JP4803570B2 - Solid nano thin film and method for producing nano thin film - Google Patents

Description

  The invention of this application relates to a solid-state nano thin film whose surface is covered with a molecular film.

  More specifically, the invention of this application is formed by evaporating a solvent from a thin film in a liquid state obtained by attaching a surfactant or a diluted solution of a compound having characteristics similar to that of a surfactant to pores. The present invention relates to a solid nano-thin film whose surface is covered with a molecular film.

  A self-supporting membrane is a membrane that can maintain its shape as a membrane at least in a predetermined area even if no other support is present. In order to maintain the shape as a membrane without a support, the membrane needs to be solid. This is because the liquid has a characteristic of “fluidity without a fixed shape”. If not fluid, even a liquid and solid intermediate layer can be a self-supporting membrane. For example, gel or glass can be a self-supporting film, but not a liquid crystal. When a straw is put on soapy water, a foam film is formed at the tip of the straw. However, because it is fluid, it cannot retain the shape of the membrane without the presence of a straw. At first glance, cell membranes and soap bubbles appear to be liquid self-supporting membranes. However, in liposomes prepared from pure biological lipids, membrane disruption and regeneration occur frequently, and in soap bubbles, the slight difference in pressure inside and outside the membrane supports its round shape. Only. On the other hand, an LB film is obtained by copying the monomolecular film at the gas-liquid interface. When the densely packed monomolecular film (solid film) is transferred to the porous substrate, a self-supporting LB film is obtained at least in the area of the pores of the porous substrate.

  Nanometer-thick self-supporting membranes (nanothin films) control various physical, chemical, or mechanical properties, such as separation of gases and ions, adsorption of specific substances, catalysts and sensors. Applications are expected. However, with current technology, it is not easy to produce a thin, stable, and uniform self-supporting nanothin film in a large area.

  If it is a solid thin film having a thickness of micrometer, it is possible to produce a self-supporting thin film with enhanced mechanical properties by sticking it to a porous substrate. However, such a pasting operation is not easy with nano thin films. For example, Whitesides et al. Adsorbed a cation and anion polymer electrolyte on the surface of an alkanethiol self-assembled film, cross-linked two polymer electrolytes with amide, and then removed the self-assembled film. A 5-10 nm self-supporting nano thin film has been obtained (Non-patent Document 1). Similarly, Kunitake et al. Produced an organic / inorganic nanocomposite thin film by a surface sol-gel method on a polymer film produced by spin coating, and removed the previous polymer film, thereby self-supporting a thickness of 10 to 20 nm. Nano-thin films. The latter nano thin film can be transferred to the surface of a porous substrate, but it is extremely difficult to transfer it uniformly to a large area substrate (Non-patent Document 2).

In order to produce a self-supporting nano thin film on pores of several micrometers to several tens of nanometers, it is easier and more reliable to use such a porous material as a film-forming substrate. . For example, the alternating adsorption method of polyelectrolyte can produce nano thin films so as to cover pores at the submicron level, and examples of producing various types of self-supporting nano thin films have already been reported. Yes. Many of them are used for research on the permeation of molecules and ions through nano-thin films, and selective permeation behavior is often observed. However, the alternate adsorption method has the disadvantages that it is difficult to cover pores larger than the molecular length of the polymer, the thickness of the film is not always constant, and a multi-step process is required for the production of nano thin films ( Non-Patent Document 3
).
WTS Huck, et al., Angew. Chem. Int. Ed., Vol. 39, p1058-1061, 2000. M. Hashizume, et al., Langmuir, Vol. 19, p10172-10178, 2003. I. Ichinose, et al., Polym. J., Vol. 31, p1065-1070, 1999.

  Various techniques have been reported for self-supporting nanofilms. However, at present, there is no satisfactory method for reliably producing a nano thin film having a uniform thickness in a wide range from nano to sub-millimeters by an extremely simple operation.

  The invention of this application has been made in view of the above circumstances, and an object thereof is to provide a solid-state nano thin film, that is, a self-supporting nano thin film.

The invention of this application provides the following inventions (1) to (11) as a result of inventor's earnest research to solve the problems of the previous period.
(1) It is formed by evaporating a solvent from a thin film in a liquid state obtained by attaching a dilute solution of a surfactant to pores, and the surface is covered with a molecular film of the surfactant Solid state nano thin film.
(2) It is formed by evaporating the solvent from a thin film in a liquid state obtained by attaching a dilute solution of a compound having characteristics similar to a surfactant to the pores, and the surface is covered with a molecular film of the compound. A solid state nano thin film characterized by comprising:
(3) The nano thin film according to the invention (1) or (2), which is formed so as to cover or close a pore having an inner diameter of 5 nm to 500 μm.
(4) The nano thin film according to any one of the inventions (1) to (3), which is formed from a diluted solution having a concentration of 1.0 × 10 ⁻⁵ M to 1.0 M.
(5) The nano thin film according to any one of the inventions (1) to (4), wherein the film thickness is 1 nm to 1000 nm.
(6) The nanothin film according to any one of the inventions (1) to (5), which has a network structure.
(7) The nano thin film according to any one of the inventions (1) to (6), which is formed from a solution in which organic, inorganic, or metal components are mixed singly or in combination.
(8) The nano thin film according to any one of the inventions (1) to (7), wherein an organic, inorganic, or metal component is coated alone or in a plurality of components.
(9) A nano thin film obtained by removing a part or all of an organic component from the nano thin film according to the invention (7) or (8).
(10) The nano thin film according to any one of the inventions (1) to (9), which is produced using a substrate having pores.
(11) The nano thin film according to any one of the inventions (1) to (9), which is produced using a substance having pores.

  According to the solid state nano thin film characterized in that the first surface is covered with a molecular film of a surfactant, a self-supporting property having a uniform thickness in a wide area from nano to sub millimeters. Nano thin films can be obtained.

  According to the second nano thin film, a self-supporting nano thin film similar to the first nano thin film can be obtained from various compounds having characteristics similar to those of the surfactant.

  According to the third nano thin film, the same effect as the first or second nano thin film can be obtained, and a mechanically more stable self-supporting nano thin film can be obtained.

  According to the fourth nano thin film, the same effects as those of the first to third nano thin films can be obtained, and a self-supporting nano thin film with high film thickness uniformity can be obtained.

  According to the fifth nano thin film, the same effects as those of the first to fourth nano thin films can be obtained, and a more stable and highly uniform self-supporting nano thin film can be reliably obtained.

  According to the sixth nano thin film, it is possible to obtain a self-supporting nano thin film through which gas and small molecules can easily pass.

  According to the seventh nanothin film, a self-supporting nanothin film containing an organic, inorganic, or metal component can be obtained.

  According to the eighth nanothin film, a self-supporting nanothin film having an organic, inorganic, or metal component on the surface can be obtained.

  According to the ninth nanothin film, a structure-controlled nanothin film can be obtained by removing a part or all of the organic component from the seventh or eighth nanothin film.

  According to the tenth nano thin film, a self-supporting nano thin film can be obtained on the surface or inside of the substrate having pores.

  According to the eleventh nano thin film, a self-supporting nano thin film can be obtained on the surface or inside of a substance having pores.

  The invention of this application has the characteristics as described above. The embodiment will be described below.

First, the point of focus of the invention of this application will be described. The basis is a foam film on a macroscopic scale. In a soap bubble, which is one form of a foam film, a surfactant is oriented on the surface of a thin water film with its hydrophobic portion facing outward to suppress the surface tension of water. Further, the surfactant is also contained in a thin water film, and by moving in the water, a new gas-liquid interface generated by deformation of the soap bubbles can be covered. However, soap bubbles quickly become unstable and break when the water film thickness reaches the nanometer level.

Moreover, a flat foam film can be produced by attaching an aqueous solution of a surfactant to a hole of several millimeters formed in the substrate. Such a foam film can be thinned to a thickness of several hundred nanometers. A bubble film thinner than the wavelength of visible light is often called a black soap film (Non-Patent Document 4 or 5). In a sealed container with strictly controlled humidity, a foam film with a thickness of 100 nanometers or less can be prepared by carefully adding a large amount of inorganic salt such as NaCl to suppress the repulsive force between surfactants. Is also possible. For example, Berger et al., In a foam film obtained from an aqueous solution of sodium dodecyl sulfate (SDS) containing 100 mM NaCl, has a film thickness of about 4 nm, and the film of water between the surface surfactant molecular layers. It has been confirmed from ellipsometry and Raman spectrum that the thickness is about 2 nm (Non-patent Document 6).
J. Th. G. Overbeek, J. Phys. Chem., Vol. 64, p1178, 1960. A. Sheludko, Adv. Colloid Interface Sci., Vol. 1, p391-464, 1967. C. Berger, et al., Langmuir, Vol. 19, p1-5, 2003.

  For example, in the foam film that exists in an equilibrium state at a constant humidity as described above, a core layer of an aqueous solution having a constant thickness exists between the surface active agent molecular layers. The foam film can exist stably in a frame of several centimeters as long as the humidity is adjusted. However, when this core layer disappears, the foam film becomes extremely unstable and disappears. As is apparent from this, the excellent stability of the foam film is due to the presence of water in the core layer. This core layer hydrates the surfactant present on the surface and gives the foam film moderate fluidity. Foam membranes that have been studied so far have always had this core water. In fact, “a film having a water layer between molecular layers of a surfactant” is generally used as the definition of the foam film.

  On the other hand, in order to produce a solid-state self-supporting nano-thin film, the inventors of this application produced a variety of liquid-state foam films as described above, and even if the solvent was sufficiently evaporated, As a result, the invention “solid nano thin film” of this application as described above was completed.

  The solid nano thin film in the invention of this application is formed by evaporating the solvent from a liquid thin film obtained by attaching a dilute solution of a surfactant to the pores, and the surface is a molecular film of the surfactant. It refers to a solid-state nano thin film characterized by being covered. A normal foam film has core water, and this part exhibits the property of a fluid liquid, whereas the solid nano-thin film of the invention of this application does not have core water as a liquid. . That is, it can be defined as a solid state foam film having no fluid property.

  In the solid nanothin film in the above definition, a surfactant molecular film is present on the surface. In a solid nano thin film formed from a pure surfactant solution, as one form thereof, the surface molecular film itself may be a solid nano thin film. In the invention of this application, even in such a case, the surface is regarded as a film covered with surfactant molecules. On the other hand, in the solid nano thin film in the invention of this application, an organic, inorganic, or metal component may exist between the molecular films on the surface. Therefore, the solid-state nano thin film in the invention of this application is more generally composed of a molecular film on the surface as one component, and an organic, inorganic, or metal component layer between the almost molecular films as one component. It can be defined as a solid nano-thin film. However, the latter component may not exist.

  Such a solid nano-thin film has not been thought to exist stably in the past. In fact, while a liquid foam film can be produced up to an area close to several square centimeters or 1 square meter, such a large-area film cannot be produced with a solid nano thin film. In addition, a normal foam film is produced by stretching or thinning a liquid having a thickness of several hundreds of micrometers, whereas a solid nano thin film is produced from a thinner liquid film. Due to the difference in area and thickness, the optimum concentration of the surfactant for forming the solid nano thin film is different from the concentration of the normal foam film.

Further, while the foam film in the liquid state has a smooth form consisting of a core layer of an aqueous solution having a uniform thickness and a molecular film of a surfactant, the solid nano-thin film is a porous film or a fibrous film. Can be a friend. This means that the former is a liquid film and is limited to a form that minimizes the surface area, while the latter is a solid film and can stably exist in various forms. Furthermore, while a normal foam film is produced using a solvent having a very large surface tension such as water, a solid nano-thin film can be produced from an organic solvent such as ethanol. In addition, solid nanofilms can be formed from compounds having characteristics similar to surfactants.
That is, it is possible to produce a solid nano thin film using a compound that gathers at the gas-liquid interface and tends to lower the interfacial tension of the liquid.

  Furthermore, since the solid nano thin film is a solid film having no core layer water, it can exist stably even under an ultrahigh vacuum. For this reason, it becomes possible to coat other materials on the surface by a method such as vapor deposition. Moreover, it is possible to fix different substances in the solid nano thin film, and in some cases, even if the organic component is removed by a method such as baking, the form as a film is maintained. In addition, the solid nano thin film is a self-supporting film, and can exist independently, and can be formed on the surface or inside of a substrate or substance having various pores.

  Thus, the solid nano thin film is formed by a method similar to the production of a foam film, but is a solid film having completely different characteristics from a general foam film. In addition, the concept of such a solid nano thin film is provided for the first time by the inventor, and can solve many technical problems that are impossible with a liquid foam film.

  Below, the manufacturing method and the characteristic of the solid nano thin film of the invention of this application will be described in more detail.

  In the method of the invention of this application, a surfactant or a compound having characteristics similar to the surfactant is used. A wide variety of commonly used surfactants can be used as the surfactant. Many surfactants have a hydrophobic group and a hydrophilic group in the molecule. Although not particularly limited, a surfactant having an alkyl chain is preferably used. In addition, surfactants having various hydrophobic groups such as those having an unsaturated bond, those having a benzene ring or a heterocyclic ring, those having a branch or a substituent, and the like can be used. Furthermore, the hydrophobic group does not need to be a single one, and has a variety of molecular structures such as a double-stranded surfactant, a triple-stranded surfactant, and a gemini-type surfactant. Can be used.

  On the other hand, the hydrophilic group is not particularly limited as long as it is a hydrophilic part of a compound that can be generally used as a surfactant. Specific examples include those having a quaternary amine such as trimethylammonium group, those having a tertiary amine such as dimethylamino group, those having a secondary amine such as methylamino group, those having an amino group Those having these amino groups protonated with an acid or the like and those having a pyridinium group are used. The hydrophilic group may be a functional group such as phosphoric acid, sulfonic acid, phenol, carboxylic acid, or a salt thereof. Further, those having a polyether such as polyethylene glycol and those having a structure having a plurality of hydroxyl groups such as sugar may be used. Those having an amide group or ester group such as diethanolamide and those having an amino acid, betaine, amine oxide or the like may be used. Furthermore, a surfactant having a combination of these hydrophilic groups can also be used. Examples of such include, but are not particularly limited to, sodium alphasulfo fatty acid ester, phosphocholine derivatives, and the like. Natural surfactants such as steroid saponins can also be used. The surfactant of the invention of this application must be soluble in a solvent. The surfactant must be present not only in the solution but also at the gas-liquid interface to lower the surface tension of the solution. On the other hand, water is used as a typical solvent, but it may be an organic solvent such as alcohol, acetone or acetonitrile, or a mixed solution of an organic solvent and water. Specifically, an ethanol solution of hexadecyltrimethylammonium bromide can be suitably used for the production of the solid nanofilm of the invention of this application. That is, the surfactant of the invention of this application has an important property of forming a molecular film at the gas-liquid interface so as to lower the surface tension of the solvent, and the solvent is not particularly limited.

The property of the surfactant that forms a molecular film at the gas-liquid interface is an essential part of the invention of this application. If the molecule has such characteristics, it is particularly useful for the production of solid nano thin films. Can be used without limitation. In other words, polymers, organic compounds, biomolecules, and the like having characteristics similar to those of surfactants can be used in the invention of this application as long as they have a tendency to dissolve in solution and form a molecular film at the gas-liquid interface. it can. Such molecules also include organometallic compounds such as metal alkoxides having an alkyl chain. Specific examples include octadecyltrimethoxysilane and octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride. On the other hand, the surfactant used in the invention of this application or a compound having characteristics similar to the surfactant needs to form a solid film in the process of evaporation of the solvent. Accordingly, those having a melting point of not more than room temperature cannot usually be used.

  In the production of the solid nanofilm of the invention of this application, a surfactant or a compound having characteristics similar to the surfactant can be used in combination.

  The solid nanofilm of the invention of this application is formed by attaching a surfactant or a solution of a compound having characteristics similar to a surfactant to the pores and drying the solvent. The pores preferably have an inner diameter in the range of 5 nm to 500 μm, more preferably in the range of 25 nm to 100 μm, and even more preferably in the range of 100 nm to 25 μm. The solid nano-thin film of the invention of this application can be produced only in extremely small pores of 500 μm or less, unlike ordinary foam films. The surface of the approximate pore is not particularly limited, but is preferably moderately hydrophilic. For example, pores made of synthetic polymers, natural polymers, metals or metal oxides are preferably used. There is no particular limitation on the shape of the approximate pores. In addition, even though the pores are holes in a flat substrate, depressions on the surface of the substance, pores on the surface of the substance having pores, or pores on the inside, fine pores of the tube-like substance are used. Even if it is a hole, the hole of the tube-shaped substance with which the one side was closed may be sufficient.

The solid nanofilm of the invention of this application is generally made using a surfactant or a dilute solution of a compound having characteristics similar to a surfactant. This is because, in order to form a nano thin film having a constant thickness, it is necessary to move a surfactant present in the solvent or a compound having characteristics similar to the surfactant during the evaporation of the solvent. Just as a foam film in the centimeter region cannot be made from a concentrated solution, a solid nanofilm in the nano to micrometer region cannot be made from a concentrated solution. The concentration of the dilute solution depends on the size of the pores to be attached, but is preferably in the range of 1.0 × 10 ⁻⁵ M to 1.0 M, 1.0 × 10 ⁻⁴ M to ^1.M. A range of 0 × 10 ⁻¹ M is more preferable, and a range of 1.0 × 10 ⁻³ M to 1.0 × 10 ⁻² M is more preferable. From another viewpoint, this preferable concentration range can be said to be close to the critical micelle concentration (CMC) of the surfactant. The CMC value varies greatly depending on the molecular structure of the surfactant. For example, a double-stranded surfactant has a CMC that is about three orders of magnitude lower than a single-stranded surfactant. For this reason, with a double-stranded surfactant, it is possible to form a solid nanofilm even at a relatively low concentration. In addition, when using a solvent other than water as compared with the case of producing a solid nano-thin film from an aqueous solution, a solution having a concentration one digit higher is required.

  As a method for attaching the diluted solution to the pores, various methods such as a spray method, a coating method, and a spin coating method can be used. In general, a substrate or substance having pores is generally diluted. A method of immersing in is preferably used. Here, a surfactant or a solution of a compound having characteristics similar to the surfactant forms a thin film in a liquid state so as to cover the pores. The thin film here does not necessarily have a certain thickness, and it is sufficient that the minimum necessary aqueous solution for covering the pores adheres. However, in the method of the invention of this application, it is considered that a thin liquid film having a uniform thickness is formed in the process of evaporation of the solvent from such a thin film.

The solid nano thin film of the invention of this application is formed by evaporating the solvent from the liquid thin film attached to the pores by the above method. The evaporation of the solvent can generally be performed by leaving it in the air for several seconds to several tens of minutes. The speed of evaporation can be increased by blowing dry air or leaving it at a temperature higher than room temperature. If necessary, it can be dried under reduced pressure.

The solid nano thin film of the invention of this application is sufficiently stable even under vacuum conditions of about 10 ⁻⁵ Pa. The absence of a liquid solvent in the solid nanofilm under such conditions is apparent from the vapor pressure of ordinary solvents. Further, the absence of a solvent in the solid nanothin film of the invention of this application can be verified separately from an infrared absorption spectrum. That is, it can be said that the solid nano thin film of the invention of this application is a solid nano thin film formed by the complete evaporation of the liquid.

  In the solid nanofilm of the invention of this application, the surface is covered with a molecular film of a compound having characteristics similar to a surfactant or a surfactant. This is because the solid nano thin film of the invention of this application is formed from a liquid thin film covered with the molecular film. The thickness of the solid nano-thin film is generally in the range of 1 nm to 1000 nm, more generally in the range of 2 nm to 200 nm, and more generally in the range of 4 nm to 40 nm. Is. The thickness of the solid nano thin film of the invention of this application is, when formed from an aqueous solution of a pure surfactant, a bimolecular film in which hydrophobic groups are arranged on the outside and hydrophilic groups are arranged on the inside. Often corresponds to. However, the solid nanofilm of the invention of this application can also be prepared from a compound having characteristics similar to a surfactant, and in this case, than the solid nanofilm obtained from an aqueous solution of a pure surfactant. Also, a thick solid nanofilm is often produced. Furthermore, the solid nanofilm of the invention of this application can also be prepared from a solution mixed with an organic, inorganic, or metal component. In this case, since these components are present in the solid nanofilm, the bimolecular A solid nano-thin film that is much thicker than the thickness corresponding to the film is formed. However, the thickness is generally 1000 nm or less. The organic, inorganic, or metal component described above is not particularly limited, but is a dye molecule, a general organic small molecule, a biopolymer such as DNA, a protein, a virus, a synthetic polymer, a sugar, an inorganic salt, Examples include metal complexes, metal clusters, polyoxometalates, inorganic nanoparticles, inorganic clusters, sodium silicates, metal alkoxides, organic silane compounds, organic silane alkoxides, and metal nanoparticles. In addition, the organic, inorganic, or metal component includes a surfactant or a compound having characteristics similar to those of the surfactant.

  Furthermore, the solid nanothin film of the invention of this application is not necessarily a homogeneous thin film, and includes a solid nanothin film having nanopores and a solid nanothin film having a network structure. Since the solid nano thin film of the invention of this application is solid and self-supporting, a nano thin film having such a special structure can be formed.

  The solid nano thin film of the invention of this application is a self-supporting nano thin film, and the surface thereof can be coated with an organic, inorganic, or metal component. As the general coating method, an existing method such as spray coating or spin coating is used without any particular limitation. Furthermore, the solid nano thin film of the invention of this application can exist stably even under vacuum conditions, and can be coated by a technique such as sputtering, CVD, or vacuum deposition.

  The solid nanofilm of the invention of this application can be mixed with a plurality of organic, inorganic, or metal components, and can be coated with a plurality of organic, inorganic, or metal components.

  Such a solid nano-thin film mixed or coated with an organic, inorganic, or metal component can be partially or entirely removed by a method such as washing, baking, or oxygen plasma treatment. In addition, the solid nano thin film of the invention of this application can be easily produced on a substrate having pores or a substance having pores.

Next, the features of the invention of this application will be described more specifically with reference to examples. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably. Therefore, the invention of this application is not limited by the following examples.
<Example 1>
As Example 1, a solid nanofilm was prepared using a cationic and anionic surfactant.

  The solid nano thin film was formed by immersing a substrate having pores in an aqueous solution of a surfactant and pulling it up vertically, followed by drying in air for 30 minutes. During the drying process, water as a solvent evaporates and a nano thin film is spontaneously formed. That is, the foam film in a liquid state is allowed to stand or is dried under reduced pressure to form a solid nano thin film. In Example 1, a copper mesh for electron microscope (Oken Shoji 150-B type, having 150 mesh per inch) was used as the substrate. This copper mesh has a form bar support membrane having pores of about 1 micrometer (FIG. 1). Formation of the solid nano thin film in Example 1 was confirmed by observation with a transmission electron microscope.

  In Example 1, dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB), and hexadecyltrimethylammonium bromide (CTAB) were used as the cationic surfactant, and water was used as the solvent. The concentration of each aqueous solution is 8.2 mM. FIG. 2A shows an electron micrograph of a solid nanofilm of DTAB. The formation of the solid nano thin film can be confirmed from the fact that the pores of the form bar support film are covered with a very thin and uniform thin film.

Since this film is very thin, it is broken or shrunk by an electron beam in high-resolution electron microscope observation. In order to solve this problem, a platinum thin film was coated on the surface of the solid nano thin film. The platinum coating was performed by sputtering with argon plasma at 10 Pa, and performed at 10 mA at a speed of 0.67 ｓ / s. FIGS. 2B and 2C show electron micrographs of a solid nanofilm strengthened against an electron beam by a 30 second platinum coating. This result shows that the solid nano thin film of this example exists stably even under reduced pressure of 1 × 10 ⁻⁵ Pa, which is an observation condition of an electron microscope, and a metal film is formed on the solid nano thin film by sputtering. It shows that nano thin films can be produced.

  For reference, FIG. 3 shows a result of an attempt to produce a solid nano thin film using TTAB and observation with an electron microscope. In the case of TTAB having a long alkyl chain compared to DTAB, it is difficult to form a uniform thin film. Further, FIG. 4 shows the result of producing a solid nano thin film using CTAB and observing it with an electron microscope. In CTAB having a longer alkyl chain than TTAB, a solid nano-thin film is partially formed, but the coverage is not high. In the electron micrograph of FIG. 4, a hole with a size of several hundred nm is seen in the solid nano thin film. Such holes clearly show that the solid nanofilm of this example is a self-supporting nanofilm and is quite different from the liquid foam film. That is, in the bubble film in the liquid state, it is generally disappeared as soon as the hole is opened, but in the solid nano thin film, the structure as a film can be maintained even if the hole is formed.

  FIGS. 5A and 5B show the results of an attempt to create a solid nanothin film using sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfate (STS) and observation with an electron microscope. In SDS or STS, it was difficult to produce a solid nanofilm from the 8.2 mM aqueous solution.

However, the results of FIGS. 3, 4 and 5 do not indicate that a solid nanofilm cannot be formed from these surfactants by the method of the present invention. Formation of a solid nano thin film largely depends on the production conditions. For example, as described in the examples below,
In the case of CTAB, a uniform solid nano thin film can be formed by changing the solvent from water to ethanol.

  The thickness of the solid nano thin film was estimated by cross-sectional observation with a scanning electron microscope. Using a G2000HS type copper mesh (having 2000 mesh per inch) as a substrate, a DTAB solid nano-thin film was prepared. Here, the solid nano thin film is formed so as to directly cover the micropores of the copper mesh (a square having a side of 7.5 micrometers). FIG. 6 shows the results of observing the cross section with a scanning electron microscope after cutting the solid nanothin film of DTAB and performing platinum coating. A part of the observation image is shown enlarged. By carefully observing the cross section of the thin film, it can be seen that the film thickness is 5 nm to 6 nm. Considering that the solid nanothin film of DTAB has a platinum coating of about 2 nm, the thickness of the solid nanothin film is 3 nm to 4 nm, which corresponds to twice the molecular length of the DTAB molecule. That is, the thickness of the solid nano-thin film corresponds to the thickness of the bilayer film in which the hydrophobic groups of the DTAB molecules are arranged on the outside and the hydrophilic groups are arranged on the inside. The structure of such a solid nano thin film is schematically shown in FIG. The molecular length of DTAB is 1.6 nm, and the thickness of the bilayer film of this surfactant can be estimated to be 3 nm to 4 nm.

Observation with a scanning electron microscope is carried out under vacuum conditions at room temperature and about 10 ⁻⁵ Pa, and under these conditions, liquid water cannot exist. That is, the solid nano-thin film of DTAB is covered with a surfactant molecular film, like a general foam film, but there is no liquid water between the molecular films. It has the characteristics of.
<Example 2>
As Example 2, a solid nanofilm was prepared using a nonionic surfactant.

  In Example 2, similar to the method of Example 1, a solid nanothin film was produced on a copper mesh having a form bar support film. As the surfactant, Brij-35 consisting of an alkyl chain and a polyethylene glycol chain was used. Its molecular structure is shown in FIG. As the surfactant solution, an aqueous solution having a concentration of 2.5 mg / ml was used. The observation image by the transmission electron microscope of the solid-state nano thin film of Brij-35 formed so that a form bar support film may be covered is shown in FIG. Unlike the solid nanothin film in Example 1, this surfactant is obtained as a discontinuous and torn film. Such a structure may be formed because the bilayer film of the surfactant contracts in the formation process of the solid nano thin film and changes to a network structure with a size of several tens of nanometers. Even in the network structure, it is considered that the surface of the solid nano thin film is covered with a molecular film of a nonionic surfactant.

The results of this example indicate that a solid nanofilm can be formed using a nonionic surfactant, and further indicate that a solid nanofilm having a network structure can be formed. .
<Example 3>
As Example 3, a solid nanofilm was prepared using a double-stranded surfactant.

In Example 3, a solid nanothin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. As the double-stranded surfactant, didodecyldimethylammonium bromide (DDAB) was used. Further, an aqueous solution having a concentration of 4.4 mM was used as the surfactant solution. FIGS. 9A and 9B show observation images of a solid nanothin film of DDAB formed so as to cover the formval support film with a transmission electron microscope. These observations were made after applying the platinum coating according to the method of Example 1. The solid nanothin film of DDAB is formed so as to cover all the pores of the formval support film, and the smoothness of the solid nanothin film is comparable to the solid nanothin film of DTAB of Example 1. This remarkably uniform solid nanothin film shows no defects such as cracks. FIG. 9C shows a transmission electron microscope observation image of DDAB solid nanofilm before platinum coating. This solid nano thin film is not torn or shrunk by an electron beam at least at the magnification in FIG. 9C. From the degree of deterioration by the focused electron beam in the electron microscope observation, it was confirmed that the solid nanothin film of DDAB is more stable than the solid nanothin film of DTAB. Since the solid nanothin film of DDAB is homogeneous and extremely thin, it is very difficult to confirm its presence. For this reason, we observed at high magnification at least at the part indicated by the arrow in FIG. 9C, and confirmed the presence of the solid nano-thin film.

The result of this example shows that a solid nano-thin film that is uniform and more stable with respect to an electron beam can be formed by using a double-stranded surfactant.
<Example 4>
As Example 4, a solid nanofilm was prepared using a zwitterionic surfactant.

  In Example 4, a solid nano thin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. As the zwitterionic surfactant, dodecylphosphocholine (D-PC) was used. As the surfactant solution, an aqueous solution having a concentration of 8.2 mM was used. FIGS. 10A and 10B show observation images of a solid nano-thin film of D-PC formed so as to cover the form bar support film by a transmission electron microscope. These observations were made after applying the platinum coating according to the method of Example 1. The solid nano thin film of D-PC is easily damaged by an electron beam. However, by applying a sufficient platinum coating, damage due to electron beams could be suppressed. As shown in FIGS. 10A and 10B, the solid nano-thin film of D-PC is formed so as to widely cover the pores of the form bar support film, and its uniformity is high.

The result of this Example shows that a solid nano-thin film having no cracks and no defects can be formed by using a zwitterionic surfactant.
<Example 5>
As Example 5, a solid nano thin film was produced from a non-aqueous solvent.

  In Example 5, a solid nano thin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. However, CTAB was used as the surfactant, and ethanol was used as the solvent. A similar experiment was conducted using an organosilane compound having a long alkyl chain, octadecyltrimethoxysilane (C18-Si). The CTAB solution used was an ethanol solution with a concentration of 8.2 mM, and the C18-Si solution was an ethanol solution with a concentration of 8.2 mM. FIGS. 11A and 11B show images of the CTAB solid nano-thin film formed so as to cover the formval support film, as observed with a transmission electron microscope. These observations were made after applying the platinum coating according to the method of Example 1. The CTAB solid nanothin film produced by the method of Example 5 is uniform and smooth, and is formed so as to cover the pores of the form bar support film. On the other hand, observation images of the C18-Si solid nano thin film with a transmission electron microscope are shown in FIGS. Also in the case of C18-Si, similarly to CTAB, a uniform and smooth solid nano thin film is formed so as to cover the pores of the form bar support membrane. Further, the C18-Si solid nano thin film was sufficiently stable against a focused electron beam, and could be observed with an electron microscope at a high magnification without applying a platinum coating.

The result of Example 5 shows that the solid nanofilm can be formed from a non-aqueous solvent by the method of the invention of this application, and from not only a water-soluble surfactant but also an organosilane compound having an alkyl chain. Also shows that a solid nanofilm can be formed.
<Example 6>
As Example 6, a G2000HS type copper mesh (having 2000 mesh per inch) as a substrate was used to produce a solid nano thin film. The production of the solid nano thin film was carried out in the same manner as in Example 1. However, the solid nanothin film in this example is formed so as to directly cover the micropores of the copper mesh (a square having one side of 7.5 micrometers). CTAB, D-PC, and C18-Si were used for producing the solid nano thin film. The solutions used were an 8.2 mM aqueous solution of CTAB, an 8.2 mM aqueous solution of D-PC, and an 8.2 mM ethanol solution of C18-Si. FIGS. 13A and 13B show observation images of CTAB and D-PC solid nanofilms formed so as to cover the micropores with a transmission electron microscope. These observations were made after applying the platinum coating according to the method of Example 1. As shown in FIG. 13, CTAB and D-PC can sufficiently cover the micropores of the copper mesh. In the G2000HS type copper mesh, since charge-up hardly occurs, it was possible to observe a uniform and smooth solid nano-thin film without applying a platinum coating. On the other hand, the C18-Si solid nano-thin film was smooth and uniform like CTAB and D-PC. An observation image of the solid nano thin film of C18-Si by a transmission electron microscope is shown in FIG. Moreover, the observation image by the scanning electron microscope is shown in FIG.

The result of Example 6 shows that a solid nanofilm can be formed using a metal substrate having micrometer pores by the method of the invention of this application.
<Example 7>
As Example 7, in order to show that different substances can be introduced into the solid nanofilm of the invention of this application, a solid nanofilm containing gold nanoparticles and proteins was prepared.

In Example 7, a CTAB aqueous solution having a concentration of 8.2 mM was prepared, and 0.5 ml of the gold nanoparticle solution was added to 9.5 ml of the aqueous solution. For the gold nanoparticle solution, purchase an aqueous solution containing 2 nm diameter particles at a concentration of 15 × 10 ¹³ particles / ml or an aqueous solution containing 5 nm diameter particles at a concentration of 5 × 10 ¹³ particles / ml from BB International. And used without purification. In Example 7, a solid nano-thin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. FIGS. 15A and 15B show observation images of a CTAB solid nanofilm containing a gold nanoparticle having a diameter of 2 nm and a gold nanoparticle having a diameter of 5 nm, respectively, using a transmission electron microscope. Next to the electron micrograph is a magnified photograph. As is clear from FIGS. 15A and 15B, gold nanoparticles can be introduced into the solid nanofilm of CTAB.

  By the same method, ferritin, which is a water-soluble protein, was introduced into the solid nanofilm. An aqueous solution of 8.2 mM D-PC was prepared, and 5 μl of 100 mg / ml ferritin aqueous solution was added to 8 ml of this aqueous solution. Next, using this solution, a solid nano thin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. FIG. 15C shows an observation image of a solid nanofilm of D-PC containing ferritin by a transmission electron microscope. The granular structure in the figure is iron hydroxide nanoparticles inside ferritin. As is clear from FIG. 15C, protein can be introduced into the solid nanofilm of D-PC.

It was also possible to produce a solid nano thin film containing a low molecular weight or high molecular compound by a similar method. The result of Example 7 shows that the solid nanofilm of the invention of this application can form various self-supporting nanocomposite films by introducing different substances therein.
<Example 8>
As Example 8, in order to show that a variety of self-supporting nano thin films can be formed by introducing different substances into the solid nano thin film of the invention of this application, a solid nano thin film into which sodium silicate was introduced was prepared. went.

In this Example 8, a DTAB aqueous solution having a concentration of 8.2 mM was prepared, and 0.82 ml of 200 mM sodium silicate (Na ₂ SiO ₃ ) aqueous solution and 0.16 ml of 1 mM sodium hydroxide aqueous solution were added to 10 ml of the aqueous solution. And stirred. Using this solution, a solid nano thin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. FIGS. 16A and 16B show images observed with a transmission electron microscope of solid nanothin films of DTAB containing sodium silicate. As is apparent from FIG. 16, the solid nanothin film of DTAB containing sodium silicate is formed so as to cover the pores of the form bar support membrane. This solid nano thin film is somewhat lacking in uniformity compared to the solid nano thin film of DTAB alone. However, it is clear that the nanotrim silicate is uniformly incorporated in the solid nanofilm. The inventors baked at 400 degrees Celsius for 30 minutes in order to convert the solid nanofilm of DTAB containing sodium silicate into a silica film. FIG. 16C shows an observation image of the solid nano thin film after firing with a transmission electron microscope. As shown in FIG. 16C, a porous and self-supporting silica film is formed even after the organic component has been burned away by firing. A similar self-supporting inorganic thin film could be formed using a metal salt or a metal alkoxide compound instead of sodium silicate.

The results of Example 8 show that the solid nanofilm of the invention of this application can be used to form various self-supporting inorganic nanofilms.
<Example 9>
As Example 9, a commercially available porous alumina film (Anodisc 25, manufactured by Whatman, having a film thickness of 60 micrometers and having pores with a diameter of 0.2 micrometers) was used as a substrate to produce a solid nano thin film. Went. The production of the solid nano thin film was carried out in the same manner as in Example 1. However, the solid nano thin film in this example is formed so as to cover the surface of the porous alumina film. For the production of the solid nanothin film, an 8.2 mM aqueous solution of CTAB was used. FIGS. 17A and 17B show images observed with a scanning electron microscope of the porous alumina film and the porous alumina film having a CTAB solid nano-thin film formed on the surface thereof. These observations were made after applying the platinum coating according to the method of Example 1. As shown in FIG. 17, the CTAB solid nano-thin film can sufficiently cover the surface of the porous alumina film. FIG. 17C shows an image observed by a scanning electron microscope of a cross section of a solid nano-thin film produced using an 8.2 mM aqueous solution of DTAB. The wavy form on the surface of the porous alumina film indicates that the surface is uniformly covered with a flexible DTAB solid nano-thin film.

The results of this example show that the solid nanofilm of the invention of this application can cover nanopores having a certain thickness and can take the form of a very thin lid.
<Example 10>
As Example 10, to demonstrate that baking the solid nanofilm of the invention of this application can form a homogeneous silica self-supporting nanofilm, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride was used. A solid nano thin film of (C18-N-Si) was prepared.

  In Example 10, C18-N-Si was added to 10 ml of water to prepare an 8 mM aqueous solution. Using this solution, a solid nano thin film was produced on a copper mesh having a form bar support film in the same manner as in Example 1. 18A and 18B show an observation image of a C18-N-Si solid nanothin film by a transmission electron microscope and an observation image at a high magnification. As is apparent from these photographs, the C18-N-Si solid nano thin film is formed so as to uniformly cover the pores of the form bar support film. This solid nano-thin film is very smooth and no defects are observed. By the same operation, a C18-N-Si solid nano thin film was prepared using a G2000HS type copper mesh. The observation images by the transmission electron microscope are shown in FIGS. 18 (C) and 18 (D). No defects were confirmed even by observation with this transmission electron microscope.

In Example 10, a C18-N-Si solid nanothin film was baked at 400 ° C. for 30 minutes to produce a silica nanothin film. FIG. 19A shows an observation image by a transmission electron microscope of the nano thin film after firing when a copper mesh having a form bar support film is used as the substrate. As is clear from FIG. 19A, a silica self-supporting nano thin film can be obtained by removing the organic component by firing. This silica thin film has a very thin and uniform thickness. Defects are not confirmed. FIGS. 19B and 19C show images observed by a scanning electron microscope of a sample obtained by firing a solid nano-thin film of C18-N—Si produced using a porous alumina film as a substrate. As apparent from FIGS. 19B and 19C, a self-supporting silica thin film can be formed on the porous alumina film by removing the organic component by firing. This silica thin film is formed so as to completely cover the surface of the porous alumina film.
<Example 11>
As Example 11, the solid nano-thin film of the invention of this application can be used as a substrate for coating other substances, and by removing organic components from the coated solid nano-thin film, a new self- In order to show that a supporting nano thin film can be formed, a solid nano thin film of dodecylphosphocholine (D-PC) was prepared.

  In this Example 11, similarly to the method of Example 4, a solid nano thin film was produced on a copper mesh having a form bar support film. 20A shows an observation image of a solid nano thin film of D-PC with a transmission electron microscope, and FIG. 20B shows a transmission electron of a sample obtained by washing the solid nano thin film with water. The observation image by a microscope is shown. As is apparent from these photographs, the solid nanofilm of D-PC can be easily removed by washing with water. On the other hand, (C), (D), and (E) in FIG. 20 show the transmission electron of a sample that was coated with 2 nm, 5 nm, and 10 nm of platinum on a D-PC solid nano thin film, respectively, and then washed with water. The observation image by a microscope is shown. As is clear from FIGS. 20C, 20D, and 20E, a self-supporting platinum nano-thin film can be formed by removing the organic component by washing.

  The invention of this application provides a new self-supporting nano thin film called a solid nano thin film whose surface is covered with a molecular film, that is, a solid nano thin film. Such a nano thin film can be produced with good reproducibility by a simple operation under mild conditions from a surfactant or a dilute solution of a compound having characteristics similar to those of a surfactant.

  If such a solid nano thin film is prepared on a substrate having pores, or the surface or inner wall of a tube, it becomes possible to control the permeability of the substance, separation membrane, reverse osmosis membrane, purification of water or bad odor. It is expected to be used as various functional membranes such as membranes for removing viruses, bacteria, facilitated transport membranes, and pervaporation membranes.

  Furthermore, the solid nano thin film of the invention of this application can be obtained as an organic material, an inorganic material, or a self-supporting nano thin film containing metal or protein, and can be obtained as a catalyst, biosensor, chemical sensor, magnetic sensor, Various film functions such as antistatic film can be designed. In addition, the self-supporting nanothin film obtained by using the solid nanothin film of the invention of the present application as a substrate can be given various film functions, for example, selectively permeable to hydrogen or concentrate oxygen. It can be used as a film for constructing a film for functioning, a film functioning as a photocatalyst, a fuel cell, a device, a display element or the like.

  Furthermore, the method of the invention of this application can form a nano thin film inside or on the surface of a substance having pores, and it is possible to design various characteristics such as gas adsorption characteristics and drug removal methods. It can also be used to close the inner pores of tubular materials in the nano to micrometer range, and can be used to control various properties of these nanomaterials. Furthermore, the method of the invention of this application can also be used as a method of covering a nano-to-micrometer-area depression existing on the surface, and can also be used to control adhesiveness, hydrophilicity or water repellency. Furthermore, the inventive method of this application can be used to improve the chemical, physical, biological and medical properties of existing materials, or to impart new properties, or as part of new nanofabrication techniques. This is an extremely important method.

It is an observation image by the transmission electron microscope of the copper mesh which has a form bar support film in Example 1. FIG. (A) Observation image of a solid nano thin film of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) formed so as to cover the form bar support film of the copper mesh in Example 1, by a transmission electron microscope (B) A transmission electron microscope observation image of a sample in which platinum is deposited on an approximately solid nano thin film, and (C) an observation image by a transmission electron microscope at a low magnification of a sample in which platinum is deposited on an approximately solid nano thin film. . 2 is an observation image of a solid nano-thin film of a cationic surfactant tetradecyltrimethylammonium bromide (TTAB) formed on a form bar support film of a copper mesh in Example 1 using a transmission electron microscope. FIG. 2 is an observation image of a solid nano thin film of a cationic surfactant hexadecyltrimethylammonium bromide (CTAB) formed so as to cover a form bar support film of a copper mesh in Example 1 by a transmission electron microscope. (A) Observation image of a solid nano-thin film of anionic surfactant sodium dodecyl sulfate (SDS) formed on a form bar support film of a copper mesh in Example 1, (B) Form of copper mesh It is an observation image by the transmission electron microscope of the solid-state nano thin film of the anionic surfactant sodium tetradecyl sulfate (STS) formed in the bar support film. Observation of a sample obtained by depositing platinum on a solid nanofilm of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) formed so as to cover the micropores of the copper mesh (G2000HS) in Example 1 using a scanning electron microscope It is an enlarged image of an image and a cross-sectional part. It is a schematic diagram of the molecular filling structure of the solid nano thin film of dodecyltrimethylammonium bromide (DTAB). It is an observation image by the transmission electron microscope of the solid-state nano thin film of the nonionic surfactant (Brij-35) formed so that the form-bar support film | membrane of the copper mesh in Example 2 might be covered. (A) Permeation of a sample in which platinum was vapor-deposited on a solid nanothin film of double-stranded surfactant didodecyldimethylammonium bromide (DDAB) formed so as to cover the form bar support film of copper mesh in Example 3 Observation image with a scanning electron microscope, (B) Observation image of the sample with a transmission electron microscope at a high magnification, and (C) Double-stranded surfactant di-layer formed so as to cover a form bar support film of a copper mesh. It is an observation image by the transmission electron microscope of the sample before vapor-depositing platinum on the solid nano thin film of dodecyldimethylammonium bromide (DDAB). (A) Permeation of a sample in which platinum was vapor-deposited on a solid nano-thin film of zwitterionic surfactant dodecylphosphocholine (D-PC) formed so as to cover the form bar support film of copper mesh in Example 4 An observation image with a scanning electron microscope, (B) an observation image with a transmission electron microscope at a low magnification of the sample. (A) Observation image of a sample obtained by depositing platinum on a solid nano-thin film of hexadecyltrimethylammonium bromide (CTAB) formed so as to cover the form bar support film of the copper mesh in Example 5, using a transmission electron microscope, (B) It is an observation image by the transmission electron microscope in the low magnification of this sample. (A) A transmission electron microscope observation image of a solid nano-thin film of octadecyltrimethoxysilane (C18-Si) formed so as to cover the form bar support film of the copper mesh in Example 5, (B) of the sample It is an observation image with a transmission electron microscope at a low magnification. (A) Observation image of a sample obtained by depositing platinum on a solid nanothin film of hexadecyltrimethylammonium bromide (CTAB) formed so as to cover the micropores of the copper mesh (G2000HS) in Example 6 using a transmission electron microscope (B) It is the observation image by the transmission electron microscope of the sample which vapor-deposited platinum on the solid-state nano thin film of dodecyl phosphocholine (D-PC) formed so that the micropore of copper mesh (G2000HS) might be covered. (A) Scanning electron microscope observation image of a sample obtained by depositing platinum on a solid nanothin film of octadecyltrimethoxysilane (C18-Si) formed so as to cover the copper mesh (G2000HS) in Example 6, ( B) An observation image of the sample by a scanning electron microscope at a low magnification. (A) A sample in which gold nanoparticles (particle size: 2 nm) were dispersed in a solid nano-thin film of hexadecyltrimethylammonium bromide (CTAB) formed so as to cover the form bar support membrane of the copper mesh in Example 7. An observation image by a transmission electron microscope and an enlarged image of a part thereof, (B) a gold nanoparticle in a solid nanofilm of hexadecyltrimethylammonium bromide (CTAB) formed so as to cover a form bar support film of a copper mesh (C) Dodecylphosphocholine (D-PC) formed so as to cover the form bar support film of the copper mesh. ) Is an image observed by a transmission electron microscope of a sample in which ferritin is dispersed in a solid nanothin film. (A) Low-magnification observation of a solid nanofilm of dodecyltrimethylammonium bromide (DTAB) into which sodium silicate formed so as to cover the form bar support membrane of the copper mesh in Example 8 was obtained with a transmission electron microscope (B) Observation image of the solid nano thin film at a high magnification with a transmission electron microscope, (C) Observation image of an inorganic thin film produced by firing the solid nano thin film with a transmission electron microscope. (A) Observation image of porous alumina film in Example 9 by scanning electron microscope, (B) Solid nano thin film of hexadecyltrimethylammonium bromide (CTAB) formed so as to cover the surface of porous alumina film It is an observation image by a scanning electron microscope, (C) An observation image by a scanning electron microscope of a solid nano-thin film of dodecyltrimethylammonium bromide (DTAB) formed so as to cover the surface of a porous alumina film. (A) Transmission electron microscope of solid nano-thin film of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (C18-N-Si) formed so as to cover the form bar support film of copper mesh in Example 10 (B) Observation image of the sample with a transmission electron microscope at a high magnification, (C) Transmission type of C18-N-Si solid nano thin film formed to cover the copper mesh (G2000HS) An image observed with an electron microscope, (D) an image observed with a transmission electron microscope at a high magnification of the sample. (A) Permeation after firing of solid nanofilm of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (C18-N-Si) formed so as to cover the form bar support film of copper mesh in Example 10 Observation image with a scanning electron microscope, (B) Observation image with a scanning electron microscope after firing a solid nano thin film of C18-N-Si formed so as to cover the surface of the porous alumina film, (C) The sample It is an observation image by a scanning electron microscope at a high magnification. (A) Observation image of solid nano-thin film of dodecylphosphocholine (D-PC) formed so as to cover the form bar support film of copper mesh in Example 11, and (B) the solid thin film Observation image of a sample washed with water by a transmission electron microscope, (C) A solid nano-thin film of D-PC formed so as to cover a form bar support film of a copper mesh is coated with a platinum film of about 2 nm, Observation image of the sample washed with a transmission electron microscope, (D) A solid nano-thin film of D-PC formed so as to cover the form-bar support film of copper mesh is coated with a platinum film of about 5 nm, and with water Observation image of the washed sample by a transmission electron microscope, (E) A platinum film of about 10 nm on a solid nano-thin film of D-PC formed so as to cover a form bar support film of a copper mesh Coated, is an observation image by a transmission electron microscope of the sample was washed with water.

Claims (13)

Formed by evaporating the solvent from a thin film in the liquid state obtained by attaching a dilute solution of a surfactant that forms a solid film in the process of evaporation of the solvent to the pores, and the surface is a molecular film of the surfactant Solid-state nano thin film characterized by being covered with The surfactant is dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, Brij-35, didodecyldimethylammonium bromide, dodecylphosphocholine, octadecyltrimethoxysilane, octadecyldimethyl (3-trimethoxysilyl) The nano thin film according to claim 1, which is any one of (propyl) ammonium chloride. The nano thin film according to claim 1 or 2, wherein the nano thin film is formed so as to cover or close a pore having an inner diameter of 5 nm to 500 µm. The nano thin film according to claim 1, wherein the nano thin film is formed from a dilute solution having a concentration of 1.0 × 10 ⁻⁵ M to 1.0 M. The nano thin film according to any one of claims 1 to 4, wherein the film thickness is 1 nm to 1000 nm. The nano thin film according to claim 1, which has a network structure. The nano thin film according to any one of claims 1 to 6, wherein the nano thin film is formed from the dilute solution in which an organic substance, an inorganic substance, or a metal is used alone or in combination with the surfactant. The nano thin film according to any one of claims 1 to 7, wherein an organic material, an inorganic material, or a metal is coated singly or in plural. A method for producing a nano thin film, comprising a step of removing at least part or all of the organic component of the surfactant from the nano thin film according to claim 7 or 8. The nano thin film according to any one of claims 1 to 8, which is prepared on a substrate having pores. The nano thin film according to any one of claims 1 to 8, which is made of a substance having pores. The nano thin film provided with the process of removing the said organic component from the nano thin film in any one of Claim 1 to 6 whose said surfactant is surfactant in which a solid inorganic component remains by removal of an organic component Manufacturing method. The nano-film according to claim 12, wherein the surfactant is octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, and the nano thin film formed by removing the organic component from the nano thin film is a silica thin film. Thin film manufacturing method.