JPS60211831A - Forming method for pattern - Google Patents

Abstract

PURPOSE:To form a sole molecular film or a mono-molecular accumulation film in a pattern shape on a primary surface by modifying the primary surface by gamma rays. CONSTITUTION:When a monomolecular accumulation film 1-2 of arachidic acid is formed by an LB method on the surface of an Si (100) substrate 1-1, placed in vacuum, and scanned on a primary surface by gamma beam with a mask, the hydrophobic base of the arachidic acid of the scanned portion 1-4 is modified to form a pattern. Then, the film 1-5 of the derivatives of arachidic acid and merocyanine is formed by the LB method, and when a supersonic wave is applied, the film of the modified primary portion 1-4 is separated, and the film 1-5 is formed only on the non-modified portion 1-3 according to the pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel pattern forming method. More specifically, the present invention relates to a method for forming a monolayer of a monomolecular film or a monomolecular cumulative film on a substrate.

[Background Art] Conventionally, the use of materials in the semiconductor technology field and the optical technology field has mainly focused on inorganic materials that are relatively easy to handle. One reason for this is that technological progress in the field of organic chemistry has lagged significantly behind that in the field of inorganic materials.

However, recent technological advances in the field of organic chemistry have been remarkable, and it is said that the development of materials for inorganic substances has almost reached its limit. Therefore, there is a demand for the development of functional organic materials as new functional materials that surpass inorganic materials. The advantages of organic materials are that they are cheap, easy to manufacture, and highly functional.On the other hand, organic materials have recently overcome their heat resistance and mechanical strength, which have been inferior until now. Materials are being created one after another. Against this technical background, some of the functional parts (mainly thin film parts) of integrated circuit devices such as logic elements, memory elements, and photoelectric conversion elements, and optical devices such as microlens arrays and optical waveguides have been developed. From the proposal to replace part or all of the conventional inorganic thin film with an organic thin film, we have started to develop molecular electronic devices and bio-related materials in which a single organic molecule has a function such as a logic element or a memory element. Several research institutions have recently announced proposals to create logical devices (e.g., biochips).

When creating the various devices mentioned above using such organic materials, thin films are prepared using the known single molecule accumulation method, namely the Langmuir-Prodgett method (LB method) (New Experimental Chemistry Course 18).
Volume 498-50? page round neck).

In the LB method, for example, in a molecule with a structure that has a parent wood group and a hydrophobic group in the molecule, when the balance between the two (balance of amphiphilicity) is maintained appropriately, one molecule is placed on the water surface with the parent wood group below. This is a method of creating a monomolecular film or a cumulative film of monomolecular layers by utilizing the fact that the film becomes a monomolecular layer.

By the way, in order to provide various functions such as photoconductivity to such a monomolecular film or a monomolecular cumulative film and to create various devices as described above, it is necessary to It is necessary to control the physical placement. However, in the above method, a monomolecular film or a monomolecular cumulative film is formed on the entire surface of the substrate, so two-dimensional patterning of a monomolecular film or a monomolecular cumulative film cannot be achieved by using special photopolymerizability or by applying lithography. There is a drawback that the method cannot be controlled except in the case of a photoresist, that is, unless the molecules constituting a monomolecular film or a monomolecular cumulative film have properties as a photoresist.

[Disclosure of the Invention] An object of the present invention is to provide a novel pattern forming method capable of controlling the two-dimensional arrangement of a monomolecular film or a monomolecular cumulative film.

The purpose of wood-generating j is achieved by the following patterning method.

That is, it is achieved by a pattern forming method characterized in that at least the underlying surface is scanned with a commer line in the absence of atmospheric gas to form a pattern of a monomolecular film or a monomolecular cumulative film, and then ultrasonic vibration is applied. .

In the present invention, the underlying surface is modified by scanning it with gamma rays. Here, the base refers to a member on which a monomolecular film or a monomolecular cumulative film is laminated according to a predetermined pattern. Such members include, for example, glass used in the various semiconductor devices mentioned above, substrates made of inorganic substances such as 5i02, substrates made of organic substances such as polyethylene, polyethylene terephthalate, polyimide, etc.
A1. Substrates made of metals such as Ta, W, In, and Cu or alloys thereof, and various layers (formed according to predetermined patterns) provided on these substrates, for example, A1. Adhesive metal films such as Ta, W, In, Cu, etc., amorphous and polycrystalline films such as silicon and germanium, single crystal semiconductor films, 5n02, ITO
Conductive oxide glass film such as (In703+5n02),
Examples include molecular amorphous semiconductor films such as. Further, such a substrate, a film, or a portion on which a monomolecular resin, a monomolecular cumulative film, or the like is further laminated on a substrate on which a hydrogen film is laminated can also be used.

Particularly preferred are substrates in which amorphous, polycrystalline or single crystal semiconductor films, monomolecular films, monomolecular cumulative films, etc. of glass, polyethylene, or polyimide core silicon are laminated.

Since gamma rays have short wavelengths, pattern formation can be achieved with a density of 100 A to 1000 A by using a mask.
It is Ding Noh. In order to modify the surface with commer rays, 10 JL// cm2~5 x 104
Energy of Joule/0m2 is required.

Surface modification by gamma rays is performed, for example, as follows. In the case of silicon, etc., when scanning with a comma line, one surface changes from hydrophobic to hydrophilic. Furthermore, in the case of polyimide and AI, when scanned with gamma rays, the surface changes from lignophilic to hydrophobic. Alternatively, even if the amphiphilicity is not reversed, the phylophilicity becomes stronger or the hydrophobicity becomes stronger. Patterning is performed by modifying the surface of the F-JM coat as described above, and monomolecules 11 or cumulative monomolecules I1 are formed on the surface of U' according to the formed pattern.

After a monomolecular H layer or a monomolecular cumulative film has been formed on the ground, applying ultrasonic vibration is effective when the force between min and f is large and the layer is close to a solid film, or when Rλ is thin. Particularly effective. That is, by applying ultrasonic vibration, fine patterning of 0.7 lb is possible.

Moreover, formation of a clear pattern becomes ++/ability. Applying ultrasonic vibrations has the advantage that it not only takes less time than providing a separate etching process, but also prevents incomplete etching. Furthermore, the range of material selection is hardly restricted.

The molecules constituting the monomolecular film or the monomolecular cumulative film in the present invention can be widely used as long as they have a hydrophobic part and a hydrophilic part in the molecule.

The most typical component of the hydrophobic portion of such a molecule is an alkyl group, which is a linear or branched group having 5 to 30 carbon atoms, preferably 10 to 25 carbon atoms. I can do it. In addition to the above-mentioned alkyl groups, examples of groups constituting the hydrophobic moiety include olefinic hydrocarbon groups such as vinylene, vinylidene, and acetylene, condensed polycyclic phenyl groups such as phenyl, naphthyl, and anthranyl, biphenyl, and terphenyl. Examples include hydrophobic groups such as a chain polycyclic phenyl group. Each of these, alone or in combination, constitutes the hydrophobic portion of the molecule.

Located at the end or middle of the molecule.

On the other hand, the most typical constituent elements of the wood-philic moiety are, for example, carboxyl groups and their metal salts and amine salts, sulfonic acid groups and their metal salts and amine salts, sulfonamide groups, amide groups, amino groups, imino group, a hydroxyl group, a quaternary amine group, an oximino group, an oximino group, a dianonium group, a guanidine group, a hydrazine group, a phosphoric acid group, a silicic acid group, an aluminate group, and the like. These also constitute the tree-like part of the above molecule either alone or in combination, and are located at the end or middle of one molecule.

Here, having a woody group and a hydrophobic group in one molecule means, for example, that the molecule has both one woody group and one hydrophobic group as described above, or one When it has the above-mentioned lignophilic groups and hydrophobic groups, in the overall structure of the molecule, a certain part is lignophilic in relation to other parts, and - the latter part is inferior in relation to the former part. It means to have a hydrophobic relationship.

The molecules constituting the monomolecular film or monomolecular cumulative film in the present invention are desired to have the following functionality.

■ Parts that carry the desired functionality, i.e., functional parts (for example, π
Molecules that have strong hydrophilic (or strong hydrophobic) properties at the same time (electronic system), or ■ The functional moiety has especially xylemophilicity or hydrophobicity, such as xylemophilic groups, hydrophobic groups, etc. Molecules that have a hydrophilic part and a hydrophobic part in the molecule by introducing them, e.g.
Those in which the functional part is on the side of the hydrophobic part, such as long-chain alkyl-substituted merocyanine dyes with photoconductivity, for example,
Those with a long-chain alkyl carboxylic acid bonded to pyrene, etc., where the functional part is near the center, that is, between the hydrophobic part and the woody part, such as anthracene derivatives, diazo dye derivatives, etc. Specific examples include those that have no functional moiety and are made only of hydrophobic and hydrophilic moieties, such as long-chain saturated fatty acids such as stearic acid and alaxic acid.

Particularly preferred are long-chain alkyl-substituted merocyanine dyes, anthracene derivatives, alaxic acid, and the like.

EXAMPLES In order to explain the present invention more specifically, Examples are shown below.

Example 1 A pattern was formed by the method shown in FIG.

A monomolecular cumulative film 1-2 of araxic acid was formed on the surface of a Si (+00) substrate 1-1 by the LB method to create a ) substrate.

Araxic acid monolayer M1ny has 1 surface pressure of 3°dyn.
One layer was laminated under conditions of e/cm and pulling rate of 5 cm/sin.

Next, the substrate was placed in a vacuum, and the surface of the substrate was scanned with gamma rays at a wavelength of 0.01 at 100 J/c+++2 using a mask. The hydrophobic group portion of araxic acid in scanning portion 1-4 was altered, and a pattern was formed as shown in ff11 diagram (C).

Next, a monomolecular cumulative film of 7-rachidic acid and merocyanine derivatives was formed by the LB method. Araxic acid and merocyanine derivative (I) were mixed at a molar ratio of 1=1, and the mixture was dissolved in chloroform to give a concentration of 1xlO'01/1. A solution was spread on the water surface, and the surface pressure was 40 dy.
Four layers were laminated at a pulling speed of 3 cm/win and a pulling speed of 3 cm/win.

Next, when ultrasonic waves are applied in water for about 5 minutes using an ultrasonic generator with an output of 100 W, the monomolecular cumulative film in the area 1-4 is peeled off, and the monomolecular cumulative film 1-4 is peeled off only in the area 1-3. 5 is the first
It was formed according to the pattern as shown in Figure (d).

As described above, by modifying the base with gamma rays, it is possible to form a monomolecular film or a monomolecular cumulative film in a pattern on the surface of the base.

By using a mask, it is possible to form fine patterns with gamma rays. Therefore, application to Si integrated circuits is also possible. In addition, by changing the intensity of gamma rays, it is possible to change the adhesion force of the monomolecular film or monomolecular cumulative film to the underlying surface, and at the same time, it is possible to By using molecules with different strengths, two-dimensional arrangement of inoculum molecules is also rifable. Moreover, by combining these, it is also possible to manufacture devices with complicated three-dimensional structures.

[Brief explanation of the drawing]

FIG. 1 illustrates an embodiment of the pattern forming method of the present invention. 1-1...Si (100) Substrate patent applicant Kimanon Co., Ltd. Figure 1 procedural amendment (voluntary) July 1980 Commissioner of the C-day Patent Office Mr. 1, Indication of case 1982 Patent application No. 087586
No. 2, Invention name pattern formation method 3, Relationship with the case of the person making the amendment Patent applicant (100) Canon Co., Ltd. 4, Agent address No. 9, Akasaka L-r, Minato-ku, Tokyo? No. 0, No. 16, Kowa Building, 8th Floor, 5, Detailed Description of the Invention, Column 6, Contents of the Amendment, page 11, line 11, general formula (I) in the specification to be amended.

Claims (1)

[Claims] A pattern forming method comprising scanning at least a base surface with gamma rays in the absence of atmospheric gas to form a pattern of a monomolecular film or a monomolecular field M1 film, and then applying ultrasonic vibration.