M structures, Gunn oscillators and photodetectors. In the manufacture of varactors (components whose reactance / Capacitance can be changed controllably using a bias) to the advantages of Deposition of thin film components, e.g. B. insulating layers, according to the Langmuir process high capacitance (due to a thin insulating film and a relatively large surface area), lower capacitance Operating voltages as a result of the thin insulating film and 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 magnitude 5.0 to 10.0 nm. With Gunn oscillators, a hot electron (0.3 eV) supplying contact is applied a single crystal is preferred. This type of contact is best made using the tunnel injection principle achieved by a thin insulating film.

A simple but effective photodetector with the one shown in FIG. 3 can be made using the Langmuir process. For example, a suitable photoconductor such. B. CdS between depositing the gate electrode and the insulator film; light falling on the photoconductor this more conductive, which leads to an increase in the voltage drop across the insulator film and onto it Way changes the conductance of the source-drain channel. Alternatively, a photosensitive material such as B. built a dye between the gate and the insulator film (or in the insulator film as a doping) will. Light falling on the photosensitive material causes charge carriers to be injected into it the dielectric under the influence of the gate voltage, where they influence the conduction of the source-drain current. The films of such composite bodies or components can be produced by the method according to the invention getting produced; for example, the insulator and / or semiconductor film can be Langmuir film as above described, to be deposited. A Langmuir film is understood to mean a film that is classified under Application of the Langmuir trough method is obtained.

The invention is hereinafter illustrated by synthetic methods for the preparation of those in the invention Process used organic materials and explained in more detail by examples.

Synthesis procedure 1 to 44
Manufacture of anthracene derivatives

Using the procedures of Sieglitz (Reports 56 (1923), 1619) and Stewart (Australia J. Chem. 1960, 478) anthrone was converted into 9-alkyl-10-hydroxymethylanthracene.

The conversion to the 10-bromomethyl derivative was carried out as follows: 0.1 mol of the 10-hydroxymethyl compound was suspended in 500 ml of dry diethyl ether. 2 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 2O ⁰ C, poured onto ice and extracted with dichloromethane to give the 10-bromomethyl compound was obtained.

A mixture of diethyl malonate (4.8 g), dry toluene (200 ml) and finely cut-up sodium (0.75 g) was heated for 2 hours at 8O ⁰ C. 9-Alkyl-10-bromomethylanthracene (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 resulting toluene layer was removed, washed twice with water, dried and evaporated to give the crude substituted malonic 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 substituted malonic acid.

The substituted malonic acid was suspended in tetrahydronaphthalene and heated. It developed Carbon dioxide, and after 30 min the solution was diluted with petroleum ether and cooled. 9-alkylanthranyI (10) propionic acid crystallized out.

Following the procedure described above, the following anthracene derivatives were synthesized (see following table):

60 65

I. 20th i $ i Tabel Ri 26 37 099 R ₃ Fp.
( ⁰ C) —- - ~ T synthesis
procedure QH ₅ H 50-52 i ^4S 1 C ₃ H ₇ H 55-59 solvent
to recrystallize 25th 40 I. 2 C ₄ H ₉ H 48 Petroleum ether I. 3 CoHu H 67-68 Methanol I ^5o 4th C ₈ Hn H 36-40 Methanol \ in E. 5 Ci ₂ H ₂₅ H 40-45 Methanol H JU i 6th C ₂ H ₅ CH ₂ OH 193-197 Methanol j 7th C ₃ H ₇ CH ₂ OH 200 Ethanol 5 9 55 8th C ₄ H ₉ CH ₂ OH 194-195 Methanol 9 C ₆ H ₁₃ CH ₂ OH 160-162 Methanol 10 CgH) ₇ CH ₂ OH 153-154 Methanol 10 11th Q ₂ H ₂₅ CH ₂ OH 147-148 Methanol 12th Ci8H ₃₇ CH ₂ OH 139-140 Methanol 13th C ₂ H ₅ CH ₂ CH ₂ CO ₂ H 169 Methanol 14th C ₃ H ₇ CH ₂ CH ₂ CO ₂ H 198-200 Cyclohexane 15th C ₄ H ₉ CH ₂ CH ₂ CO ₂ H 127-128 ") Petroleum ether 16 C ₆ H ₁₃ CH ₂ CH ₂ CO ₂ H 164-166 Petroleum ether 17th CeH) ₇ CH ₂ CH ₂ CO ₂ H 136-137 Petroleum ether 18th C) ₂ H ₂₅ CH ₂ CH ₂ CO ₂ H 112-113 Petroleum ether 19th C ₂ H ₅ CHO 87-88 Petroleum ether 20th C ₃ H ₇ CHO 94-95 Methanol 21 C ₄ H ₉ CHO 78 Ethanol 22nd C ₆ H) ₃ CHO 70 Petroleum ether-toluene 23 CgHi ₇ CHO 57-58 Petroleum ether 24 CuH ₂₅ CHO 80 Petroleum ether 25th C ₂ H ₅ CH ₂ Br 173-175 Petroleum ether 26th C ₃ H ₇ CH ₂ Br 145 Ethanol 27 C ₄ H ₉ CH ₂ Br 139 Petroleum ether-toluene 28 CfH ₁₃ CH ₂ Br 139-140 Petroleum ether 29 CgH ₁₇ CH ₂ Br 105-107 Petroleum ether 30th C] ₂ H ₂₅ CH ₂ Cl ") 99-100 Pctrolether 31 Petroleum ether Petroleum ether

Notes on the table:

^a ) This anthracene derivative crystallizes in two forms (melting point 151-152 ° C and 127-128 ° C) with identical spectroscopic properties. The form with a melting point of 127-128 ° C is only obtained after 4 or 5 recrystallizations from petroleum ether, and this form was used in all Langmuir-Trog experiments

^h ) Prepared according to the method of Stewart (Australian J. Chem. 1960, 478).

Other anthracene derivatives were prepared as described below

Synthesis method 32
Production of 9-butyl-10-carboxyanthracene

9-Butyl-10-anthraldehyde (6.6 g) was treated with silver oxide prepared from silver nitrate (6.5 g), 50% aqueous ethanol (150 ml) and sodium hydroxide (4 g) for 4 hours Brought reflux conditions. The mixture was diluted with 300 ml of water, filtered hot and then acidified. The product was filtered off and recrystallized from toluene; Mp. 176 ⁰ C.

Synthesis method 33
Production of 9-butylanthranylacetic acid

A solution of 9-butyl-10-bromomethylanthracene (5.74 g) in dioxane (10 ml) was treated with is Combined potassium cyanide (1.4 g) in water (35 ml), diluted with water and filtered. The crude 9-butylanthranylacetonitrile was refluxed with potassium hydroxide (12.5 g) in ethoxyethanol (125 ml) for 3 h brought, cooled and acidified. The product was filtered off and recrystallized from benzene; Fp. 189 ° C (2 g).

20th

Synthesis method 34
Production of 9-butyl-10-thiomethylant.hracene

25th

P-butyl-10-bromomethylanthracene (0.05 mol) in dioxane (25 ml) was refluxed with thiourea (0.38 g) in dioxane (25 ml) and water (10 ml) and then evaporated. The thiouronium salt obtained on evaporation 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 recrystallized from acetic acid (mp. 225-228 ⁰ C).

Synthesis method 35
Production of 9-butyl-10-methylthiomethylanthracene

A mixture of 9-butyl-10-bromomethylanthracene (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 recrystallized from petroleum ether; Mp 120-122 ⁰ C (0.8 g)..

Synthesis method 36

45

Preparation of [9-butylanthranylmethyl] methyl sulfoxide
C ₄ H ₉

50

§ A 30% solution of hydrogen peroxide (0.3 ml) was stirred into a solution of 9-butyl-10-

methylthiomethylanthracene (0.72 g) in acetone (20 ml) was added dropwise, and the solution was left overnight at room temperature left and diluted with water. The product was filtered off and recrystallized from toluene-petroleum ether; M.p. 167-168 ° C.

Synthesis method 37
Production of [9-butylanthranyimethyl] methyl sulfone

A further oxidation (3 h reflux) of the sulfoxide obtained according to synthesis method 36 by the same method (H ₂ O ₂ acetone) gave the sulfone, which was recrystallized from toluene; Mp. 200-202 ⁰ C.

Synthesis procedure 38
Manufacture of iJ-butyl-10-aminomethylanthracene

9-Butyl-10-bromomethylanthracene (7.2 g) in dioxane (100 ml) was added dropwise with stirring to a solution of ammonia with a density of 0.88 g / cm ³ (40 ml) in dioxane (100 ml), and the mixture was brought to reflux 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; M.p. 178 to 180 ^° C (3.7 g).

Synthesis method 39 I.

9-butyl-10-dimethylaminomethylanthracene I.

§

A solution of 9-butyl-10-bromomethylanthracene (2 g) in dry dioxane (50 ml) became dimethylamine (5 ml) in dry dioxane (20 ml) was added dropwise. The mixture was stirred for 2 hours at 10% Poured aqueous sodium carbonate and extracted with ether in the usual way. The product was extracted from ff

Ethanol-water crystallizes; M.p. 73-75 ° C. /:

^ i

Synthesis method 40 fe

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 mixed with a solution of 9-butyl-10-anthraldehyde (5.1 g) in ethyl acetate (10 ml). The mixture was over Stirred overnight, diluted with acetic acid (10 ml) and poured into water. Extraction with chloroform allowed V

after evaporation produced a solid which was recrystallized from ethanol-water; M.p. 75-77 ° C (1.2 g). 30th

Synthesis method 41 ^!

3- (9-butyl-10-anthryl) -2-propenoic acid
35

The ester obtained according to synthesis method 40 was refluxed with alcoholic NaOH for 1 hour, cooled and acidified. The product was filtered off, dried and recrystallized from petroleum ether; Mp 170-175 ° C. Another recrystallization from acetic acid increased the mp. 185-186 ⁰ C. to

Synthesis method 42
2- (9-butylanthranylmethyl) -1,3-propanediol

9-Butyl-10-anthrylmethylmalonic acid was treated by refluxing with a trace of sulfuric acid Methanol converted into their methyl ester. The ester (1.0 g) was dissolved in dry ether (30 ml) dissolved, before a suspension. Lithium aluminum hydride (0.5 g) was added to dry ether (100 ml) for 3 hours brought to reflux conditions, cooled and decomposed with water and dilute sulfuric acid after extraction with ether, the product was recrystallized from toluene; Mp 147 ° C.

;

Synthesis method 43
Methyl 3- (9-butyl-10-anthracene) propionate

9-Butyl-10-anthracene propionic acid (2 g) was dissolved in methanol and 2 drops of concentrated sulfuric acid were added. The mixture was brought to reflux for 1 hour, cooled and diluted with water. The product was filtered and recrystallized from ethanol whereby needles were obtained with a mp. Of 98-100 ⁰ C.

Synthesis method 44
3- (9-butyl-10-anthracene) propanol

Lithium aluminum hydride reduction of methyl 3- (9-butyl-10-anthracene) propionate provided this desired product recrystallized from petroleum ether; M.p. 114-115 ° C.

Synthesis method 45
3- (1-ethyl-6-pyrenoy I! -Propionic acid

3-Ethylpyrene (10 g), Ni: robenzene (80 ml) and succinic anhydride (5.22 g) were mixed together at 5 ° C stirred while powdered aluminum chloride (20 g) was added over 50 minutes. The mixture was stirred overnight at room temperature, acidified with concentrated HCl and then for separation of nitrobenzene subjected to steam distillation. The aqueous mixture was made with chloroform extracted and the extracts dried. Evaporation gave a solid consisting of acetic acid was recrystallized; Mp 136-147 ° C.

Synthesis method 46
4- (6-ethylpyrene) butyric acid

The acid (2.7 g) obtained by Synthesis Procedure 45, diethylene glycol (18 ml), sodium hydroxide (1.1 g) and hydrazine hydrate (2.8 ml) were refluxed for 1 hour, after which the 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 give a brown solid (mp 105-120 C ^0th) was obtained, which gave, after recrystallization from acetic acid white crystals; Mp 125-127 ° C

Synthesis method 47

Methyl 4- (1-pyrenyl) butyrate

Pyrene butyric acid (5 g). Methanol (250 ml) and sulfuric acid (0.5 ml) were refluxed for 3 hours, evaporated to a small mass and partitioned between ether and water. The ether layer was dried and evaporated, and the solid obtained was recrystallized from hexane. M.p. 52 ° C (4.0 g).

Synthesis method 48

35 4- (1-pyrenyl) butanol

The ester (1.5 g) obtained according to synthetic method 47, dry ether (200 ml) and lithium aluminum hydride (0.5 g) was stirred overnight at room temperature and carefully diluted with water. The ether layer was dried and evaporated, and the product was crystallized from petroleum ether, whereby plate-shaped Crystals (m.p. 76-78 ° C) were obtained.

Synthesis procedure 49

45 4-pyrenylbutyric acid amide

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

Synthesis method 50

Production of perylenebutyric acid

Peryienoylpropionic acid was prepared by reacting perylene (7 g) with succinoyl chloride and aluminum chloride according to the method of Zinke [Reports 73 (1940), 1042]. To obtain a pure product 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 off and washed several 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. The solid was then acidified with HCl and extracted into chloroform. After drying, the solution gave the desired peryienoylpropionic acid in the form of a green solid on evaporation; Mp 18O ⁰ C (0.6 g)..

The acid obtained as the product was reduced by the Huang-Minlon method by adding a mixture of the acid (0.6 g), hydrazine (0.25 ml), diethyl glycol (4 ml) and sodium hydroxide (0.25 g) 4 was heated to 200 ^° C. for h. The product of the reduction was isolated by acidification with dilute HCl and filtered off.

trier!. The brown solid obtained was extracted with toluene in a Soxhlet. The toluene solution provided the Cooling yellow crystals of perylenebutyric acid; M.p. 222-224 ° C.

Synthesis method 51

6- (N-acridonyl) hexanoic acid

A mixture of sodium hydride (1.2 g), methanol (4.7 m!) 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 resulting mixture was 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 resulting 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 filtered off. Recrystallization from petroleum ether-acetone to obtain a product with a mp. Of 165-170 ⁰ C.

Synthesis method 52

(4-octylnaphthalene) butyric acid

Octylnaphthalene (3.06 g), nitrobenzene (30 ml) and aluminum chloride (3.1 g) were ^{stirred at 0 °} C. and succinic anhydride (1.3 g) was slowly added. The mixture was stirred overnight, then acidified and extracted with chloroform. The extracts were dried to give a solid on evaporation (crude octylnaphthalinoylpropionic acid).

The solid was washed with hydrazine hydrate (2 ml), sodium hydroxide (1.7 g) and diethylene glycol (50 ml) for 1 hour.

brought to reflux conditions after which the water was distilled off. After three hours of heating to 220 ^° C., 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.

Synthesis method 53
35

4-butoxy-4'-cyanstilbene

Butoxybenzaldehyde was made by treating p-hydroxybenzaldehyde (61 g) in ethanol (200 ml) with

Prepare sodium hydroxide (20 g in 50 ml water) and add butyl bromide (1 mol) in ethanol (100 ml).

After refluxing for two hours, the mixture was partitioned between ether and water and with

Of ether, etc., an oil was obtained which was distilled (b.p. 120-128 ⁰ C at 1.3 hPa;. 40 g).

A solution of 4-cyanobenzyl triphenylphosphonium bromide (18.4 g) in warm ethanol (250 ml) was added

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)] 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 recrystallized from ethanol; Mp. 115 ⁰ C.

Synthesis method 54
4-butoxy-4'-carboxystilbene

A mixture of the cyano compound prepared according to Synthesis Procedure 53 (1 g) with potassium hydroxide (1.2 g) and diethylene glycol (50 ml) was heated in a still, removing any water and ammonia as it formed. After 30 minutes of heating at 150 to 200 ⁰ C, the mixture was cooled and diluted with water and the product filtered off (the sodium salt of the desired acid). 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 obtained solid was recrystallized from a large amount of ethanol; Mp. 265-270 ° C.

example 1
Thin film transistor

fts A 10 μm thick cadmium sulfide film was deposited on a surface of a carefully cleaned quartz disk as a substrate (2.5 cm diameter; 2 mm thickness) by deposition from the vapor phase while heating cadmium sulfide to 1000 ^° C. in an evaporation chamber at 1.3 mPa Pressure formed. The disk was kept at 200 ^° C. during the deposition.

Two indium / tin source drain electrodes (50 .mu.m thick) were placed on top of the cadmium sulfide film deposited, the electrodes being separated from one another by a 25 · ιηι wide gap.

The quartz disk was then repeatedly immersed in a trough with a sub-phase (carrier liquid) of ultra-pure water with cadmium chloride (0.25 mmol / I) of pi I 6.2, on which a monomolecular layer of cadmium arachinate (applied to the sub-phase as I mg / ml solution in chloroform) was distributed. The quartz disk was immersed vertically with its flat surfaces forming a right angle to the surface of the subphase. The diving speed was 3.7 mm / min and the surface pressure on the layer was (0.30 ± 0.01) mN / cm. 40 monomolecular cadmium arachinate layers were deposited on the quartz disk. After each immersion process, the quartz disk was air-dried ^{at 20 ° C. for 1 min;} after the completion of the immersion treatment, it was dried in the desiccator for 1 day.

Then a gate electrode made of gold (40.0 nm thickness) was vapor-deposited through a mask, thereby transversely a disc-shaped zone (1 mm diameter) above the space between the source and drain electrodes, separated from these electrodes by the cadmium arachinate film.

The composite body obtained was tested using voltages up to 1 V, with characteristics of the pentode type were observed.

Example 2
Thin film transistor

On one surface of a substrate in the form of an n'-indium phosphide crystal with one on the other side An indium / tin contact was vapor-deposited on the grown indium phosphide epitaxial layer. The crystal was purified by treatment with bromine in methanol, and onto the one having the indium phosphide epitaxial layer As mentioned above, source / drain electrodes made of indium / tin were vapor-deposited on the surface. The crystal was then subjected to an immersion treatment as described in Example 1 (but at pH 5.7) for production a cadmium arachinate film comprising 20 monomolecular layers over the source-drain electrodes subjected. A gate electrode made of gold was applied as described above. The received The composite body showed characteristics of the pentode type.

k example 3

| f varactor

p The procedure described in Example 2 was followed up to and including the treatment with bromine in methanol

1 repeated. The substrate was used to make one composed of 20 monomolecular layers

ψ Subjected the cadmium arachinate film to an immersion treatment, after which a gate electrode made of gold

|| was brought.

H By plotting the capacitance against the bias voltage (DC voltage), a curve was obtained which for

pi MIS (metal-iso! ator-semiconductor) composite body is characteristic, with depletion effects and a black

jk chen inversion when applying negative bias.

Example 4

k A glass substrate (7.5x2.5x0.1 cm; microscope slide) was brushed in hot water for 2 hours in

i saturated chromosulfuric acid cleaned from 10 ° C, an ultrasonic rinse in ultrapure water (15 min

I 'long), in an 18% solution of a phosphate-free cleaning agent concentrate (a complex emulsion

! anionic and nonionic surfactants in an aqueous base (15 minutes), in ultrapure

_t water (15 min for) and in isopropanol (15 min) and then for 12 h in NaOH at pH 11

1 to 12 held ultra-pure water. Before use, the slide was treated with an anti-

1. Static air dryer blown dry.

! ■ A glass substrate treated as described above was subjected to a dipping treatment to obtain

l · to deposit a Langmuir film made of 3 monomolecular cadmium arachinate layers on its surface

j (this treatment is suitable for making the surface of the glass substrate hydrophilic), from which «» I a

Immersion treatment with a sub-phase of ultrapure water of pH 4.5 with 0.25 mmol / l barium chloride 1 followed, on which a monomolecular layer of the cadmium salt of 9-butyl-IO-anthrylpropionic acid

[(applied as a 1 mg / ml solution in chloroform). The immersion took place at 19 to 21 ° C

a speed of 3.7 mm / min and a surface pressure of (0.15 ± 0.01) mN / cm. 20 monomolecular Layers of the anthracene derivative were deposited by dipping.

Two gold electrodes (each 7x2 mm; 50.0 nm thickness) with a distance of 25 μm were on the surface of the film thus obtained, and electrical contact was made with the electrodes by means of silver paste manufactured. : The surface conductivity of the film was observed in the dark and under irradiation with white light. |: tet. A photocurrent clearly above the dark current (approx. Factor 3) was observed, which is called hot · ■■ 1 V applied voltage had a value of about 3 pA.

Example 5

On a surface of a cleaned as in Example 4 (but leaving the treatment with NaOH white) A 50.0 nm thick aluminum layer was vapor-deposited onto a glass slide. The slide was then 5 subjected to a dip treatment as described in Example 4, except that the Langmuir film from the Barium salt of 9-butyl-10-anthrylpropionic acid was formed. 467 monomolecular layers were on deposited on the slide. A pattern of aluminum dots, each 2.5 mm in diameter and 30.0 nm Thickness was evaporated through a mask on the Langmuir film thus obtained.

When a direct or alternating current of 40 V (Au ~, ΑΓ ') was applied, there was an emission of blue 10 light. Figures 4 and 5 show the varactor and photocurrent curves reported in Examples 3 and 4, respectively.

For this purpose 3 sheets of drawings

20th

Claims (16)

Patent claims: 1. A method for producing a film or layer of organic material with a high Degree of molecular orientation on a substrate, characterized in that on the surface a suitable liquid a very thin layer of organic material with a flat delocalized vr electron system generated and the substrate is moved through the layer in such a way that on a film of the organic material is deposited on a surface of the substrate. 2. The method according to claim 1, characterized in that a monomolecular layer is deposited will. 3. The method according to claim 1 or 2, characterized in that the substrate is repeated through the Layer is moved therethrough so that a composite film is deposited on the surface of the substrate. 4. The method according to any one of the preceding claims, characterized in that as organic Material a material with a cyclic structure that has both hydrophilic and hydrophobic substituents, is used. 5. The method according to claim 4, characterized in that an organic material is used at which the hydrophobic substituent is a linear hydrocarbon group with a linear chain length of not is more than 10 carbon atoms. 6. The method according to claim 5, characterized in that an organic material is used at in which the hydrophobic substituent is a hydrocarbon group with a chain length of 3 to 8 carbon atoms is. 7. The method according to claim 3, characterized in that the film is made of the organic material by depositing up to 10 monomolecular layers on the substrate. 8. The method according to claim 3, characterized in that the film is made of the organic material by depositing 20 to 200 monomolar layers on the substrate. 9. The method according to claim 4, characterized in that an anthracene, Pyrene or perylene derivative is used. 10. The method according to claim 9, characterized in that an anthracene derivative is used as the organic material is used that is in the 9-position with a hydrophobic linear alkyl group that is 3 to 8 and preferably Contains 3 or 4 carbon atoms, is substituted and in the 10-position a hydrophilic one Has substituents. 11. The method according to any one of the preceding claims, characterized in that a substrate Electrode material is used. 12. The method according to claim 11, characterized in that the film of the organic material deposited on a substrate having more than one separate electrode. 13. The method according to claim 11 or 12, characterized in that the free surface of the film with another electrode is brought into contact. 14. The method according to any one of the preceding claims, characterized in that on the substrate an organic material containing a dopant is deposited. 15. The method according to any one of the preceding claims, characterized in that alternately the organic material and another organic or an inorganic material are deposited. 16. Use of the film or layer produced by the method according to any one of the preceding Claims was made in connection with the substrate as an electrical or electronic composite body for components.