JPH05135631A - Wiring formation on lb film - Google Patents

Abstract

PURPOSE:To finely form a wiring on an LB film under ordinary temperature or under ordinary temperature with ordinary pressure by imparting a functional group to become a biotin mark to the surface of the LB film, and forming a biotin pattern on the surface, followed by being combined with avidin. CONSTITUTION:When a wiring is formed on an LB film 2, a functional group to become a mark of biotin 4 is imparted to the surface of the film 2 so as to form a biotin pattern to be combined with the surface of the film 2 through the functional group. Next, avidin 5 having metal colloid is combined with this biotin pattern by using specific combination of avidin 5 with biotin 4 so as to obtain the wiring. In this case, the functional group to become the mark of this biotin 4 is determined to be an amino group or a carboxyl group. Then, since a series of treatments can be under ordinary conducted under ordinary temperature, a desired wiring can be formed while allowing to be also formed cold. Further, since biotin pattern formation can be performed by a present fine pattern making technique such as electron ray exposure, untraviolet ray exposure and X-ray exposure, a desired fine pattern can be obtained.

Description

Detailed Description of the Invention

[0001]

This invention relates to LB as an organic thin film.
The present invention relates to a method for forming wiring on a film.

[0002]

2. Description of the Related Art Organic molecules have various excellent electrical and optical functions. For this reason, many researches and developments have been carried out to utilize it as a next-generation electronic material.

Among these, the LB method, which is capable of forming an ultra-thin film by generally controlling the arrangement of the organic molecules, which are weak against heat, in the process of normal temperature and normal pressure, and by the unit of the molecule, is drawing attention. The LB method basically includes a vertical immersion method and a vertical attachment method. The former is a method of moving the substrate in and out of the water surface (sub-phase) where the molecules are deployed so that it crosses the sub-phase, and transferring the developed film on the sub-phase. This is a method of transferring the developed film on the substrate. Further, as a modification of these methods, a so-called hetero accumulation method in which different molecules are developed in a plurality of water tanks, a substrate is moved between these water tanks, and these developed films are sequentially accumulated on this substrate, further, for example, in Document a
As shown in (Proceedings of the Spring 1991 Society of Applied Physics, p. 1088, Takatsuka, Xie, Nakamoto, Moriizumi et al.), The arrangement of molecules that differ also in the two-dimensional direction (in the plane) of the membrane by the so-called partial expansion method. Have been developed.

By the way, in order to operate the LB film thus produced as a device, an electric signal is input to a desired position of the film, an electric signal is taken out from a desired position, and a plurality of functional regions are provided. Need to be electrically connected, and it is indispensable to provide electrical wiring on the LB film. Conventionally, LB has been used as a method of forming wiring on the LB film.
A vacuum vapor deposition method is used in which a mask having a wiring pattern-shaped slit is interposed between the film and the vapor deposition source (usually, the mask is used in close contact with the LB film) to form a metal wiring pattern on the LB film. Was there.

[0005]

However, when the wiring is formed on the LB film by the vacuum deposition method, 1)
The function of the organic thin film deteriorates due to radiant heat during vapor deposition. 2) Since the mask for forming the wiring pattern must be a slit type because vapor deposition particles must pass through, it is difficult to form a thin wiring of 0.1 mm or less. 3) LB for wiring formation
The membrane needs to be placed in an evacuated system. There was a problem such as.

The present invention has been made in view of the above points, and therefore an object of the present invention is to provide a method for finely forming wirings on an LB film as an organic thin film at room temperature or at room temperature and atmospheric pressure. To provide.

[0007]

In order to achieve this object, according to the present invention, when forming a wiring on the LB film, a functional group serving as a biotin label is attached to the surface of the LB film, and the above-mentioned LB film is formed. It is characterized in that a biotin pattern that binds via the above-mentioned functional group is formed on the surface, and avidin having a metal colloid is bound to the biotin pattern using specific binding between avidin and biotin to obtain wiring.

In carrying out the present invention, the above-mentioned functional group is imparted to the LB film by using an LB film-forming material containing the functional group or by injecting a molecule containing the functional group into the LB film. It is preferable to do so.

Further, in carrying out the present invention, it is preferable that the above-mentioned biotin pattern is formed by any of the following methods (1) to (3).

(1) The above-mentioned functional group is provided on the entire surface of the LB film, and the LB film having the functional group is selectively irradiated with an energy ray to form a functional group pattern corresponding to the above-mentioned biotin pattern, and thereafter. How to bind biotin. (2) A method in which the above-mentioned functional group is applied to the entire surface of the LB film, biotin is bound to the functional group-added LB film, and the biotin-bonded LB film is selectively irradiated with energy rays.

(3) A method of selectively injecting a molecule having a functional group into the LB film to form a functional group pattern corresponding to the above-mentioned biotin pattern, and then binding biotin.

Here, the energy beam used is an electron beam,
It is preferable to use any one of X-ray, laser and ultraviolet ray.

Further, in carrying out the present invention, it is preferable that the functional group serving as a biotin label is an amino group or a carboxyl group.

[0014]

According to the constitution of the present invention, the LB film and biotin are bound via a functional group, and this biotin and avidin having a metal colloid are bound by a specific binding reaction of avidin-biotin, resulting in Thus, a wiring made of a metal colloid is formed on the LB film. Here, since the series of processes can be performed at room temperature, desired wiring can be formed at room temperature. In addition, the bond between the functional group and biotin is a covalent bond and thus is strong. Furthermore, the bond-dissociation constant between biotin and avidin is as strong as 10 ¹⁵ M ⁻¹ or more. Therefore, the gold colloid particles are firmly bonded on the LB film.

Further, in forming the biotin pattern, it is necessary to place the sample in a vacuum system in the structure using an electron beam, but a structure using a laser, a structure using ultraviolet rays and a structure in which a molecule having a functional group is separately injected. Then
Both biotin patterns can be performed at atmospheric pressure. As a result, it is possible to obtain a desired wiring at room temperature and atmospheric pressure.

Further, since the pattern formation of biotin can be performed by a technique established as a fine pattern production technique in the current semiconductor device manufacturing, such as electron beam exposure, ultraviolet exposure, X-ray exposure, a desired fine pattern can be obtained. Therefore, the metal colloid pattern obtained by combining with this biotin pattern is sufficiently finer than the conventional wiring formed using the vapor deposition mask.

[0017]

EXAMPLES Examples of the method for forming wiring on the LB film of the present invention will be described below. However, the materials used in the following description, the usage fee of the materials, the processing temperature, the processing time, and the LB
Numerical conditions such as the cumulative number of membranes are but one example within the scope of this invention.

<First Example> First, an example in which the LB film-forming material has a functional group serving as a biotin label will be described.

1. Preparation of LB film 1-1. When the LB film is composed of molecules containing amino groups 2 mM of docosylamine (CH ₃ (CH ₂ ) ₂₁ NH ₂ )
A (mmol) chloroform solution was spread on a sub-phase aqueous solution (pure water), and the water surface was compressed after waiting about 10 minutes until the chloroform was sufficiently evaporated. The temperature of the sub-phase aqueous solution was 20 degrees, and the compression pressure was 30 mN / m. After forming a monomolecular film on the surface of the water in this way, it was submerged in water in advance (15 mm wide, 40 m high)
m, thickness 0.5 mm) to form a first layer LB film. After that, a total of 21 layers of cumulative films were formed on the substrate by successively lowering and raising the substrate. Subsequently, the substrate was lowered to accumulate the 22nd layer, and then single molecules on the water surface were removed by suction, and the substrate was pulled up. The substrate descending and raising speed is 20 mm
Every minute.

1-2. When the LB film is composed of molecules containing a carboxyl group 2 mM of arachidic acid (CH ₃ (CH ₂ ) ₁₈ COOH)
The (mmol) chloroform solution was spread on a sub-phase aqueous solution (pure water), and the water surface was compressed after waiting for about 10 minutes until the chloroform was sufficiently evaporated. The temperature of the sub-phase aqueous solution was 20 degrees, and the compression pressure was 30 mN / m. After forming the monomolecular film on the water surface in this way, the surface of the glass substrate having a hydrophobic treatment (width 15 mm, height 40 mm,
The LB film was formed by lowering the thickness (0.5 mm). Then, the single molecule on the water surface was removed by suction, and the substrate was pulled up. The hydrophobizing treatment of the substrate was performed by accumulating three layers of arachidic acid spread on the subphase aqueous solution containing cadmium ions on the substrate in advance. The descending speed of the substrate was 10 mm / min.

2. Pattern formation with biotin on LB film First, in order to selectively remove amino groups or carboxyl groups on the surface of the film with an electron beam or the like to form a biotin-binding region of a predetermined shape on the film, 1-1 The obtained LB film cumulative substrate was selectively irradiated with an electron beam using an electron beam exposure apparatus (manufactured by Elionix Co., Ltd.) so that a line-and-space pattern of 5 μm was formed in this case. By this operation, amino group removal regions having a width of 5 μm are formed on the line at intervals of 5 μm on the LB film. The electron dose at this time was 5 × 10 ^-2 Ccm ^-2 .

Next, the substrate that had been selectively irradiated with the electron beam was immersed in a sample bottle containing 10 ml of a bicarbonate buffer (pH 8.5), and then the sample bottle had an amino group-labeled site. Made by Funakoshi Pharmaceutical as biotin N
HS-LC-BIOTIN (Sulfosuccinimidyl 6- (biot
inamido) Hexanoate) 30mg / ml DMF (dim
100 μl of ethylformamide) solution was added. After addition
Immediately, the sample bottle was shaken and reacted for about 1 hour. By this operation, biotin is bound to the remaining portion of the amino group, so that a biotin pattern can be obtained.

On the other hand, regarding the LB film-forming substrate prepared in 1-2, BLAH (Biochin (long arm) hydrazide, product number, manufactured by Funakoshi Chemical Co., Ltd., was used as biotin for carboxyl group labeling.
41-4111-00) 500mg of 20mg / ml DMF solution
And carbodiimide (EDC: (1-ethyl-
3 (3-dimethylaminopropyl) carbodiimide hydrochlorid
e) was dissolved in 150 mM NaCl solution at a concentration of 100 mg / ml, and 150 μl of the solution was added to 150 mM Na
Cl aqueous solution (pH adjusted to 6.0 with HCl) 10 m
Immediately after the accumulation of the LB film, it was immersed in a biotin solution obtained by dissolving in 1 and left at room temperature for 8 hours for reaction. By this operation, biotin is bound to the LB film by the dehydration condensation reaction of the carboxyl group of the LB film and the hydrazide of BLAH with carbodiimide (a substrate having a biotinylated LB film is obtained).

Next, the substrate having the biotinylated LB film was selectively irradiated with an electron beam by using an electron beam exposure apparatus (manufactured by Elionix Co., Ltd.) so that a line-and-space pattern of 5 μm was formed in this case. did. By this selective irradiation of the electron beam, biotin inactive regions having a width of 5 μm are formed on the LB film at intervals of 5 μm, so that a biotin pattern is obtained. The electron dose at this time was 5 × 10 ^-2 Ccm ^-2 .

In forming the biotin pattern, biotin was first bound to the entire surface of the LB film substrate prepared in 1-1, and then biotin was selectively inactivated by an electron beam to form a biotin pattern. Good again
The LB film substrate prepared in 1-2 may be selectively irradiated with an electron beam to selectively remove a carboxyl group, and then biotin may be bound to form a biotin pattern.

3. Binding of colloidal gold avidin to biotin on the substrate Colloidal avidin used in the experiment was Streptavidin Go
ld Conjugate (manufactured by BioCell: product number RL-1121-50,
The colloidal gold particle size is 15 nm). A 2 μl aliquot of this Streptavidin solution was added to the wells with phosphate buffer (pH 7.4).
Diluted to ml. Streptavidin adjusted in this way
Substrate with biotin pattern formed in diluted solution at room temperature 1
Soak for hours. As a result, the colloidal gold bound to Streptavidin will be immobilized along the biotin that has been previously patterned on the substrate via Streptavidin.

4. Confirmation of formed wiring pattern When the substrate was taken out from the buffer, naturally dried and then observed with an optical microscope, it was confirmed that gold colloid wiring was formed at 5 μm intervals.

L of the gold colloid prepared as described above
The state of adhesion to the B film is schematically shown in FIGS. 1 (A) and 1 (B). In FIGS. 1A and 1B, 1 is a substrate, 2 is an LB film, 3 is a binding site between the LB film 2 and a biotin molecule, 4 is a biotin molecule, and 5 is avidin (gold colloid). Avidin), 6 is an avidin molecule, 7
Is a gold colloid, I is a region irradiated with an electron beam, and II is a region not irradiated with an electron beam.

In the above-described first embodiment, an example using docosylamine or arachidic acid as the material for forming the LB film has been shown, but the same molecule is used as long as it can form an LB film having an amino group or a carboxyl group on the surface. Wiring patterns can be formed. Other molecules that can form an LB film having an amino group on the surface include, for example, octadecylamine, 4-tetradecylaniline, 4-octadecylaniline, docosyl 4-aminobenzoate, and the like. LB with
Other molecules that can form a film include, for example, 4-octadecylaminophenylacetic acid, 4-docosylaminophenylacetic acid, 4-octadecylaminobenzoic acid, 4-docosylaminobenzoic acid, 3- (carboxypropyl) perylene, and 9-butyl-10. (Carboxyethyl) anthracene, 4- (4′-octadecyloxyphenylazo) benzoic acid and the like can be mentioned.

Further, in the above-mentioned first embodiment, LB
As the film, one having an amino group or a carboxyl as a functional group on the surface was used. This is because biotin having an amino group labeling site or a carboxyl group labeling site is used as biotin. However, this functional group is not limited to the amino group and the carboxyl group, and can be changed to another group in relation to biotin.

Further, in the above-mentioned first embodiment, the electron beam was used for forming the biotin pattern, but in addition, ultraviolet rays, X
Any substance capable of removing functional groups such as rays, lasers, amino groups, and carboxyl groups or deactivating biotin may be used.

In addition to the use of energy rays, a desired biotin pattern can also be obtained by masking the portions of amino groups and carboxyl groups which are desired to avoid biotin binding.

Further, although gold colloid avidin is used as the wiring material in the above-described first embodiment, it is naturally possible to use other metal colloid avidin such as silver colloid avidin. However, considering the conductivity and the like, it is preferable to use gold colloid avidin or silver colloid avidin.

<Second Embodiment> Next, an example in which a functional group serving as a biotin label is separately provided on the surface of the LB film will be described.

1. Preparation of LB film 1-1. When a molecule having an amino group is separately added to the LB film 2 mM of arachidic acid (CH ₃ (CH ₂ )) ₁₈ COOH)
The chloroform solution of was spread on a subphase aqueous solution (aqueous solution containing cadmium ions), and the water surface was compressed after waiting for about 10 minutes until the chloroform was sufficiently evaporated. Sub-phase aqueous solution temperature is 20 degrees, compression pressure is 30mN
/ M. After forming a monolayer on the water surface in this way,
The glass substrate (width 15 mm, height 40 mm, thickness 0.5 mm) that had been submerged in water in advance was pulled up to form the first-layer LB film. After that, by repeating the descending and raising of the substrate successively, a total of 10 layers of LB are obtained.
A film was formed. The speed of descending and raising the substrate is 20m.
m per minute. Then, octadecylamine was linearly injected by the partial expansion method when the substrate was pulled up to attach the 11th-layer cumulative film. A bubble jet nozzle was used for partial development. It is a mechanism to eject a small amount of the injecting solution by the pressure of bubbles generated by heating the heater in a pulsed manner. Specifically, octadecylamine was injected in a line by using a 2 mM chloroform solution of octadecylamine as an injection solution and ejecting it while moving the nozzle at intervals of 5 mm along the meniscus formed when the substrate was pulled up. . In this way, an LB film was obtained in which molecules having amino groups were provided on the surface at intervals of 5 mm.

1-2. When a molecule having a carboxyl group is separately added to the LB film: A 2 mM chloroform solution of N-docosanoyl-4-nitroaniline is developed on a subphase aqueous solution (pure water),
The water surface was compressed after waiting for about 10 minutes until chloroform was completely evaporated. Sub-phase aqueous solution temperature is 20
The compression pressure was 30 mN / m. After forming the monomolecular film on the water surface in this way, the glass substrate (width: 15 mm, height: 40 mm, thickness: 0.5 mm) whose surface has been subjected to hydrophobic treatment is lowered in the same manner as in the first embodiment to lower the first layer LB film. Formed. Then, the substrate was repeatedly lowered and raised to form a total of 11 layers of LB film. Then, stearic acid was linearly injected by the partial expansion method when the substrate was pulled up in order to attach the 12th-layer cumulative film. A bubble jet nozzle was used for partial development as in the case of octadecylamine described above. The substrate descending / pulling speed was set to 20 mm / min, and the injection was stopped while the accumulation was stopped. Thus, a molecule having a carboxyl group is 5 m
An LB film provided on the surface at intervals of m was obtained.

2. Binding of Biotin to Injection Portion The partially expanded LB membrane substrate prepared in 1-1 above was dipped in a sample bottle of 10 ml of bicarbonate buffer (pH 8.5), and was subjected to the procedure described in Section 2 of the first embodiment. Similarly, immediately after adding the same amount of biotin solution, the sample bottle was shaken and reacted for about 1 hour. On the other hand, the partially expanded LB film substrate prepared in 1-2 was immersed in a sample bottle containing the same amount of biotin solution as in 2 of the first embodiment, and allowed to react at room temperature for 8 hours.

3. Confirmation of the binding of gold colloid avidin and the formed wiring pattern The confirmation of the binding of gold colloid avidin and the formed wiring pattern was performed in the same manner as in the first example. As a result, 5 mm
It was confirmed that an array of colloidal gold was formed at intervals.

In the second embodiment described above, an example of partially injecting octadecylamine into an LB film formed using arachidic acid, and an LB film surface formed using N-docosanoyl-4-nitroaniline An example of partially injecting stearic acid was shown. However, the material for forming the LB film and the material for injecting into the LB film are not limited to the above examples. Any combination may be used as long as a material that does not form a biotin-labeled functional group on the surface of the LB film is used as the LB film-forming material and a material that has a biotin-labeled functional group is used as the injection material. As a specific example corresponding to the second embodiment, another molecule capable of forming an LB film in which an amino group is not formed on the film surface is used instead of arachidic acid, and another molecule having an amino group is used instead of octadecylamine. Combination using molecules, and other molecule capable of forming an LB film that does not form a carboxyl group on the membrane surface instead of N-docosanoyl-4-nitroaniline, and another molecule having a carboxyl group instead of stearic acid It is a combination.

Depending on the design, an LB film is formed by using a material capable of forming a biotin-labeled functional group on the LB film surface as an LB film-forming material, and the LB film does not have a biotin-labeled functional group. The material can also be partially injected to form the biotin pattern.

Further, in the above-mentioned second embodiment, the example in which the molecules are separately injected into the meniscus portion at the time of pulling up the substrate has been described, but the monomolecular film formed on the water surface as described in the above-mentioned document a. It is also possible to inject from the lower phase.

[0042]

As is apparent from the above description, by using the wiring forming method for an LB film of the present invention, a fine metal wiring pattern can be formed on the LB film at room temperature or room temperature and pressure. It is possible to manufacture various LB devices.

[Brief description of drawings]

FIG. 1A and FIG. 1B are diagrams for explaining a wiring forming method of each example, and are diagrams schematically showing a state of a gold colloid wiring pattern formed on an LB film.

[Explanation of symbols]

1: Substrate 2: LB film 3: Binding site between LB film and biotin molecule (site where biotin labeling site and functional group serving as a label are bound) 4: Biotin molecule 5: Gold colloid avidin 6: Avidin molecule 7 : Gold colloid I: Area irradiated with electron beam II: Area not irradiated with electron beam

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumi Kaifu 1-7-12 Toranomon, Minato-ku, Tokyo Oki Electric Industry Co., Ltd. (72) Masaichi Kato 1-7-12 Toranomon, Minato-ku, Tokyo Oki Electric Industry Co., Ltd.

Claims (5)

[Claims] 1. When forming a wiring on an LB film, a functional group serving as a biotin label is provided on the surface of the LB film, and a biotin pattern that binds to the surface of the LB film via the functional group is formed. A method for forming a wiring on an LB film, which comprises obtaining a wiring by binding avidin having a metal colloid to the above using a specific binding between avidin and biotin. 2. The method for forming a wiring on an LB film according to claim 1, wherein the functional group is imparted to the LB film by using an LB film forming material containing the functional group or by applying the functional group to the LB film. A method for forming a wiring on an LB film, which is performed by injecting a molecule containing a functional group 3. The wiring forming method according to claim 1, wherein the biotin pattern is formed by any one of the following methods (1) to (3). .. (1) A method of imparting the functional group to the entire surface of the LB film, selectively irradiating the functional group-provided LB film with an energy beam to form a functional group pattern corresponding to the biotin pattern, and then binding biotin .. (2) A method in which the functional group is applied to the entire surface of the LB film, biotin is bound to the functional group-added LB film, and the biotin-bonded LB film is selectively irradiated with energy rays. (3) A molecule containing a functional group is selectively injected into the LB film to form a functional group pattern corresponding to the biotin pattern,
After that, a method of binding biotin. 4. The L according to any one of claims 1 to 3.
A method for forming a wiring on a B film, wherein the functional group serving as a biotin label is an amino group or a carboxyl group. 5. The method for forming a wiring on an LB film according to claim 3, wherein the energy beam is any one of an electron beam, an X-ray, a laser and an ultraviolet ray.