JPH0327932A - Organic thin film material - Google Patents

Abstract

PURPOSE:To make the molecular orientation and film thickness of a laminated film uniform by laminating on a substrate the monomolecular film of a long- chained organic molecule containing hydrophilic radical in the molecular chains and molecular ends and a compound molecular layer consisting of the molecular layer of a hydrophobic molecule. CONSTITUTION:A mixed solution is adjusted in solving a long-chained organic molecule containing hydrophilic radical in the molecular chains and molecular ends and hydrophobic molecule in a soluble organic solvent. After the mixed solution is dropped on the water, the solid film of a compound molecular layer consisting of the two-layer structure of long-chained organic molecule monomolecular layer and hydrophobic molecular layer is formed by increasing the surface pressure of the water surface. The hydrophobic molecular layer is a monomolecular layer or multimolecular layer. The mixing rate of the long- chained organic molecule/hydrophobic molecule for forming the compound molecular layer is 0.01-10, and more preferably, 0.1-5. Thus, the molecular orientation and film thickness of the laminated film can be made uniform.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to organic thin film materials, and more particularly to organic thin film materials containing hydrophobic organic molecules.

[Prior art and problems]

A Langmuir-Blodgett film (hereinafter referred to as r
It is called LB membrane. ) is well known. Functional molecules such as conductivity, luminescence, nonlinear optical properties, switching properties, and memory properties are introduced into the molecular layer of this LB film to produce conductive materials, light emitting element materials, nonlinear optical materials, switching elements, memory materials, etc. Research is actively underway to apply this technology to the electronics and optoelectronics fields. As this functional molecule, molecules having a molecular structure into which a long chain alkyl group is introduced for the LB film type are widely used.

However, there is a problem that introducing a long-chain alkyl group into a functional molecule reduces or dilutes the functionality of the molecule. Furthermore, if it is difficult to synthesize a molecule into which a long-chain alkyl group is introduced, there is a problem that a desired functional molecule cannot be introduced into the LB film.

Attempts have also been made to stack on a substrate a film in which only functional molecules without long-chain alkyl groups are developed on the water surface. However, in this case, it is difficult to stack the functional molecules on the substrate because they aggregate on the water surface, and even if they are stacked, the molecular orientation of the stacked films is random and the film thickness is non-uniform.

[Means to solve the problem]

Regarding the above-mentioned problems, the present inventors have conducted intensive studies to obtain an organic thin film material in which functional molecules are introduced in an orderly layered manner. The present inventors have discovered that a mixed molecule with a hydrophobic molecule as a hydrophobic molecule forms a two-layered solid membrane composite molecular layer on the water surface, and the organic thin film material of the present invention has been obtained.

That is, the present invention relates to an organic thin film material in which a composite molecular layer consisting of a monomolecular film of long-chain organic molecules containing hydrophilic groups in the molecular chains and at the molecular ends and a molecular layer of hydrophobic molecules is laminated on a substrate. Further, the present invention provides an organic film in which two or more types of composite molecular layers consisting of a monomolecular film of long-chain organic molecules containing hydrophilic groups in the molecular chain and at the molecular ends and a molecular layer of hydrophobic molecules are laminated on a substrate. Regarding thin film materials.

Furthermore, the present invention relates to an organic thin film material in which two types of composite molecular layers are alternately laminated. The present invention also relates to an organic thin film material characterized in that two types of hydrophobic molecules in the composite molecular layer are an electron-donating organic molecule and an electron-accepting organic molecule, respectively.

The present invention will be explained in detail below.

A method for laminating the organic thin film material of the present invention on a substrate is, for example, the Langmuir-Blodgett method (hereinafter referred to as rLB method).
That's what it means. ) can be used to stack a composite molecular layer on a water surface on a substrate.

First, a stacking method using the LB method will be explained.

A mixed solution is prepared by dissolving a long-chain organic molecule containing a hydrophilic group in the molecular chain and at the end of the molecule and a hydrophobic molecule in a soluble organic solvent. After dropping this mixed solution onto the water surface, by increasing the surface pressure of the water surface, a solid film of a composite molecular layer consisting of a two-layer structure of a monolayer of long-chain organic molecules and a layer of hydrophobic molecules is formed.

This hydrophobic molecular layer is a monolayer or a multilayer. This composite molecular layer can be laminated on a substrate by a method such as a vertical dipping method or a horizontal deposition method.

The mixing ratio of long chain organic molecules/hydrophobic molecules to form this composite molecular layer is 0.01-10, more preferably 0.01-10. 1 to 5. When this mixing ratio is 10 or more, long chain organic molecules are incorporated into the hydrophobic molecular layer, so that a composite molecular layer is not formed.

On the other hand, if the mixing ratio is 0.01 or less, hydrophobic molecules are likely to be incorporated into long-chain organic molecules, so that a composite molecular layer is not formed. A method for producing an organic thin film material containing two or more types of composite molecular layers includes, for example, spreading a mixed molecular solution in which long-chain organic molecules and hydrophobic molecules are dissolved in a soluble organic solvent on the water surface of a plurality of water tanks (troughs), After forming the composite molecular layer on each water tank, the substrate can be immersed in each tank to stack the composite molecular layer. In this case, one or both of long-chain organic molecules and hydrophobic molecules in the mixed molecule solution developed in each water tank is used.

Next, a method for producing an organic thin film material in which composite molecular layers are alternately laminated (alternate lamination method) will be described.

After forming respective composite molecular layers in two water tanks (troughs) in the same manner as described above, the substrate is immersed in one of the two troughs (trough 1).

Next, the substrate is moved from trough 1 to the other trough (trough 2) under the water surface, and then the substrate is pulled up above the water surface of trough 2. In this way, move the board from trough 1 → trough 2 → trough l
By repeatedly moving , it is possible to obtain an organic thin film material in which two types of composite molecular layers are alternately laminated on a substrate.

The long-chain organic molecule having a hydrophilic group in the molecular chain and at the end of the molecule used in the present invention will be explained.

The long-chain organic molecule used in the present invention has the following general formula H-(CH
2)-7R2(CHI}-R2(1) (where m+n is 8
The integers above and below 28, Rl and R' represent hydrophilic groups. ) As the hydrophilic group Rl in the molecular chain, functional groups and derivatives thereof that are more hydrophilic than saturated alkyl groups can be used. For example, -(:=C--C=C- SS1-c=c-c=c--c=c-c=c-,-
c-s-, 1c 10- so2-, -s-, -c-o - 0 -O-, -C-, -NHCS-, -NHCO-
, -NHCOO- -NHCSS-, -NH-, -N
=N −, etc. can be mentioned.

As R2, for example -SO. H. -COOH, -do-
, -OH and other ionic functional groups and their metal salts,
Halogen salts can be used.

Furthermore, as a long chain organic molecule of the present invention, the following general formula (2)
A double-stranded long-chain organic molecule with the structure can be used.

[In the formula, m'+n' (or n'') represents an integer of 8 to 28, Rl' and R2 represent a hydrophilic group.] Rz is the same group as above, and R1 is =N −
, =NCO. =NCS, (OC
O)2cH -(SCS)! CI{-. =NCO
O-, =NCSS-OCO (CHz)i C
H (CH!)l Coo-(k and l are each 1
to 5) can be used.

Furthermore, long-chain organic molecules in which a plurality of hydrophilic groups R1 are present in the molecular chain can also be used in the present invention. In this case, since long-chain organic molecules form the LB film, the number of carbon atoms in the saturated hydrocarbon in the molecular chain is preferably an integer of 8 or more and 28 or less.

As the long chain organic molecule of the present invention, for example, H-(CH2)
TTCMiC-C3C- (CHz) "COOHH-
C3C-C3C - (CH!)r COOHH-C
3C-C3C - (CH.)l'TCOOHH -
(CH,)TT C3C-C3C (CHz)a
COOHH - (CH.)TT C3C-C3C
- (C}I.)r OHH-(CHt)TTC3C
-C3C (CHz)s C5H5N” Br
(H (CHt)+a Coo (CHt) row 1N
CO CH2 N(CH3)”Cl[H-(CH,)
TTC3C-C3C (CH2)rCoo (CHz
)-rFTN(C}Is)"BrH-(CI-12)=
CmiC-C3C-(CH2). COO-(CI{2)
2N(CH)"Br and the like.

In addition, as a hydrophilic group Rl, -C3C-, 1CmiC-C
When a long chain organic molecule containing a functional group having an unsaturated bond such as 2C1 is used, the obtained organic thin film material can be exposed to light.
Patterning can be performed by irradiating energy such as electrons and ions.

When the hydrophilic group has a photosensitive function as described above, the organic thin film material of the present invention has the characteristic that the thin film can be patterned into any shape through both energy irradiation and development processes.

The hydrophobic molecules used in the present invention will be explained.

In order to form the composite molecular layer of the present invention, it is preferable that the hydrophobic molecule does not contain a highly hydrophilic functional group (for example, the functional group represented by R1 above).

In addition, when the hydrophobic molecule contains a long-chain alkyl group,
Such hydrophobic molecules are not preferred because they form a mixed molecular layer with the long-chain organic molecules, making it impossible to obtain the composite molecular layer of the present invention.

The molecular structure of the hydrophobic molecule used in the present invention is not particularly limited because it varies depending on the use of the obtained organic thin film material (conductive material, nonlinear optical material, switching element, memory material, etc.).

For example, a conductive organic thin film material can be obtained by the above-mentioned layer-by-layer method using electron-donating molecules and electron-accepting molecules as hydrophobic molecules.

Examples of electron-donating organic molecules used for conductive organic thin film materials include tetrathiafulvalene, tetramethyltetrathiafulvalene, bisethylenedithiotetrathiafulvalene, tetraselenafulvalene, tetramethyltetraselenafulvalene, aniline, and thiophene. ,
Mention may be made of hydrophobic molecules such as pyrrole, ferrocene, phthalocyanine, phenylenediamine N-methylphenazine, anthracene, perylene, hexamethylbenzene. Examples of electron-accepting organic molecules include tetracyanoquinodimethane, tetracyanonaphthoquinodimethane,
Mention may be made of hydrophobic molecules such as chloranil, tetrafluorotetradianoquinodimethane, dimethyldicyanoquinodimethane, and tetradianoethylene.

In addition, hydrophobic molecules used for nonlinear optical materials include nitroaniline, nitromethylaniline, nitroaniline derivatives, urea derivatives, methyl-(2,4-dinitrophenyl) monoaminopropanate, 4-methoxynitrotran, N[ Examples include 5-(2-nitro)pyridyl]prolimol, 5-nitroindole, N-(4-nitrophenyl)N-methylaminoacetonitrile, and the like. Examples of hydrophobic molecules used for memory materials include porphyrin, porphyrin derivatives, azobenzene derivatives, fulgide, spiropyran, quinizarin, futacyanine, and futacyanine derivatives. Hydrophobic molecules used for luminescent materials include naphthalene, anthracene, anthracene derivatives, perylene, phthalocyanine, phthalocyanine derivatives,
Examples include thioindigo derivatives and stilbene derivatives.

Examples of substrates used in the present invention include quartz, Ca
b. , MgF 2 , sapphire, MgO, alumina and other ceramic substrates, Au, Pt, Cu, Ni and other metal substrates, and polystyrene, polyethylene terephthalate, polyethylene, anthracene crystal and other organic substrates.

Next, a method for manufacturing the conductive organic thin film material will be explained.

Two types of solutions are prepared in which an electron-donating organic molecule, the long-chain organic molecule, and an electron-accepting organic molecule are each fused to an organic solvent. According to the layer-by-layer method, a solution containing an electron-donating organic molecule and a long-chain organic molecule and a solution containing an electron-accepting organic molecule and a long-chain organic molecule were placed in two troughs (the former solution was placed in trough 1, the latter solution was placed in trough 1, The solution is spread in trough 2) and surface pressure is applied until it becomes a solid film, forming two types of composite molecular layers.

Next, by repeatedly immersing the substrate in trough 1 and lifting it up in trough 2, a composite molecular layer of electron-donating organic molecules and long-chain organic molecules and a composite molecule layer of electron-accepting organic molecules and long-chain organic molecules are formed on the substrate. An organic thin film material having alternating layers can be obtained.

The mixed molecules of the above-mentioned long-chain organic molecules containing hydrophilic groups in the molecular chain and at the molecular ends and the above-mentioned hydrophobic molecules are spread on the water surface and surface pressure is applied until it becomes a solid film. It has a composite molecular layer structure in which a monolayer of molecules and a molecular layer of the hydrophobic molecules are formed into layers.

The structure of this composite molecular layer is determined by the surface pressure-1 molecule occupied cross-sectional area curve (π-8 curve) of the film developed on the water surface, the film thickness of the film stacked on the substrate, the X-ray diffraction pattern, and the FT-IR spectrum. It can be confirmed by etc.

According to the results of the π-AJ line, the occupied cross-sectional area on the water surface per long-chain organic molecule does not change due to the mixture of hydrophobic molecules. This means that a mixture of long-chain organic molecules and hydrophobic molecules has a two-layer structure, each formed in separate layers (
composite molecular layer).

In addition, the film thickness of the organic thin film material in which a composite molecular layer formed on a water surface is laminated on a substrate is the same as that of a film in which only a monomolecular film of long-chain organic molecules that does not contain hydrophobic molecules is laminated on a substrate. The increase in thickness compared to the thickness also indicates that the organic thin film material has a composite molecular layer structure as referred to in the present invention.

Furthermore, the (00n) diffraction peak position changes from the X-ray diffraction pattern, and the distance between molecular layers changes compared to a film that does not contain hydrophobic molecules. This also indicates that a monomolecular layer of long-chain organic molecules and a molecular layer of hydrophobic molecules form a layered composite molecular layer.

On the other hand, in a membrane in which a long-chain organic molecule that does not have a hydrophilic group in its molecular chain and has a hydrophilic group only at the end of the molecule is used and a mixture of hydrophobic molecules is spread on the water surface, 1, in which sexual molecules are incorporated into a layer of long-chain organic molecules and mixed.
It has a layered structure and the composite molecular layer of the present invention is not formed.

This is confirmed in the π-A curve. That is, it can be seen that by incorporating two hydrophobic molecules into the long-chain organic molecule layer, the occupied cross-sectional area per molecule of the long-chain organic molecule increases. Furthermore, the fact that the film thickness of the film laminated on the substrate and the (OOn) diffraction peak position of the X-ray diffraction pattern do not change also indicates that a composite molecular layer structure as defined in the present invention is not formed.

Therefore, in order to obtain an organic thin film material in which the composite molecular layer of the present invention is laminated on a substrate, it is necessary that the long-chain organic molecules contain hydrophilic groups in the molecular chains and at the molecular ends.

It is not clear why this mixture of long-chain organic molecules and hydrophobic molecules that contain hydrophilic groups in the molecular chain or at the end of the molecule forms a layered structure in which they are separated from each other on the water surface. This is thought to be because the hydrophilic groups contained in the molecular chain repel hydrophobic molecules that have entered the long-chain organic molecule layer to the outside of the long-chain organic molecule layer.

The organic thin film material can be provided with a protective layer or an electrode layer for stabilizing the film, if necessary.

Furthermore, if necessary, patterning treatment for forming circuits, resist layers, etc. can be performed by annealing treatment to reduce defects in the laminated structure of molecules or by energy irradiation with light, electrons, ions, etc.

The organic thin film material of the present invention has a structure in which hydrophobic organic molecules and long-chain organic molecules are stacked in layers, and contains hydrophobic molecules as functional molecules, so it can be used as a conductive material, a light emitting element material, Nonlinear optical materials, switching element materials,
It can be applied to electronic materials such as memory materials and is extremely useful industrially.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 10.12-Pentacosadiynoic acid (PDA) and tetradianoquinodimethane (TCNQ) were each dissolved in chloroform to prepare solutions with a concentration of 2 mmol/A. After mixing PDA solution 10- and TCNQ solution 5- to form a PDA-TCNQ mixed solution, the mixed solution 0.
1 5- to CdClz 5 x1 0 -'mol
/C 2 The mixture was spread on a trough (manufactured by Lauda, West Germany) adjusted to 0°C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and while maintaining the surface pressure at 25 mN/m, the CaF substrate was repeatedly immersed and pulled up using the vertical immersion method to form 39 layers of composite molecular layers on the Cab2 substrate. A stacked organic thin film material could be obtained.

The trough area (converted to the occupied cross-sectional area per PDAI molecule) and surface pressure change (π-A curve) when the PDA-TCNQ mixed solution is spread on the trough and the trough water surface is compressed is P
This is shown in FIG. 1 together with the π-A curve of a PDA monomolecular film in which only the DA solution is spread on the trough. From now on PDA
It can be seen that the π-A curve of the -TCNQ mixed molecular layer and the π-A curve of the PDA monolayer match. Therefore, P on the water surface
DA/TCNQ composite molecular layer consists of PDA monolayer and TCN
It shows that each Q molecular layer has a two-layer structure formed in a layered manner.

The thickness of the obtained organic thin film was 1,500 layers, which was increased compared to the film thickness (1,100 layers) obtained by laminating 39 layers of PDA monolayers only. Moreover, the X-ray diffraction pattern is (00n) (n=1~
6) Surface diffraction points were observed, indicating that the organic thin film material had a layered structure.

This organic thin film material is covered with a photoresist mask.
After exposure with an OOW low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

Example 2 10. Dissolve 12-pentacosadiynoic acid (PDA) and chloranil (TCQ) in chloroform and add 2 m
Solutions with a concentration of mof/l were prepared respectively. Mix 107nl of PDA solution and 57nl of TCNQ solution and make PDA
- After making the TCQU mixture solution, the mixed solution 0.1
5- to Cdi25X 1 0-'moA/17, 2
The mixture was spread on a trough (manufactured by Lauda, West Germany) adjusted to 0°C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and Ca was added by vertical immersion method while maintaining the surface pressure at 25 mN/m.
b. CaF. An organic thin film material in which 39 composite molecular layers were laminated on a substrate could be obtained.

After spreading the PDA-TCQ mixed solution on the trough, the trough area (converted to the occupied cross-sectional area per PDA molecule) and surface pressure change (π-A curve) when compressing the trough water surface are measured when only the PDA solution is spread on the trough. This is shown in FIG. 1 along with the π-A curve of the PDA monomolecular film developed. From this P
It can be seen that the π-A curve of the DA-TCQ mixed molecular layer and the π-A curve of the PDA monolayer match. Therefore, the PDA-TCQ composite molecular layer on the water surface has a two-layer structure in which a PDA monolayer and a TCQ molecular layer are each formed in layers.

The thickness of the obtained organic thin film was 1,400 layers, which was increased compared to the film thickness of 39 layers of PDA monolayer (1,100 layers). In addition, the X-ray diffraction pattern is (00n) (n = 1~
8) Diffraction points on the surface were observed, indicating that the organic thin film material had a layered structure.

This organic thin film material is covered with a photoresist mask.
After exposure with an OOW low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

Example 3 22. 24-pentacosadiynoic acid (ω-PDY),
Tetracyanoquinodimethane (TCNQ) was dissolved in chloroform to prepare a solution having a concentration of 2 mmof/ff. ω-PDY solution lO7nl and TCN
After mixing 5 parts of the Q solution to obtain a combined solution of ω1 PDY-TCNQ, the mixed solution 0. 157nl to CdCj2z
The mixture was spread on a trough (manufactured by Lauda, West Germany) adjusted to 5 x 10-'moI2/ff and 20°C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a polymer layer solid film, and the surface pressure was increased to 25 mN.
By repeating dipping and pulling up of the CaF2 substrate by the vertical dipping method while maintaining the temperature at /m, it was possible to obtain an organic thin film material in which 39 composite molecular layers were laminated on the CaF2 substrate.

The trough area (ωPDY
Change in surface pressure (converted to occupied cross-sectional area per molecule) (π
-A curve) is shown in FIG. 2 together with the π18 curve of the ω1 PDY monomolecular film in which only the ω1 PDY solution is spread on the trough. From this, ω-PDY-TCNQ mixed molecular layer π-A
It can be seen that the curve matches the π-A curve of the PDA monolayer. Therefore, the ω-PDY-TCNQ composite molecular layer on the water surface has a two-layer structure in which the ω-PDY monolayer and the TCNQ molecular layer are each formed in a layered manner.

The thickness of the obtained organic thin film was 1500 mm and ω-PDY
This increased compared to the film thickness of 39 monolayers (1,100 people). Also, the X-ray diffraction pattern is (00n) (n= 1
-5) Diffraction points were observed, indicating that the organic thin film material had a layered structure.

Cover this organic thin film material with a photoresist mask 1
After exposure with a 00W low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

Example 4 Sodium-1,2-bis(dodecyloxycarbonyl)
Monoethane-1-sulfonate (BDS) and tetramethyltetrathiafulvalene (T) JT) were each dissolved in chloroform to prepare solutions with a concentration of 2 mmo6/n. After mixing 10-nl of BDS solution and 57 nl of TMT solution to obtain a BDS-TMT mixed solution, 0.0-nl of the mixed solution was prepared. 157 nl was spread on a pure water trough (manufactured by Lauda, West Germany) adjusted to 20°C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and while maintaining the surface pressure at 25 mN/m, the polyethylene terephthalate substrate was repeatedly immersed and pulled up by vertical dipping and removal to form a composite molecular layer on the polyethylene terephthalate substrate for 40 minutes. A layered organic thin film material could be obtained. After the BDS-TMT mixed solution was spread on the trough, the trough area (converted to the occupied cross-sectional area per molecule of BD3) and surface pressure change (π-A curve) when the trough water surface was compressed was investigated. As a result, BDS-
π-A curve of TMT monolayer and π of BDS monolayer
- It was found that the A curves matched. Therefore, B on the water surface
DS-TMT composite molecular layer consists of BDS monolayer and TM
This shows that the T molecule layer has a two-layer structure in which each layer is formed in a layered manner.

The thickness of the obtained organic thin film was 1,500 layers, which is increased compared to the film thickness of 39 layers of BDS monolayer (1,000 layers).
It was found that the organic thin film material in which diffraction points of planes 1 to 8) were observed had a layered structure.

Example 5 10. 12-pentacosadiynoic acid (PDA). Tetracyanoquinodimethane (TCNQ) and tetrathiafulvalene (TTF) were each dissolved in chloroform to prepare a solution with a concentration of 2 mmol/j'. PDA-TC mixed with PDA solution 1〇1 and TCNQ solution 5-
A PDA/TTF mixed solution was prepared by mixing the NQ mixed solution, PDA solution 10-, and TTF solution 5-. These mixed solutions were transferred to two troughs (CdCi' t 2 5 x
1 0-'mol/I! , adjusted to 20° C.) to form a mixed molecular layer on the water surface of each trough. Next, the trough water surface is compressed to form a mixed molecular layer solid film, and CaF. The substrate was immersed in a trough shaped with TTF-PDA composite molecular layer, TCNQ-P
Cab. We were able to obtain an organic thin film material in which 39 TTF-PDA composite molecular layers and TCNQ-PDA composite molecular layers were laminated on a substrate.

The thickness of the obtained organic thin film material was 1800 mm, and the PD
This increased compared to the film thickness of 39 layers of A monolayer (1,100 people). Also, the X-ray diffraction pattern is (00n) (n=
Diffraction points on planes 1 to 10) were observed, and the organic thin film material
It was found that it has a layered structure.

Cover this organic thin film material with a photoresist mask 1
After exposure with a 00W low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

The organic thin film material having this negative pattern is made of gold (A
u) As a result of forming electrodes by vapor deposition and measuring the conductivity, l
XIO-'S/cm.

Example 6 10. 12-pentacosadiynoic acid (PDA), tetracyanoquinodimethane (TCNQ) and tetrathiafulvalene (TTF) were each dissolved in chloroform to prepare a solution with a concentration of 2 mmon/1. P.D.
A solution 5ml and TCNQ solution 51rI. PD mixed with
A - A PDA/TTF mixed solution was prepared by mixing the TCNQ mixed solution, PDA solution 5-, and TTF solution 57 nl. These mixed solutions were poured into two troughs (CdCf 2 5
X 10 -'mob / (!, adjusted to 200C), respectively, to form a mixed molecular layer on the water surface of each trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and the surface pressure was increased to 25 mN.
TT of the quartz substrate by alternating lamination while maintaining the
Immersed in the trough in which the F-PDA composite molecular layer was formed;
TTF-P was deposited on a quartz substrate by repeatedly pulling up the TCNQ-PDA composite molecular layer using the formed trough.
An organic thin film material in which 39 DA composite molecular layers and TCNQ-PDA composite molecular layers were laminated could be obtained.

The film thickness of the obtained organic thin film material was 2200 mm, and PDA
This increased compared to the film thickness of 39 monolayers (1,100 people). Also, the X-ray diffraction pattern is (00n) (n=1
-8) Diffraction points were observed, indicating that the organic thin film material had a layered structure.

This organic thin film material is covered with a photoresist mask.
After exposure with an OOW low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

The organic thin film material having this negative pattern is made of gold (A
u) As a result of forming electrodes by vapor deposition and measuring the conductivity, 5
X 10-'S/cm.

Example 7 10. 12-pentacosadiynoic acid (PDA). 2
-Methyl-4-nitroaniline (MNA) was dissolved in chloroform to prepare a solution having a concentration of 2 mma6/f. After mixing PDA solution 10- and MNA solution 5-1 to obtain a PDA-MNA mixed solution, the mixed solution 0. l5- to CdC125X10-
'man/(1) was developed on a trough (manufactured by Lauda, West Germany) adjusted to 20°C to form a mixed molecular layer on the water surface of the trough.

Next, the trough water surface was compressed to form a mixed molecular layer solid film, and the CaF2 substrate was repeatedly immersed and pulled up using the vertical immersion method while maintaining the surface pressure at 25 mN/m.
aF. An organic thin film material in which 39 composite molecular layers were laminated on a substrate could be obtained.

After the PDA-MNA mixed solution was spread on the trough, the trough area (converted to the occupied cross-sectional area per PDA molecule) and surface pressure change (π-A curve) when the trough water surface was compressed were measured. As a result, it was found that the π-A curve of the PDA-NMA mixed molecular layer and the π-A curve of the PDA monolayer matched. This indicates that the PDA/MNA composite molecular layer on the water surface has a two-layer structure in which a PDA monolayer and a 1,000-layer MNA layer are each formed in a layered manner.

The thickness of the obtained organic thin film was 1,300 layers, which was increased compared to the thickness of 39 layers of PDA monolayer (1,100 layers). Also, the X-ray diffraction pattern is (00n) (n=1
-6) Diffraction points were observed, indicating that the organic thin film material had a layered structure.

This organic thin film material is covered with a photoresist mask.
After exposure with an OOW low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed. This material also exhibits nonlinearity (χ”
=5 x l O-"esu).

Example 8 0.0'-Didodecanoyl N-(α-trimethylammonioacetyl)-diethanolamine chloride (O
DA). Anthracene (ANT) was dissolved in chloroform to prepare a solution having a concentration of 2 mmoj'/j'. DDA solution IO- and ANT solution 201nl
After mixing to obtain an ODA-ANT mixed solution, 0.0% of the mixed solution was prepared. 15d as CdCj2 2 5 X 1
The mixture was spread on a trough (manufactured by Lauda, West Germany) adjusted to 0 -'mon/Il and 20°C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and while the surface pressure was maintained at 25 mN/m, the InSnOx-coated quartz substrate was repeatedly immersed and pulled up by the vertical immersion method, and the composite was deposited on the quartz substrate. It was possible to obtain an organic thin film material in which 39 molecular layers were laminated.

After the ODA-ANT mixed solution was spread on the trough, the trough area (converted to the occupied cross-sectional area per DDA molecule) and surface pressure change (π-A curve) when the trough water surface was compressed were measured. As a result, π of the ODA-ANT mixed molecular layer
It was found that the -A curve and the π-A curve of the ODA monolayer matched. Therefore, the ODA/ANT composite molecular layer on the water surface has a two-layer structure in which the ODA monolayer and the ANT molecular layer are each layered.

The thickness of the obtained organic thin film was 1,500 layers, which was increased compared to the film thickness (1,100 layers) obtained by laminating 39 layers of DDA monolayer only. Moreover, the X-ray diffraction pattern is (0 0 n) (n=
Diffraction points on planes 1 to 6) were observed, indicating that the organic thin film material had a layered structure.

The A1 electrode deposited on this organic thin film material emitted light when an electric field was applied between both electrodes (0.0
1W/rrI').

Example 9 9,11-nonacosadiinamide trimethylene glycine (NAG) and tetrathiafulvalene (TTF) were each dissolved in chloroform to prepare solutions with a concentration of 2 mmol/1. 107nl of NAG solution and TT
After mixing 1 l of the F solution to obtain a NAG-TTF mixed solution, 0. 157nl to CdCj22
5 X 10-'rno (1/1, developed on a trough (manufactured by Lauda, West Germany) adjusted to 20 °C to form a mixed molecular layer on the trough water surface.Then, the trough water surface was compressed. A mixed molecular layer solid film is formed with a surface pressure of 25 m.
The CaF2 substrate was repeatedly immersed and raised using the vertical dipping method while maintaining the CaF2 substrate at N/m. An organic thin film material in which 39 composite molecular layers were laminated on a substrate could be obtained.

After the NAG-TTF mixed solution was spread on the trough, the trough area (converted to the occupied cross-sectional area per molecule of NAG) and surface pressure change (π-A curve) when the trough water surface was compressed were measured. As a result, it was found that the π-A curve of the NAG-TTF mixed molecular layer and the π-A curve of the NAG monolayer matched. This indicates that the NAG/TTF composite molecular layer on the water surface has a two-layer structure in which a NAG monolayer and a TTF molecular layer are each formed in layers.

The thickness of the obtained organic thin film was 1,200 layers, which was increased compared to the thickness of 39 layers of NAG monolayer (1,070 layers). Moreover, the X-ray diffraction pattern is (OOn)(n-1~
6) Surface diffraction points were observed, indicating that the organic thin film material had a layered structure.

Cover this organic thin film material with a photoresist mask 1
After exposure with a 00W low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

Example 10 10.12-Tridecadiynoic acid (TDY) and tetracyanonaphthoquinodimethane (TNAQ) were each dissolved in chloroform to prepare solutions with a concentration of 2 mmof/41'. One TDY solution and one TNAQ solution
After mixing 0J to make a TDY-TNAQ mixed solution, 0.15- of the mixed solution was mixed with CdlJ' 2 5 x
10-'mol/l, and was spread on a trough (manufactured by Lauda, West Germany) adjusted to 20°C to form a mixed molecular layer on the water surface of the trough.

Next, the trough water surface was compressed to form a mixed molecular layer solid film, and Cab. The substrate is repeatedly immersed and pulled up.
b. An organic thin film material in which 39 composite molecular layers were laminated on a substrate could be obtained.

After the TDY-TCNQ mixed solution was spread on the trough, the trough area (converted to the occupied cross-sectional area per TDY molecule) and surface pressure change (π-A curve) when the trough water surface was compressed were measured. As a result, it was found that the π-A curve of the TDY-TNAQ mixed molecular layer and the π-A curve of the TDY monolayer matched. Therefore, TDY/TNAQ on the water surface
The composite molecular layer has a two-layer structure in which a TDY monolayer and a TNAQ molecular layer are each formed into layers.

The thickness of the obtained organic thin film was 2,300 layers, which was increased compared to the thickness of 39 layers of TDY monolayer (800 layers). Moreover, the X-ray diffraction pattern is (0 0 n) (n=
Diffraction points on planes 1 to 6) were observed, indicating that the organic thin film material had a layered structure.

This organic thin film material is covered with a photoresist mask.
After exposure with an OOW low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

Example 11 Bis(ethylene-9,l1-pentacosadiinoate)
Dimethylammonium bromide (BPA) and bisethylene dithiotetrathiafulvalene (BET) were each dissolved in chlorobenzene to a concentration of 2 mmar1/4.
Solutions with a concentration of 1' were prepared respectively. BPA-BET by mixing BPA solution 5 and BET solution
After making a mixed solution, 0.15 ml of the mixed solution was heated at 20°
The mixture was spread on a pure water trough (manufactured by Lauda, West Germany) adjusted to a water temperature of C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and while the surface pressure was maintained at 25 mN/m, the quartz substrate was repeatedly immersed and pulled up by the vertical immersion method to form a composite molecular layer on the quartz substrate for 39 mN/m. A layered organic thin film material could be obtained.

After the BPA-BET mixed solution was spread on the trough, the trough area (converted to the occupied cross-sectional area per molecule of BPA) and surface pressure change (π-A curve) when the trough water surface was compressed were measured. As a result, π of the BPA-BET mixed molecular layer
It was found that the 18 curve and the π-A curve of the BPA monolayer matched. Therefore, the BPA/BET composite molecular layer on the water surface has a two-layer structure in which the BPA monolayer and the BET molecular layer are each formed into layers.

The thickness of the obtained organic thin film was 2,300 layers, which was increased compared to the thickness of 39 layers of BPA monolayer (1,150 layers). The X-ray diffraction pattern is (00n) (n=1
-6) Diffraction points were observed, indicating that the organic thin film material had a layered structure.

This organic thin film material is covered with a photoresist mask.
After exposure with an OOW low-pressure mercury lamp and development with ethanol, only the unexposed portions were dissolved and a negative pattern could be formed.

Comparative Example 1 Arachidic acid (ARA) and chloranil (TCQ) were each dissolved in chloroform to prepare solutions with a concentration of 2 mmoA/j2. AR,A solution 107nl
After mixing 57 nl of TCQ solution and ARA-TCQ mixed solution, 0.15-nl of the mixed solution was mixed with CdCl2.
25 x 10-'man/1 and spread on a trough (manufactured by Lauda, West Germany) adjusted to 20°C to form a mixed molecular layer on the water surface of the trough. Next, the trough water surface was compressed to form a mixed molecular layer solid film, and the surface pressure was increased to 25 mN/
By repeating dipping and pulling up of the CaF2 substrate by the vertical dipping method while maintaining the temperature at m, a film in which 39 composite molecular layers were laminated on the CaF2 substrate could be obtained.

After spreading the ARA-TCQ mixed solution on the trough, the trough area (converted to the occupied cross-sectional area per ARA molecule) and surface pressure change (π-A curve) when compressing the trough water surface are measured when only the ARA solution is spread on the trough. Fig. 3 shows the π-A curve of the ARA monolayer developed in Figure 3. AR from this
It can be seen that the occupied cross-sectional area per ARA molecule of the π-18 curve of the A-TCQ mixed molecular layer is increased compared to the occupied cross-sectional area of the π-A curve of the ARA monolayer.

The thickness of the obtained membrane was 1,050 layers, which corresponded to the thickness (1,050 layers) of laminating 39 layers of ARA monolayers.

Further, in the X-ray diffraction pattern, diffraction points on the (OOn) (n=1 to 6) plane were observed.

Therefore, these results revealed that the ARA-TCQ composite molecular layer on the water surface has a structure in which TCQ molecules are incorporated into the ARA monolayer.

Comparative Example 2 Arachidic acid (ARA) and tetracyanoquinodimethane (TCNQ) were each dissolved in chloroform to a size of 2 nm.
Solutions with a concentration of off/N were prepared.

After combining 10 mA' of ARA solution and 57 nl of TCNQ solution to obtain an ARATCNQ mixed solution, 0.0 mA' of the mixed solution was prepared.
157nl to CdCfl2 2 5 x 10-'m
ob / (1, developed on a trough (manufactured by Lauda, West Germany) adjusted to 20°C to form a mixed molecular layer on the trough water surface.Then, the trough water surface was compressed to form a mixed molecular gas solid film. A film in which 39 composite molecular layers were laminated on a CaF 2 substrate was obtained by repeating dipping and pulling up of the CaF 2 substrate using a vertical immersion method while maintaining the surface pressure at 25 mN/m.

FIG. 3 shows the trough area (converted to occupied cross-sectional area per ARA molecule) and surface pressure change (π-A curve) when compressing the trough water surface after spreading the ARA-TCNQ mixed solution on the trough. From this ARA-TCNQ
It can be seen that the occupied cross-sectional area per ARA molecule of the π-A curve of the folded molecular layer is increased compared to the occupied cross-sectional area of the π-A curve of the ARA monolayer.

The thickness of the obtained membrane was 1,050 layers, which corresponded to the thickness (1,050 layers) of laminating 39 layers of ARA monolayers.

Further, in the X-ray diffraction pattern, diffraction points on the (00n) (n=1 to 3) plane were observed.

Therefore, from these results, ARA-TCNQ on the water surface
The composite molecular layer was found to have a structure in which TCNQ molecules were incorporated into the ARA monolayer.

[Brief explanation of drawings]

Figure 1 shows PDA-TCQd composite layer, PDA-
The π-A curves of the TCNQ mixed molecular layer and the PDA monolayer, Figure 2 are the π-A curves of the ω-PDY-TCNQ mixed molecular layer, the ω-PDY-TCQ mixed molecular layer, and the ω-PDY monolayer. Figure 3 shows the π-A curves of ARA-TCNQ mixed molecular layer, ARA-TCQ mixed molecular layer and ARA monolayer, respectively.

Claims (4)

[Claims] (1) An organic thin film material in which a composite molecular layer consisting of a monomolecular film of long-chain organic molecules containing hydrophilic groups in the molecular chain and at the molecular ends and a molecular layer of hydrophobic molecules is laminated on a substrate. (2) Organic thin film material in which two or more types of composite molecular layers consisting of a monomolecular film of long-chain organic molecules containing hydrophilic groups in the molecular chain and at the molecular ends and a molecular layer of hydrophobic molecules are laminated on a substrate. . (3) The organic thin film material according to claim (2), in which two types of composite molecular layers are alternately laminated. (4) The organic thin film material according to claim (3), wherein the two types of hydrophobic molecules in the composite molecular layer are an electron-donating organic molecule and an electron-accepting organic molecule, respectively.