JP3044168B2 - Method for producing thin film of organic molecule and method for producing thin film pattern - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film of organic molecules and a method for producing a thin film pattern, and more particularly, to a method for producing a high-performance or high-performance thin film by forming a high-quality thin film having a controlled structure. And a thin film pattern manufacturing method.

[0002]

2. Description of the Related Art Conventionally, various thin film manufacturing methods have been used as a technique for forming a thin film composed of organic molecules. An important point when forming an organic thin film is to align molecules in a certain direction in the thin film (molecular orientation control),
Controlling the crystallinity, aligning the crystal orientation in a certain direction (crystal arrangement control), controlling the aggregation form to form a dense and uniform continuous film, patterning to a desired position and form, and the like. . If array control is not performed,
The function anisotropy at the molecular level is offset and the function is reduced at the bulk level. In addition, taking an island-shaped non-uniform film as an example of the aggregation form, such a form causes a large loss of function. For these reasons, quality improvement of thin films by controlling molecular orientation, crystallinity, crystal size, crystal arrangement, aggregation morphology, etc., is aggressively using the ultra-thin film, which is an aggregate of molecules, to transfer the micro physical properties of individual molecules. This is important from the viewpoint of application as a material for optical and electronic devices that reflects this.

One of the general methods for producing a thin film composed of organic molecules is a vacuum deposition method. The vacuum evaporation method is a method in which a thin film is formed by heating an evaporation source in which organic molecules are present, releasing the molecules into a vacuum, and transporting the molecules to a substrate.
The transported molecules adhere to the substrate for a certain period of time. Depending on the growth mode, the attached molecules stay on the substrate and form nuclei while repeating collisions between the molecules. The generated nucleus captures a flying molecule or forms a film with fusion of the nuclei. Since the above-mentioned thin film formation process greatly affects the quality of a molecular thin film such as molecular orientation, crystallinity, crystal arrangement, and aggregation form, film formation conditions such as evaporation rate and substrate temperature during the thin film formation process are adjusted. (For example, “Journal of Crystal Growth” 69, 231
1984). The speed at which the evaporated molecules are supplied to the substrate (molecular beam intensity) is proportional to the evaporation speed, and adjusting this evaporation speed means adjusting the molecular beam intensity applied to the substrate. means.

Taking a one-dimensional linear molecule as an example, when a film is formed with a high molecular beam intensity and / or a high substrate temperature, supersaturation of molecules on the substrate surface is determined by both the molecular beam intensity and the substrate temperature. The degree increases, and the molecular axis is oriented in the lateral direction with respect to the substrate. When a film is formed with a small molecular beam intensity and / or a low substrate temperature, the degree of supersaturation decreases and the molecular axis is normally oriented with respect to the substrate. Thus, molecular orientation can be controlled by molecular beam intensity and substrate temperature. However, by simply controlling the film forming conditions such as molecular beam intensity and substrate temperature, the crystallinity, crystal size, and aggregation morphology that determine the quality of the film other than molecular orientation are determined at the same time. There were restrictions.

In the case of two-dimensional planar condensed polycyclic aromatics such as phthalocyanines and perylene derivatives, the higher the substrate temperature, the higher the crystallinity and the larger the crystal size (for example, “Shin Solid Films” Thin
Solid Films), 215: 213, 1992 or Applied Physics Letters (Appl.Phys.
Lett.) 60, 3223, 1992). However, only by controlling the film forming conditions such as the substrate temperature, the molecular orientation, crystal arrangement, aggregation form, and the like that determine the quality of the film are determined at the same time, and the quality controllability of the film is limited. A typical example is that at high temperatures, the crystal size increases, but the denseness of the film is impaired. As described above, the structure factors such as molecular orientation, crystallinity, crystal arrangement, and aggregation morphology, which determine film quality, and selective adsorptivity are individually determined only by controlling the molecular beam intensity and substrate temperature, which are the film formation conditions. There was a problem that it could not be controlled.

A solution to this problem is to process the surface of the substrate. For example, a dangling bond existing on the surface of a covalent silicon substrate requiring strict lattice matching is terminated with a hydrogen atom, and an attempt is made to arrange and grow an organic crystal thereon (for example, “Applied Physics Letters (Appl. .Phys.Lett.) Vol. 61, 2021
(See p. 1992) or an attempt to cover the surface of an amorphous substrate or the like having no periodicity in the interaction and in which the orientation / arrangement in the in-plane direction cannot be controlled with a polymer rubbing film, and to epitaxially grow thereon. (For example, “Applied Physics Letters (Appl.Phys.Let)
t.) ", 54, 2287, 1989 or" Journal of Chemical Physics (J. Chem. Phy
s.), 88, 6647, 1988). However, such a method of processing the substrate surface may not work effectively due to a difference in material, which has been a problem.

On the other hand, generally, the organic molecules constituting the molecular thin film are connected to adjacent organic molecules by a relatively weak bond represented by van der Waals force. Therefore, after forming a molecular thin film made of organic molecules in a vacuum on the entire surface of the substrate, applying the resist film by a spin coating method or the like, exposing, developing, etching and other ordinary semiconductor processing processes to use the molecular process. When a functional thin film pattern is provided, there has been a problem that the above-described multi-stage semiconductor processing process adversely affects the quality of the film determined by the molecular orientation, crystallinity, crystal arrangement, aggregation form, and the like of the molecular thin film.

[0008]

In the method for producing a thin film of organic molecules as described above, the molecular orientation and crystallinity, which determine the quality of the film, are determined only by controlling the production conditions when producing a thin film composed of organic molecules. In addition, there has been a problem that the structure such as the crystal arrangement and the aggregation form and the patterning processability cannot be individually controlled. The present invention has been made in order to solve such problems, and it is possible to control the quality and patterning processability of a thin film more broadly from the viewpoint of adhesion of organic molecules or growth in an early stage of film formation. An object of the present invention is to obtain a method for producing a thin film of a molecule and a method for producing a thin film pattern.

[0009]

According to the first aspect of the present invention, there is provided a process which involves a change in shape such that the adsorptivity of organic molecules evaporated in vacuum is higher than that of a smooth substrate surface. A first step of performing a treatment on the substrate surface, and a second step of supplying organic molecules in a vacuum to the processed substrate to form a thin film on the substrate surface, the first step Controls the initial stage of the formation of the thin film in the second step.

According to a second aspect of the present invention, as a first step, atoms or molecules evaporated in a vacuum are attached to form particles made of the deposit on the surface of the substrate. In the second step, a thin film is formed by growing organic molecules around the particles by adjusting the supply rate of the organic molecules evaporated in vacuum and / or the substrate temperature.

In the invention according to claim 3 of the present invention, the vapor deposition material constituting the particles in the first step is different from the organic molecules forming the film in the second step.

According to a fourth aspect of the present invention, in the first step, light or light and a magnetic field are applied to give a photochemical reaction to form particles, or light, light and a magnetic field are applied to the formed particles. To give a photochemical reaction.

[0013] In the invention according to claim 5 of the present invention, at least one evaporate supplied to form particles on the substrate surface in the first step is a radical atom or radical molecule.

According to a sixth aspect of the present invention, in a first step, a liquid crystal compound is identified by applying a magnetic field to a thermotropic liquid crystal compound attached to the substrate surface. In a second step, a thin film made of organic molecules is formed on the liquid crystal compound to orient the organic molecules or crystal orientation in a desired direction.

According to a seventh aspect of the present invention, there is provided a first step of performing processing with a change in shape at a desired position on a smooth substrate surface, and a step of forming a substrate surface of organic molecules in an initial step of forming a thin film. The organic molecule supply speed and / or the substrate temperature or both are adjusted so that the difference between the adhesion rate at the step and the adhesion rate of the organic molecule at the selected processing site is increased, and the arrangement and shape of the organic thin film pattern on the substrate are controlled. And two steps.

In the invention according to claim 8 of the present invention, as a first step, a smooth substrate surface is etched to form an uneven portion, or a thin film is formed on a smooth substrate surface and this thin film is formed. Patterning to form an uneven portion, and in the second step, adjusting the organic molecule supply rate or the substrate temperature or both to grow organic molecules in a specific direction from the side surface of the convex portion of the uneven portion. is there.

According to a ninth aspect of the present invention, as a first step, a thin film made of a material different from that of the substrate is formed on a smooth substrate surface, and the thin film is patterned to form a projection. In the second step, the organic molecule supply speed and / or the substrate temperature are adjusted to selectively attach organic molecules to the side walls of the projections, thereby controlling the molecular orientation.

According to a tenth aspect of the present invention,
As a first step, 1 μm is measured by a fine probe used in a scanning tunnel microscope or an atomic force microscope.
In the second step, a micropattern having a size of 1 μm or less is formed at a specific position by adjusting the organic molecule supply rate and / or the substrate temperature.

[0019]

According to the first aspect of the present invention, it is possible to control the film structure or to improve the quality of the film, which has not been achieved conventionally, by utilizing the adsorption characteristics in the initial stage of film growth.

According to the second aspect of the present invention, the crystal size, the size of atoms, the ions or the molecules of which are adjusted in advance on the substrate surface,
The form of aggregation of the film can be controlled, and the film structure can be controlled or the quality of the film can be improved.

According to a third aspect of the present invention, a nucleus formed of thin-film constituent molecules is formed by pre-existing atoms, ions or particles of different molecules from thin-film constituent molecules on the substrate surface. The crystal size, the cohesive form of the film, and the like can be controlled while suppressing the fluctuation, and a high-quality thin film can be obtained under a wider range of conditions.

According to a fourth aspect of the present invention, by pre-existing stable particles of the same molecule whose density has been adjusted on the surface of the substrate, the crystal size can be reduced while suppressing the nucleation of the thin film constituent molecules. Thus, a high-quality thin film can be obtained by controlling the form of aggregation of the film.

According to a fifth aspect of the present invention, the crystal size and the cohesion of the film are suppressed by suppressing the nucleation of the thin film constituent molecules by pre-existing stable particles having a controlled density on the substrate surface. The morphology can be controlled and a high-quality thin film can be obtained.

According to the sixth aspect of the present invention, a high-performance thin film made of an organic compound whose orientation is controlled by the applied magnetic field can be obtained.

According to the seventh aspect of the present invention, the crystal arrangement or molecular orientation or the shape and arrangement of the pattern on the substrate surface can be controlled by the difference in the adhesive force between the selective processing portions.

According to the eighth aspect of the present invention, a thin film pattern having a crystal grown in a desired direction can be directly obtained by the configuration of the uneven portion.

According to the ninth aspect of the present invention, a molecular orientation or crystal arrangement which cannot be obtained by the conventional method can be obtained.

According to the tenth aspect of the present invention, a fine thin film pattern can be arranged at a desired position, and the molecular orientation or the crystal shape in the pattern can be controlled.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS It is generally believed that defects or steps on a substrate act as sources of nuclei, but these are not controlled. In addition, the mode of growth of nuclei formed by collision of molecules developing diffusion motion on the substrate surface and capture of other molecules is controlled to some extent by molecular beam intensity and substrate temperature. Although controllability is poor when conditions during film growth are constant. However, according to the present invention, it is possible to control the film structure or improve the quality of the film by using the adsorption characteristics in the initial stage of film growth. Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to only these examples.

Embodiment 1 In the present invention, the first step of performing a processing with a change in shape on a smooth substrate surface, and
Next, a thin film is manufactured by combining the second step of forming the organic molecular thin film on the processed substrate. The substrate is not particularly limited. The processing in the first step may be any processing as long as it gives a change in the substrate surface shape that can control the formation of the organic thin film in the second step on a smooth substrate surface. The shape change may be, for example, a particle shape (particle 2) as shown in FIG. 1 or a rectangular pattern (concave pattern 3, convex pattern 4) as shown in FIG. The size can be applied in the range from the molecular size level to the order of μm.

The method for producing the organic thin film in the second step includes vacuum deposition, molecular beam deposition, molecular beam epitaxial growth, cluster ion beam, CVD, plasma CVD, plasma deposition, and ion plating. Vacuum processes such as can be used. Among these, vacuum evaporation, molecular beam evaporation, and molecular beam epitaxial growth are preferred from the viewpoint of film quality such as molecular orientation and crystal alignment.

In addition, for example, when particles are applied to the substrate surface in the first step, the first step is preferably performed in the same manner as the second step, from the viewpoint that the second step can be continued with the same vacuum apparatus. Among them, a vacuum evaporation method, a molecular beam evaporation method, a molecular beam epitaxial growth method and the like are suitable.
In the case of vacuum deposition, molecular beam deposition, or molecular beam epitaxial growth, particles are uniformly formed on the substrate on which an organic film is to be formed by controlling the molecular beam intensity, substrate temperature, and deposition time. . Here, the molecular beam intensity is monitored and controlled by a molecular beam monitor or the like. However, the deposition rate may be monitored and controlled by using a method in which the deposition rate is read from, for example, a frequency change due to a film attached on the quartz oscillator.
The molecular beam intensity can be controlled by the degree of vacuum, the crucible shape, and the crucible temperature.

On the other hand, for example, when a rectangular pattern is provided on the substrate surface, an uneven pattern (an uneven portion) is formed at a desired position in the first step. The method for forming the concavo-convex pattern is not particularly limited, and is not limited to a vacuum process, and may be any method. As in the above example, the substrate processed in the first step by giving a pattern of particles or irregularities to the surface is placed in a vacuum chamber, and the organic molecules evaporated in a vacuum in the second step Is irradiated on the substrate to form a thin film. At this time, the conditions for forming the thin film are not particularly limited, but the degree of vacuum is 10 ⁻² P
a or more is preferable. The particles or the concavo-convex pattern formed on the substrate surface act when the organic molecules forming the thin film are evaporated in a vacuum and reach the substrate.

That is, as shown in the schematic diagrams of FIGS. 3 and 4, by adjusting the substrate temperature and the molecular beam intensity which are the film forming conditions in the second step, the organic molecules to be supplied to the substrate surface can be selectively formed. Then, an initial stage of the growth of the organic thin film is controlled by capturing at the shape change site. If the process of adsorbing and adsorbed molecules on the substrate surface is defined as the initial stage of film formation, conventional film growth conditions, such as substrate temperature and molecular beam intensity, alone will result in poor control of the initial growth process. On the other hand, in the present invention, the controllability can be improved by the particles 2 introduced into the surface or the uneven pattern (the convex pattern 3 in FIG. 4).

In the present invention, the organic molecular thin film material applicable is not particularly limited, and can be applied to any organic molecular compound. However, it is preferable that the organic molecular thin film material be an organic molecule which does not decompose by heating in vacuum and can be evaporated. For example, porphyrin, metal porphyrin, phthalocyanine, metal phthalocyanine, merocyanine, perylene, naphthalene, phenanthrene, pentacene, tetracene, chrysene, coronene, pyrene and other fused polycyclic aromatic compounds and derivatives thereof, or coumarin, perinone, thiadiazole pyridine, Hydrazine, oxadiazole, pyrazoline, thiadiazopyridine, pentaphenylcyclopentadiyne, xanthene dyes such as rhodamine dyes and fluorescein dyes, acridine dyes, oxazine dyes,
Compounds such as pyrylium dyes and oxobenzanthracene dyes and derivatives thereof, or tetrathiafulvalene (TTF), tetracyanoquinodimethane (TCN)
Q), a charge transfer complex represented by a TTF-TCNQ complex, diacetylene and derivatives thereof.
Further, the number of repeating units composed of acetylene, pyrrole, thiophene, phenylene, furan, selenophene, benzothiophene, bensofuran, indole, pyridazine, phenylenevinylene, thienylenevinylene, isothianaphthene, aniline, azulene, carbazole, or the like is 3 or more. Or a copolymer composed of two or more kinds of unit molecules.

Embodiment 2 FIG. As shown in FIG. 1, first, in a first step, metals, organic metals, semiconductors, ionic crystals, ceramics, organic molecules, and the like are evaporated in a vacuum to deposit these particles 2 on a clean and smooth substrate 1. . When forming an organic thin film composed of microcrystals by the second step,
In the first step, the substrate temperature is set to be low and / or the organic molecule supply rate is set to be high, or both, so that the particles have a density of, for example, 50 μm ⁻² existing on the substrate surface.
A large amount and evenly scattered so that

In the case where an organic thin film made of a large single crystal is formed in the second step, the temperature of the substrate and / or the supply rate of the organic molecules is set to be low in the first step, or both, and the particles are treated, for example, on the surface of the substrate. Are dispersed in small amounts so that the particle density of the particles becomes, for example, about 1 μm ⁻² . As described above, the density of the particles present on the substrate surface must be adjusted as necessary according to the production conditions such as the substrate type, the degree of vacuum, the substrate temperature, and the organic molecule supply rate.
The particles obtained in the first step are those in which atoms, ions or molecules are aggregated, and there is no particular limitation on the size, but those having a diameter of 1 to 500 nm can be used, and a large amount of particles are deposited on the substrate surface. For example, if the diameter is 1 to 1
Reduce the size to 0 nm.

Here, the vacuum deposition method has been described as an example of the method for producing the particles formed in the first step. However, the method for producing the material for forming the particles can be applied by any method as long as it is a vacuum process. Molecular beam deposition, molecular beam epitaxial growth, cluster ion beam, CVD, plasma CVD, plasma deposition, ion plating, and the like can be used. Any substrate may be used as long as it is smooth, such as sapphire crystal, quartz, glass,
Alkali halide crystal, silicon, germanium, Ga
Substrates such as compound semiconductors such as As, various plastics, and molecular crystals can be applied. Further, a substrate coated with a film or processed may be used.

Next, as shown in FIG. 3, as a second step, organic molecules are evaporated and attached in vacuum to the surface of the substrate 1 on which the particles 2 formed in advance in the first step are present. At this time, it is necessary to set the film forming conditions so that the speed at which the organic molecules forming the film adhere at least on the particles 2 and on the surface of the substrate 1 where no particles are present changes. For example, it is easy to increase the molecular beam intensity, increase the substrate temperature, or perform both. In the case where the temperature of the substrate 1 is increased in the second step,
It is necessary to set the temperature within a temperature range where the particles 2 exist on the surface of the substrate 1 so that the particles 2 formed in the first step do not detach from the surface of the substrate 1. Thus, by forming the organic molecular film in the second step, the crystal size and the aggregate size are controlled by the type and density of the particles 2 formed in the first step. Although it is not always clear how the particles 2 formed on the surface of the substrate 1 in the first step act in the second step, they act as nuclei or organic nuclei when organic molecules grow as a film, The film growth proceeds from the point where the particles 2 are present.

As schematically shown in FIG. 5, in the case of an organic compound having high crystallinity and giving a heterogeneous or discontinuous organic molecular thin film 6 as a result of taking a unique crystal form in a normal vacuum deposition method, the present invention According to the first step, a high-density particle is present on the surface of the substrate 1 in advance in the first step to form a uniform or continuous organic molecular thin film 7 made of extremely fine crystals or amorphous as schematically shown in FIG. Can be given. On the contrary, as schematically shown in FIG. 5, in the case of an organic compound which gives a heterogeneous or discontinuous organic molecular thin film 6 as a result of forming a polycrystalline aggregate having a high crystallinity and a certain size, According to the invention, as shown in FIG. 7, an organic molecular thin film 8 composed of a large single crystal can be provided by pre-existing low density particles on the substrate surface in the first step.

Embodiment 3 FIG. Here, a more specific example regarding the second embodiment will be described. In the first step, the degree of vacuum is 10
^In a vacuum of ^-5 Pa, biphenyldithiol represented by the following chemical structural formula 1 contained in a Knudsen cell (K cell) is heated and evaporated to form biphenyl dithiol on the (001) surface of a KCl substrate which is a kind of alkali halide. Particles composed of dithiol molecules were deposited.

[0042]

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At this time, the substrate temperature was set at -160.degree. The density of the particles was adjusted by the deposition rate and the opening and closing of the shutter, and the target of the supply amount was monitored by a film thickness sensor composed of a quartz oscillator. The deposition rate is 0.1n
m / min (min). In the first step, the display film thickness is 2
nm. Subsequently, as a second step, the same biphenyldithiol powder as in the first step was heated and evaporated in a K cell, and adhered to the substrate surface. At this time, the substrate temperature was 25 ° C., and the deposition rate was 3 nm / min. The final film thickness was 100 nm. When the film did not go through the first step, the film was formed of a heterogeneous crystal having a diameter of, for example, 2 to 10 μm. On the other hand, in the case of passing through the first step, a homogeneous thin film composed of extremely fine crystals having a diameter of 500 nm or less could be obtained.

Embodiment 4 FIG. First, as a first step, metals, organometallics, semiconductors, ionic crystals, ceramics, or organic molecules different from the organic molecules used in the second step are evaporated in a vacuum to form these on a clean and smooth substrate. Particles. In the case of forming an organic thin film composed of microcrystals, the substrate temperature is set low and the organic molecule supply rate is set high so that the particles are dispersed in a large amount and uniformly. In the case of forming an organic thin film made of a large single crystal, the substrate temperature is set high and the organic molecule supply rate is set low to disperse a small amount of the particles. The density and size of the particles are the same as described in Example 2. At this time, it is preferable to control the density of the particles on the substrate surface as necessary according to the production conditions such as the substrate type, the degree of vacuum, the substrate temperature, and the organic molecule supply rate.

Here, the vacuum deposition method has been described as an example of the method for producing the particles formed in the first step, but any method may be used for producing the material for forming the particles. A cluster ion beam method, a CVD method, a plasma CVD method, a plasma deposition method, an ion plating method, or the like can be used. Any substrate can be used as long as it is clean and smooth, such as sapphire crystal, quartz,
Substrates such as glass, alkali halide crystals, compound semiconductors such as silicon, germanium, and GaAs, and various plastics can be used. Further, a substrate coated with a film or processed may be used.

Next, as a second step, organic molecules are evaporated and attached in vacuum to the surface of the substrate on which the particles formed in advance are present. At this time, it is preferable to set the evaporation conditions so that the organic molecules forming the film do not form growth nuclei on the surface of the substrate where the particles do not exist. For example, increasing the deposition rate or controlling the substrate temperature can be mentioned. When the substrate temperature is increased, the temperature is set within a temperature range in which particles exist on the substrate surface. The crystal size and aggregate size of the organic molecular film thus deposited are controlled by the density of the particles. The function of the particles formed on the substrate surface is not always clear, but the organic molecules act as nuclei or nuclei when growing as a film, and the film grows from the point where the particles are present.

According to the present invention, in the case of an organic compound having extremely high crystallinity and giving a heterogeneous or discontinuous thin film as a result of taking a unique crystal morphology in a normal vacuum deposition method, according to the present invention, the substrate surface must be prepared in the first step. The presence of high-density particles makes it possible to provide a homogeneous or continuous film made of extremely fine crystals or amorphous. In the case of an organic compound that gives a heterogeneous or discontinuous thin film as a result of forming a polycrystalline aggregate of a certain size due to crystallinity, according to the present invention, according to the present invention, a low density The presence of the particles makes it possible to provide a thin film composed of a large single crystal.

Embodiment 5 FIG. Here, a more specific example regarding the fourth embodiment will be described. In the first step, the degree of vacuum is 10
Au was evaporated by an EB heating method in a vacuum of ^-5 Pa to attach particles composed of Au atoms to the (001) surface of a KCl substrate, which is a kind of alkali halide. At this time,
The substrate temperature was set at 200 ° C. The density of the particles was controlled by the deposition rate and the opening and closing of the shutter, and the target of the supply amount was monitored by a film thickness sensor composed of a quartz oscillator. The deposition rate was 1 nm / min. The first step was completed when the display film thickness was 2 nm. As a second step, from a different evaporation source from Au in the same growth chamber,
The powder of biphenyldithiol, which is an organic compound, was heated and evaporated in a Knudsen cell to adhere to the substrate surface. At this time, the substrate temperature was 25 ° C., and the deposition rate was 1 nm / m.
in. Without passing through the first step, at a substrate temperature of 25 ° C. and a deposition rate of 1 nm / min, a film could not be formed, or even if it could be formed, a film was formed of heterogeneous crystals. On the other hand, when the first step according to the present invention was performed, a homogeneous thin film made of extremely fine crystals having a diameter of 500 nm or less could be obtained.

Embodiment 6 FIG. First, as a first step, evaporate organometallic molecules or organic molecules in a vacuum,
Irradiate on a smooth substrate surface. At this time, as shown in the schematic diagram of FIG. 8, light or light and a magnetic field are given to the evaporated organometallic molecule or organic molecule 10 to cause a photochemical reaction, and via the bond 11 generated after the photochemical reaction, the surface of the substrate 1 The particles 9 are formed thereon. The light or the light and the magnetic field may be applied to the molecules existing in the vacuum and flying toward the surface of the substrate 1 or to the molecules on the substrate surface. Alternatively, as a first step,
An organic metal molecule or an organic molecule is evaporated in a vacuum to irradiate the molecule on a smooth substrate surface. By this operation, particles are first formed on the substrate surface. That is, as shown in FIG. 9, light or light and a magnetic field are applied to the particles 9 on the substrate surface (FIG. 9A). Next, a photochemical reaction may be caused in the solid phase (FIG. 9B).

As the photochemical reaction, any reaction may be used, but a reaction which generates a bond between molecules is preferable. As the molecular species, any organic metal or organic molecule that causes a photochemical reaction can be applied. By performing the photochemical reaction, it becomes possible to widen the range of conditions for forming particles or to fix the particles. It is necessary to adjust the wavelength of the light to be applied and the irradiation intensity according to the photochemical reaction induced together with the formation conditions such as the organic molecule supply rate and the substrate temperature. The applied magnetic field is
Install a magnet that can generate a strong magnetic field in the vacuum chamber,
It is desirable to perform at or above Tesla. The density and size of the particles are the same as those shown in Example 2. The density of the particles is preferably adjusted as necessary according to the production conditions such as the substrate type, the degree of vacuum, the substrate temperature, and the organic molecule supply rate. Here, the same substrate as in the first embodiment can be used as the substrate.

As a second step, organic molecules are evaporated and attached in vacuum to the surface of the substrate on which the particles formed in the first step are present. At this time, it is preferable to set deposition conditions such as increasing the deposition rate or controlling the substrate temperature so that the organic molecules forming the film do not form growth nuclei on the substrate surface where the particles are not present. . Here, compared to the formation of particles without using a photochemical reaction, the stability is high in the region where the substrate temperature is high, but when the substrate temperature is raised, it is necessary to set the temperature within the temperature region where the particles exist on the substrate surface. is there. The crystal size and the aggregate size of the organic molecular film thus attached can be controlled by the particle density. The function of the particles formed on the substrate surface is not always clear, but the organic molecules act as nuclei or nuclei when growing as a film, and the film grows from the point where the particles are present.

According to the present invention, in the case of an organic compound having extremely high crystallinity and giving a heterogeneous or discontinuous thin film as a result of taking a unique crystal morphology in a normal vacuum deposition method, according to the present invention, the substrate surface must be prepared in the first step. The presence of high-density particles makes it possible to provide a homogeneous or continuous film made of extremely fine crystals or amorphous. In the case of an organic compound that gives a heterogeneous or discontinuous thin film as a result of forming a polycrystalline aggregate of a certain size due to crystallinity, according to the present invention, according to the present invention, a low density The presence of the particles makes it possible to provide a thin film composed of a large single crystal.

Embodiment 7 FIG. Here, a more specific example of the sixth embodiment will be described. In the first step, the degree of vacuum is 10
^In a vacuum of ^-5 Pa, biphenyldithiol represented by the chemical formula 1 and biphenyldiethynyl represented by the following chemical formula 2 are simultaneously evaporated from another evaporation source by a heating method, and the KCl substrate mirror-polished surface ( 001) was irradiated with a KrF excimer laser (wavelength: 248 nm) simultaneously with the evaporation of the molecules.

[0054]

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The light irradiation energy at this time is 5 mj /
cm ² · pulse (pulse), 10 Hz, and light was constantly applied while supplying evaporated molecules to the substrate. The substrate temperature was set at 25 ° C. The particles formed on the substrate were controlled by the organic molecule supply speed and the opening and closing of the shutter, and the standard of the supply amount was monitored at the deposition rate by a film thickness sensor comprising a quartz oscillator. Deposition rate of 0.2 nm / sec
(Seconds), and the first step was completed with a display film thickness of 2 nm.
In a second step, a powder of biphenyldithiol, which is an organic compound, was heated and evaporated in a Knudsen cell from the same evaporation source as described above, and adhered to the substrate surface. At this time, the substrate temperature was 25 ° C., and the deposition rate was 0.1 nm / sec.

In the case where the first step was not performed, no matter how the film forming conditions were set, no film could be formed, or even if the film was formed, the film was formed of heterogeneous crystals. However, through the first step, a homogeneous thin film composed of extremely fine crystals could be obtained. The particles formed in the first step in this example are composed of the molecules shown in Chemical Formula 3 although the two types of molecules undergo a photochemical reaction and the distribution of the number of repeating units n is uncertain. Was.

[0057]

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Embodiment 8 FIG. In the first step, a vapor composed of organic molecules or inorganic molecules is converted into plasma by glow discharge to generate reactive species such as radical molecules in a high energy state. As shown in FIG. 10, the reactive species 12 generated by the reactive species generator 15 are introduced into a vacuum chamber 14 and irradiated on the substrate 1 as a beam. At this time, the type or structure of the generated particles or the density on the substrate surface is controlled by the beam intensity of the reactive species 12, the substrate temperature, the beam irradiation time of the reactive species 12, and a combination thereof. When the reactive active species 12 is irradiated with the beam, the substrate 16 may be simultaneously irradiated with the second organic molecules 13 used in the first step by the cell 16. Further, a reaction on the surface of the substrate 1 may be controlled by applying light or a magnetic field when irradiating the beam composed of the reactive species 12.
In FIG. 10, reference numeral 17 denotes a cell for generating organic molecules forming a thin film in the second step.

One example of a method for producing the reactive species converted into plasma will be described. O ₂ , N ₂ , Cl ₂ ,
F ₂ , CCl ₂ F ₂ , CH ₄ , SiH ₄ , H ₂ Se, C ₂ H ₆ ,
C _n H _n-2, is introduced _{(CH 3) 6 (SiO)} 2 hexamethyldisiloxane, spiropyran, coronene, perylene, phthalocyanine, fullerene, etc. in the cell installed in the thin film manufacturing vacuum apparatus. Next, gas pressure 10-1000P
The radio wave is applied and discharged by the RF coil wound around the outside of the cell in a, and energy is supplied to the plasma by inductive coupling. The radicalized reactive species can be confirmed by monitoring the emission spectrum from the discharged plasma. The reactive species may include ionized species. The reactive species converted into plasma by the discharge are introduced from a cell into a vacuum chamber for growing a thin film through a pinhole or a nozzle. By setting the degree of vacuum in the vacuum chamber to 10 ^-5 to 10 ^-8 Pa, which is higher than the degree of vacuum in the cell, the introduced reactive species are irradiated on the substrate surface in a beam form.

The reactive species irradiated on the substrate surface cause a chemical reaction on the substrate to generate a chemical bond. At the same time, the organic molecules irradiated on the substrate surface are activated to cause a chemical reaction between the organic molecules or between the organic molecules and the reactive species, or with the organic molecule or the reaction product which has previously reacted with the reactive species. The reaction at this time is considered to be a reaction via a radical, and this reaction gives a reaction product in which organic molecules are covalently bonded to each other. At this time, by adjusting the molecular beam intensity, the beam intensity of the reactive species, the substrate temperature, the reaction time, and the like, or a combination thereof, the structure or aggregation form of the particles on the substrate surface or the density on the substrate surface can be controlled.

The reaction product is chemically and physically stable because organic molecules are covalently bonded to each other.
The conditions at the time of forming the organic molecular thin film in the subsequent second step do not cause aggregation or re-evaporation which adversely affects the quality of the film. In the second step, the organic molecules form a film while being acted on by the particles previously formed on the substrate surface in the first step. Further, in the first step, when the substrate surface is irradiated with the second organic molecule simultaneously with the reactive species generated by the discharge, a chemical reaction is induced in the organic molecule, and the second organic molecule or the second organic molecule is induced. And the reactive species can form particles that are constituent materials. At this time, in many cases, the chemical structure of the generated particles is not clear, but a particle having a structure in which molecules are crosslinked irregularly is formed.

Further, in the first step, when light is irradiated on the second organic molecule irradiated on the substrate surface simultaneously with the reactive species on the substrate surface, the second organic molecule in the ground state is excited. In some cases, particles can be formed more efficiently because they can be chemically activated. There is no particular limitation on the light used, but it is desirable to select the wavelength of the light according to the organic molecular species. As long as the organic molecule can transition from the ground state to the excited state, the excited state of the organic molecule can be controlled by the wavelength of the applied light. Thus, the organic molecules activated by the light irradiation react with the reactive species previously generated by the discharge, and can form particles of the second organic molecule or the second organic molecule and the reactive species as constituent materials.

In the second step, a method similar to that shown in Embodiments 1 and 2 is used. As described above,
According to the present invention, in the case of an organic compound that has a very high crystallinity and gives a heterogeneous or discontinuous thin film as a result of taking a unique crystal form in a normal vacuum deposition method, a radical active species is used in the first step according to the present invention. Thereby, particles having a high density are previously present on the substrate surface, and a uniform film or a continuous film made of extremely fine crystals or amorphous can be provided.
According to the present invention, in the case of an organic compound which gives a heterogeneous or discontinuous thin film as a result of forming a polycrystalline aggregate of a certain size due to crystallinity, according to the present invention, the radical active species is used in the first step. A low-density particle is previously present on the substrate surface, and a thin film composed of a large single crystal can be provided.

Embodiment 9 FIG. Here, a more specific embodiment of the eighth embodiment will be described. Oxygen was introduced into the radical molecule generation cell attached to the vacuum chamber to 100 Pa, and oxygen radicals were generated by applying radio waves. The generated oxygen radicals were introduced into the vacuum chamber by adjusting a valve separating the cell and the vacuum chamber. The introduced oxygen radicals were irradiated onto the mirror-polished surface (001) of the KCl single crystal substrate simultaneously with biphenyldiethynyl as the second organic molecule evaporated from the K cell. The degree of vacuum in the vacuum chamber when oxygen radicals were introduced was 10 ⁻⁴ Pa, and in addition, the degree of vacuum when the second organic molecule was evaporated was 10 ⁻³ Pa. At this time, the substrate temperature was 25 ° C. By the first step, particles having a crosslinked structure containing biphenyldiethynyl as a constituent raw material are formed on the substrate surface by 50 μm ^−2.
It was formed with a moderate density. In a subsequent second step, biphenyldithiol molecules were evaporated from the K cell and irradiated onto the substrate surface on which the particles were formed. At this time, the degree of vacuum was 10 ⁻⁴ Pa, and the deposition rate was 5 nm / min.
Met. As a result, a homogeneous film composed of polycrystalline biphenyldithiol was formed.

Embodiment 10 FIG. As a first step, liquid crystal molecules are developed on a substrate. As the liquid crystal phase, nematic,
Any of smectic A, smectic C, chiral nematic, chiral smectic and discotic phases may be used. The liquid crystal molecules used are not particularly limited, and may be a composition such as Merck ZLI1132 (trade name). Further, a polymer having a mesogen group in a polymer skeleton or a polymer having a mesogen group as a side chain and pendant to a polymer main chain may be used. The substrate is not particularly limited, and substrates such as metal, sapphire crystal, quartz, glass, alkali halide crystal, silicon, germanium, compound semiconductors such as GaAs, and various plastics can be applied. Further, a substrate coated with a film or a substrate subjected to a treatment such as rubbing and oblique deposition may be used.

As shown in the schematic diagram of FIG. 11, in a first step, a liquid crystal molecule 19 developed on a substrate is introduced into a vacuum, and the liquid crystal molecule 19 on the substrate 1 is
Orientation in a magnetic field according to The strength of the magnetic field for alignment depends on the liquid crystal molecules 19, but is preferably 1 Tesla or more. Next, as the second step, the aligned liquid crystal molecules 1
Organic molecules 20 forming a thin film on the substrate 1 where
Is evaporated. Note that the magnetic field applied to the liquid crystal may be generated during the evaporation of the organic molecules 20. Through the above first step, the orientation of the organic molecules in the thin film formed in the second step is controlled.

Embodiment 11 FIG. Here, a more specific embodiment of the tenth embodiment will be described. As the first step,
Merck 5CB (trade name), which is a cyanobiphenyl-based liquid crystal represented by the following chemical structural formula 4, was dropped on a quartz substrate.

[0068]

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This substrate was placed in a vacuum chamber open to the atmosphere, and the temperature was set to 30 ° C., which indicates a nematic phase. Thereafter, a magnetic field of 10 T (tesla) was generated by the superconducting magnet, and the magnetic field was applied in the normal direction of the substrate. Thereafter, the inside of the vacuum chamber was evacuated and the substrate was cooled to -100 ° C. Next, as a second step, the magnetic field was shut off when the substrate temperature reached -100 ° C, and the oligophenylenevinylene derivative represented by the following chemical structural formula 5 was evaporated from the K cell and irradiated on the substrate to form a film.

[0070]

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At this time, the degree of vacuum was 10 ⁻⁶ Pa, and the deposition rate was 1 nm / min. A film having a random molecular orientation was formed on a quartz substrate which had not been subjected to the above-described treatment with the liquid crystal. On the other hand, an oligophenylenevinylene derivative film having a long molecular axis oriented in a direction perpendicular to the substrate surface could be formed on the quartz substrate subjected to the surface treatment with the liquid crystal according to the present invention.

Embodiment 12 FIG. As a first step, an uneven portion is formed on a clean and smooth substrate. Any substrate may be used as long as it is clean and smooth, such as sapphire crystal, quartz, glass, alkali halide crystal, silicon,
Substrates such as compound semiconductors such as germanium and GaAs and various plastics can be applied. Further, various organic / inorganic crystal thin films may be formed on the substrate.
As the concavo-convex portion, any material having a controlled shape can be used. For example, a groove of a substrate formed by etching using a resist pattern and a resist can be given. Further, a thin film pattern made of another metal, semiconductor, insulator, or the like formed using a resist pattern may be used. It is preferable to use a conventional semiconductor process for forming the thin film pattern.

Next, as a second step, the organic molecules evaporated in a vacuum are irradiated onto the substrate surface which has been processed with the change in the shape of the irregularities. At this time, by adjusting the intensity of the molecular beam to be irradiated and the substrate temperature, the organic molecules 20 are prevented from adhering to the entire surface of the substrate 1 as shown in the schematic diagram of FIG. The organic molecular thin film pattern 21 is provided on the surface of the substrate by controlling so as to adhere only to the portion subjected to. Here, the molecular beam intensity and the substrate temperature are appropriately adjusted according to the molecular species used.

FIG. 12 will be described in detail. A convex pattern 3 is formed on a substrate 1 at a desired position in a first step. Next, in a second step, the organic molecules 20 are evaporated in a vacuum and supplied to the substrate 1. At this time, the vaporized molecular weight and the substrate temperature are adjusted, and the vaporized molecules are selectively adsorbed on the side portions of the convex pattern 3 without being adsorbed on the entire surface of the substrate 1. By setting these conditions, the convex pattern 3
The organic molecular thin film pattern 21 which is evaporated in the direction of the normal to the side surface of the convex pattern 3 is grown with the side portion of the substrate as a growth starting point. In addition, the convex pattern 3 formed from a resist or the like
After forming the single crystal thin film pattern 21 composed of organic molecules, it is possible to remove the single crystal thin film pattern with a solvent that does not dissolve the single crystal thin film pattern.

Embodiment 13 FIG. Here, a more specific embodiment of the twelfth embodiment will be described. Quartz was used as a substrate. As a first step, a positive resist AZ1 is formed on a substrate.
350 (trade name) was applied by spin coating, exposed and developed to form a resist pattern.
A typical size of the resist pattern is 500 nm thick,
The length was 5 μm and the width was 1 μm. After forming the resist,
Heat treatment was performed at 100 ° C. for 1 hour in a vacuum to remove adsorbed substances on the substrate surface. The degree of vacuum at this time was on the order of 10 ^-8 Pa. Subsequently, as a second step, vanadyl phthalocyanine represented by the following chemical structural formula 6 contained in the K cell was evaporated in a vacuum, and the substrate on which the resist pattern was formed was irradiated as a molecular beam.

[0076]

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The evaporation of vanadyl phthalocyanine includes:
K cell heating temperature is set to 450 ° C, substrate temperature is 300
° C. With the evaporation of vanadyl phthalocyanine, the degree of vacuum in the growth chamber became 10 ^-7 Pa. 100 μm length extending from the side of the resist pattern by the above manufacturing method
A molecular crystal thin film pattern of vanadyl phthalocyanine having a thickness of m, a width of 5 μm, and a thickness of 300 nm was formed. afterwards,
By removing the resist pattern with acetone, only a vanadyl phthalocyanine pattern was obtained.

Embodiment 14 FIG. As a first step, first, an uneven portion is formed on a smooth substrate. Any substrate may be used as long as it is smooth, such as sapphire crystal, quartz,
Substrates such as glass, alkali halide crystals, compound semiconductors such as silicon, germanium, and GaAs, various plastics, and metal plates can be used. Further, various organic / inorganic crystal thin films may be formed on the substrate. At this time, it is possible to control the molecular orientation or crystal arrangement of the thin film pattern. Among them, in order to grow a molecular crystal in a specific direction, it is preferable to use a single crystal substrate, a substrate coated with a polymer rubbing film, a substrate coated with an obliquely deposited film, an LB film coated substrate, or the like. Any irregularities may be used as long as their shapes are controlled. For example, a groove of a substrate formed by etching using a resist pattern and a resist can be given. Further, a thin film pattern made of another metal, semiconductor, insulator, or the like formed using a resist pattern may be used. It is preferable to use a conventional semiconductor process for forming the thin film pattern.

Next, as a second step, the organic molecules evaporated in a vacuum are irradiated onto the substrate surface which has been processed with a change in the shape of the unevenness. At this time, by adjusting the intensity of the molecular beam to be irradiated and the substrate temperature, as shown in the schematic diagram of FIG. 13, organic molecules are prevented from adhering to the entire surface of the substrate, and pattern processing is selectively performed. A thin film pattern is provided on the substrate surface by controlling so that it adheres only to the portion that has been made. Here, the molecular beam intensity and the substrate temperature are adjusted according to the molecular species used. At this time, it is possible to control the molecular orientation or crystal arrangement of the thin film pattern. In order to perform molecular orientation or crystal arrangement, it is preferable to use a single crystal substrate, a substrate coated with a polymer rubbing film, a substrate coated with an obliquely deposited film, an LB film coated substrate, or the like.

FIG. 13 will be described in detail. When the single crystal substrate 22 is used, the convex pattern 3
Is formed so that its side faces are aligned with the crystal axis direction of the single crystal substrate surface. The direction of the side surface of the convex pattern 3 with respect to the crystal axis of the single crystal substrate is selected according to the organic molecules used. Next, in a second step, the organic molecules are evaporated in a vacuum and supplied to the substrate. At this time, the evaporated molecular weight and the substrate temperature are adjusted so that the evaporated molecules are selectively adsorbed on the side portions of the convex pattern 3 without being adsorbed on the entire surface of the substrate. By setting such conditions, a crystal composed of organic molecules evaporated in the normal direction of the side surface of the convex pattern 3 is grown with the side portion of the convex pattern 3 as a growth starting point. According to this embodiment, the organic molecule (single) crystal thin film pattern 23 can be formed at a desired position.

Embodiment 15 FIG. Here, a more specific embodiment of the fourteenth embodiment will be described. A KCl single crystal surface (001) plane was used as a substrate. As a first step, a negative resist ONNR-2 is formed on the KCl single crystal substrate 24.
0 (trade name) was applied by spin coating, exposed and developed to form a resist pattern. A typical size of the resist pattern is 500 nm in thickness and 5 in length.
μm and a width of 1 μm. As shown in FIG. 14, the resist pattern 25 has a length direction corresponding to the crystal axis direction [1] of the KCl substrate.
10] in the horizontal or vertical direction. The resist pattern 26 was formed so as to be located horizontally or vertically in the crystal axis direction [100] of the KCl substrate. After forming the resist, 100 ° C, 1
Heat treatment was performed for a period of time to remove adsorbed substances on the substrate surface.

At this time, the degree of vacuum was on the order of 10 ⁻⁶ Pa. Subsequently, as a second step, 4,4′-biphenyldithiol represented by the chemical structural formula 1 was evaporated in a vacuum, and a molecular beam was irradiated on the substrate on which the resist pattern was formed. The heating temperature was set to 60 ° C. using a K cell for the evaporation of the biphenyldithiol. The substrate temperature was room temperature. With the evaporation of biphenyldithiol, the degree of vacuum in the growth chamber became 10 ^-4 Pa. By the above manufacturing method, a molecular crystal thin film pattern of biphenyldithiol having a length of 100 μm, a width of 5 μm, and a thickness of 500 nm extending from the side of the resist pattern 25 in a direction perpendicular or horizontal to the KCl crystal substrate axis [110] was formed. .
Furthermore, a biphenyldithiol molecular crystal thin film pattern 27 having a length of 100 μm, a width of 5 μm, and a thickness of 500 nm was formed so as to branch from the side of the resist pattern 26 in both directions perpendicular and horizontal to the KCl crystal substrate axis [110].

Embodiment 16 FIG. As a first step, first, a convex pattern made of a material different from the material constituting the substrate surface is formed on a smooth substrate. As a substrate, a smooth, sapphire crystal, quartz, glass, alkali halide crystal,
Substrates such as compound semiconductors such as silicon, germanium, and GaAs, various plastics, and metal plates can be used. Further, various organic / inorganic crystal thin films may be formed on the substrate. It is preferable that the substrate has a small adhesive force of the organic molecules constituting the thin film provided in the second step described later. As the convex pattern, any pattern can be applied as long as its shape is controlled and the organic molecule given in the second step has a higher adhesive force or an adhesive rate than the substrate. For example, a resist pattern or a thin film pattern made of another metal, semiconductor, insulator, or the like can be used. It is preferable to use a conventional semiconductor process for forming the thin film pattern.

In the second step, the substrate on which the resist pattern or other thin film pattern is formed is irradiated with organic molecules evaporated in vacuum. As shown in FIG. 15, by adjusting the organic molecule supply rate of the molecules and / or the substrate temperature, the organic molecules 5 on the substrate 1 are adjusted.
Is controlled so as not to adhere and selectively adhere only to the convex pattern 28. Usually, the organic thin film pattern 29 can be selectively formed on the substrate by reducing the organic molecule supply rate and increasing the substrate temperature so that the organic molecules 5 adhere only to the convex pattern 28. In addition, the influence of the substrate surface on the quality of the film such as crystallinity, crystal arrangement, molecular orientation, and film form is suppressed, and the quality of the thin film can be controlled by the formed convex pattern 28.

For example, as shown in FIG. 15, just by setting the growth conditions such as the organic molecule supply rate or the substrate temperature by the ordinary vapor deposition method, for example, the molecular orientation becomes normal to the substrate and the molecular orientation becomes lateral to the substrate. If this is difficult, this embodiment allows lateral orientation. When two separate convex patterns are formed of a metal or a semiconductor, a microelectronic device can be formed by forming an organic molecular film having controlled film properties between them. Examples of the electronic device include a capacitor, a rectifier, a field-effect transistor, a photoelectric converter, a light-emitting diode, and a nonlinear optical element. Further, by injecting the evaporated molecules from the oblique direction to the normal direction of the substrate surface, the intensity of the incident molecular beam can be increased with respect to the side of the convex pattern, and the organic molecules can be more selectively applied to the side of the convex pattern. A film can be formed. In particular, by stopping rotation in the in-plane direction of the substrate during the second step, an organic thin film can be formed only on one side surface of the convex pattern.

Embodiment 17 FIG. Here, a more specific embodiment of the sixteenth embodiment will be described. When the substrate temperature is room temperature, the biphenyldiethynyl molecule represented by the chemical structural formula 2 can form a film by increasing the supply rate of the organic molecule, and the molecule is oriented in the normal direction of the substrate surface as the molecular orientation at that time. Since a crystal having a major axis oriented is formed, it has been difficult to form a crystal thin film having a major axis oriented in the in-plane direction of the substrate. This embodiment is an example in which a crystal thin film pattern composed of biphenyldiethynyl molecules is oriented such that the major axis direction of the molecules constituting the crystal is in the in-plane direction of the substrate.

First, in the first step, a line-shaped gold pattern was formed on the mirror-polished surface (100) of the silicon wafer substrate by a usual photolithography method. The typical size of the gold pattern was 0.5 mm in length, 0.5 μm in width, and 2 μm in height, and the distance between the pair of gold patterns was 2 μm. This gold-patterned substrate is
^It was introduced into a vacuum of the order of ^-6 Pa and heat-treated at 200 ° C. for 1 hour. The biphenyldiethynyl shown in Chemical Formula 1 is converted to K
The cell was filled and heated to evaporate biphenyldiethynyl, so that the surface of the substrate introduced in vacuum was irradiated as a molecular beam. The substrate temperature was set to 25 ° C., and the substrate was rotated in the in-plane direction during irradiation with the molecular beam. The incident angle of the molecular beam from the normal direction of the substrate surface was 30 °, and the deposition rate was 10 nm / min. During the vapor deposition, the degree of vacuum was on the order of 10 ^-4 Pa. By the above-mentioned vapor deposition process, the biphenyldiethynyl thin film was formed on the gold pattern and between the pair of gold patterns.

This is presumably because at the substrate temperature of 25 ° C. and at the above-mentioned deposition rate, the vapor pressure of biphenyldiethynyl was so high that it did not adhere to the substrate surface but adhered only to gold. It is also presumed that biphenyldiethynyl molecules were adsorbed and crystal-grown not only on the gold pattern but also on the side walls of the gold pattern, and the biphenyldiethynyl thin film covered the substrate surface between the gold patterns. FT-
In the IR spectrum, the C of the benzene ring at 808 cm ^-1 having a transition dipole moment perpendicular to the long axis of the molecule.
The molecular orientation was investigated by comparing the absorption due to H-plane out-of-plane bending vibration and the absorption of the CH stretching vibration of an ethynyl group at 1477 cm ^-1 having a transition dipole moment parallel to the molecular long axis. As a result, the thin film pattern in this example shows that the absorption intensity of the CH stretching vibration of the ethynyl group with respect to the absorption intensity due to the CH out-of-plane bending vibration of the benzene ring was measured by the KBr tablet method in which the molecular direction was random. 0.5
It was 1.93 larger than 83. This indicates that the major axis of the biphenyldiethynyl molecule constituting the thin film pattern is oriented parallel to the substrate.

Embodiment 18 FIG. Here, a more specific embodiment of the sixteenth embodiment will be described. This embodiment provides a simple process that does not require patterning of an organic thin film in a device manufacturing process using the organic thin film. First, a chromium pattern was formed on a non-alkali glass wafer by ordinary vapor deposition and photolithography. The width of the chrome pattern is 5 μm and the thickness is 5
0 nm. An SiO ₂ film was formed thereon by a sputtering method in an Ar / O ₂ gas atmosphere. On the substrate thus formed, in the first step, as in Example 17 described above,
A line-shaped gold pattern was formed by a normal photolithography method. The typical size of the gold pattern was 0.5 mm in length, 0.5 μm in width, and 2 μm in height, and the distance between the pair of gold patterns was 2 μm. This gold-patterned substrate is introduced into a vacuum of the order of 10 ⁻⁶ Pa,
Heat treatment was performed at 0 ° C. for 1 hour.

In the second step, the nickel phthalocyanine represented by the chemical structural formula 7, which was subjected to sublimation purification twice, was charged into a K cell, and heated to evaporate the nickel phthalocyanine, thereby introducing the nickel phthalocyanine into a vacuum. The surface of the substrate was irradiated as a molecular beam.

[0091]

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The substrate temperature was set to 200 ° C., and the substrate was rotated in the in-plane direction while the molecular beam was being irradiated. The molecular beam incident angle from the normal direction of the substrate surface was 30 °. During the deposition, the degree of vacuum was on the order of 10 ^-6 Pa. Substrate temperature is 20
Since the temperature was as high as 0 ° C., the nickel phthalocyanine molecules did not adhere to the substrate surface, and the nickel phthalocyanine thin film was formed only on the gold pattern, between the pair of gold patterns, and on the side surfaces of the gold pattern by the above-described vapor deposition process.

Further, by using a pair of gold patterns 28a as a source / drain electrode and a chromium pattern as a gate electrode 31 as shown in the sectional view of FIG. 16, nickel phthalocyanine which is an organic thin film pattern 29 functions as a semiconductor. The field effect transistor was formed on the substrate 30. The transistor shown in this embodiment is made of SiO ₂
This is an insulated gate transistor in which an electric field is applied from a gate electrode 31 to a semiconductor via a gate insulating film 32 made of a film. When a negative voltage was applied to the gate electrode 31, the channel current flowing between the source and the drain increased. Carrier mobility determined from static electrical characteristics is 10 ^-2 cm ² / V
sec.

Embodiment 19 FIG. As shown in FIG. 17, as a first step, a thin-film micro pattern 35 is formed on the substrate 1 by using a fine probe 33 used for a scanning tunneling microscope (STM), an atomic force microscope (AFM), or the like. To form As the substrate 1, any substrate may be used as long as it is smooth, and substrates such as sapphire crystal, quartz, glass, alkali halide crystals, compound semiconductors such as silicon, germanium, and GaAs, various plastics, and molecular crystals can be used. Also, various organic / inorganic crystal thin films or amphiphilic organic molecule LB films may be formed on the substrate.

The method of forming the micropattern in the first step is not particularly limited. For example, by applying a voltage to the STM probe, atoms or constituent molecules constituting the substrate are adsorbed to the probe and pulled out. Atoms or constituent molecules of the substrate are ablated by applying a voltage to the substrate, an AFM probe is brought close to the surface of the substrate, and atoms or molecules constituting the substrate surface are pulled out by an attractive force acting on the probe and the substrate surface. Use a probe to pull out atoms or molecules adsorbed on the entire surface of the substrate using the same method as described above, or use an STM or AFM probe to move atoms or molecules adsorbed onto the substrate using the same method as described above. And disposing it at a desired position.

When the adsorbed molecule or the amphiphilic organic molecule LB film is used, the molecule is heated by an inert gas or air or light irradiation, or both, so that the substrate is not evaporated in vacuum by heating the substrate during the preparation of the organic thin film. It is preferable to allow the reaction to take place between them and to fix them. In the case of this fixing, a magnetic field may be used. As a second step, the substrate 1 on which the thin film micropattern 35 is formed is irradiated with the organic molecules 2 evaporated in a vacuum. At this time, the organic molecule supply speed and / or the substrate temperature are adjusted so that the organic molecules 2 do not adhere to the surface of the substrate 1 other than the micropattern forming portion. The surface of the substrate 1 is schematically etched by the minute probe 33 to form a minute concave pattern 34.

Embodiment 20 FIG. Here, a more specific embodiment of the nineteenth embodiment will be described. In the first step, first, poly (methyl methacrylate) (PMMA) represented by the chemical structural formula 8 was spin-coated on a silicon substrate (100) coated with a gold vapor-deposited film (thickness: 200 nm).

[0098]

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The spin coating of PMMA was carried out from a 0.5% chlorobenzene solution at 2000 rpm (rotation), 6 rpm.
This was performed in 0 sec (second), and the film thickness was set to 20 nm. After spin coating, the PMMA film was heated at 170 ° C. in a vacuum of 10 ⁻¹ Pa.
Was heated. AFM mounted on a cantilever
The pointed probe was brought into contact with the PMMA film by a piezoelectric actuator. The atomic force between the probe and the PMMA film was measured by detecting reflected laser light from above the cantilever. The repulsive force acting on the probe and the PMMA film is 10 ^-20 nN by feedback control of the piezo actuator.
Held. A probe made of silicon nitride and coated with 50 nm of gold was used as a probe.

Between the gold-coated probe and the gold-deposited film under the PMMA film, a DC voltage of -10 was applied to the probe against the gold-deposited film.
V was applied. The current at this time was 1-10 pA.
In such a state, the probe is set to 0.1 μm on the PMMA surface.
An area of × 0.1 μm was scanned. Thereafter, development was performed with a 1: 1 solution of methyl isobutyl ketone and isopropyl alcohol. After the development, the film was rinsed with methanol and dried by blowing dry air. By the above operation, 0.1μ
A concave portion was formed in an area of m × 0.1 μm.

Next, in the second step, the substrate having the concave pattern was set in a vacuum chamber evacuated to 10 ⁻⁸ Pa. The vanadyl phthalocyanine represented by the chemical formula 6 filled in the K cell was heated and evaporated, and the molecular beam was irradiated on the substrate. The substrate temperature was 200 ° C., and the deposition rate was 0.1 nm / min. The configuration up to this point is shown in FIG.
It becomes as shown in. In the figure, 36 is a PMMA spin coat film. In this example, by providing a micro concave pattern on the substrate surface in advance, it was possible to selectively form vanadyl phthalocyanine in the micro convex pattern portion.

[0102]

As described above, the first aspect of the present invention relates to a processing process involving a change in shape such that the adsorptivity of organic molecules evaporated in vacuum is higher than that of a smooth substrate surface. A thin film composed of organic molecules because it includes a first step of applying organic molecules in a vacuum to the processed substrate, and a second step of forming a thin film on the substrate surface. Has the effect of being able to control the structure of the substrate and to provide a high-quality thin film. As a result, a high-performance or high-performance organic molecular thin film can be provided. From an applied point of view, the key of optical devices, optical waveguides, or electronic devices such as transistors, photoelectric conversion elements, light-emitting diodes, and molecular elements that apply nonlinear optical effects in the future optical information communication, optical computer, and optical information processing fields It also has an effect that it can be used for manufacturing a thin film as a component.

A second aspect of the present invention is that, as a first step, atoms or molecules evaporated in a vacuum are adhered to form particles made of the deposit on the surface of the substrate. By adjusting the supply rate of the organic molecules evaporated in vacuum to the substrate and / or the substrate temperature, the organic molecules are grown around the particles to form a thin film. And the like can be controlled, and the effect that the film structure can be controlled or the quality of the film can be improved can be achieved.

The third aspect of the present invention is that the vapor deposition material constituting the particles in the first step and the organic molecules forming the film in the second step are different from each other. The crystal size, the aggregation form of the film, and the like can be controlled while suppressing the occurrence of a high-quality film under a wider range of conditions.

A fourth aspect of the present invention is that, as the first step, light or light and a magnetic field are applied to form a particle by performing a photochemical reaction, or light or light and a magnetic field are applied to the formed particle. Since the photochemical reaction is performed, the crystal size, the aggregation form of the film, and the like can be controlled while suppressing the formation of nuclei composed of thin film constituent molecules, and an effect that a high-quality film can be obtained under a wider range of conditions is exerted.

A fifth aspect of the present invention is that, since at least one evaporant supplied to form particles on the substrate surface in the first step is a radical atom or a radical molecule, a nucleus composed of thin film constituent molecules is used. The crystal size, the aggregation form of the film, and the like can be controlled while suppressing the formation, and an effect is obtained in that a high-quality film can be obtained under a wider range of conditions.

A sixth aspect of the present invention is that, as a first step, a magnetic field is applied to a compound having a thermotropic liquid crystal property attached on a substrate surface to orient the liquid crystal compound in a specific direction. Then, as a second step, since the orientation or crystal orientation of the organic molecules is oriented in a desired direction by forming a thin film made of organic molecules on the liquid crystal compound, the orientation direction is controlled by the applied magnetic field. This has the effect that a highly functional thin film made of a compound can be obtained.

A seventh step of the present invention is to provide a first step of processing a desired position on a smooth substrate surface with a change in shape, and a method of adhering organic molecules to a substrate surface in an initial stage of thin film formation. The second step of adjusting the organic molecule supply rate and / or the substrate temperature or both so as to increase the difference between the rate of adhesion and the adhesion rate of the organic molecules at the selectively processed portion, and controlling the arrangement and shape of the organic thin film pattern on the substrate Therefore, there is an effect that the crystal arrangement or molecular orientation or the shape and arrangement of the pattern on the substrate surface can be controlled by the difference in the adhesive force between the selective attachment sites.

According to an eighth aspect of the present invention, as a first step, a smooth substrate surface is etched to form an uneven portion, or a thin film is formed on a smooth substrate surface and the thin film is patterned. Forming the irregularities, in the second step, adjusting the organic molecule supply rate or the substrate temperature or both, and growing organic molecules in a specific direction from the side surfaces of the convexities in the irregularities. According to the configuration, there is an effect that a thin film pattern having a crystal grown in a desired direction can be directly provided.

In a ninth aspect of the present invention, as a first step, a thin film made of a material different from that of the substrate is formed on a smooth substrate surface, and the thin film is patterned to form a projection. In the second step, the organic molecule supply rate and / or the substrate temperature are adjusted to selectively attach the organic molecules to the side walls of the projections and control the molecular orientation. Is obtained.

A tenth aspect of the present invention is that, as a first step, a 1 μm-sized probe formed by a fine probe used in a scanning tunneling microscope or an atomic force microscope or the like.
A micropattern of the following size is formed, and as a second step, a fine organic crystal having a size of 1 μm or less is formed at a specific position by adjusting the organic molecule supply rate and / or the substrate temperature, so that a fine thin film is formed. There is an effect that the pattern can be arranged at a desired position and the molecular orientation or crystal shape in the pattern can be controlled.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a substrate that has been subjected to a processing (formation of particulate matter) involving a change in shape in a first step in Examples 1 to 3 of the present invention.

FIG. 2 is a schematic perspective view of a substrate subjected to a processing (rectangular shape) accompanied by a change in shape in a first step in Embodiment 1 of the present invention.

FIG. 3 is a schematic diagram showing a state in which organic molecules adhere to a substrate on which particulate matter is formed in Examples 1 to 3 of the present invention.

FIG. 4 is a schematic diagram showing a state where organic molecules adhere to a substrate that has been subjected to rectangular processing in Example 1 of the present invention.

FIG. 5 is a schematic view showing an organic molecular thin film manufactured by a conventional method.

FIG. 6 is a schematic view showing an organic molecular thin film manufactured in Example 2 of the present invention.

FIG. 7 is a schematic view showing an organic molecular thin film manufactured in Example 2 of the present invention.

FIG. 8 is a schematic diagram showing a state of particle formation when light and / or a magnetic field is applied at the time of supplying an organic metal or organic molecule in the first step in Examples 6 and 7 of the present invention.

FIG. 9 is a schematic diagram showing a particle formation state when light and / or a magnetic field is applied to particles formed at the time of supplying an organometallic or organic molecule in the first step in Examples 6 and 7 of the present invention. .

FIG. 10 is a schematic view of an apparatus used when at least one feed material is a radical in the first step in Examples 8 and 9 of the present invention.

FIG. 11 is a schematic view of an apparatus used when applying a magnetic field to liquid crystal molecules on a substrate surface in a first step in Examples 10 and 11 of the present invention.

FIG. 12 is a schematic diagram showing a state in which organic molecules are supplied in a second step to form an organic molecular thin film pattern on a substrate which has been subjected to rectangular processing in Examples 12 and 13 of the present invention.

FIG. 13 is a schematic diagram showing a state in which organic molecules are supplied on a single crystal substrate in a second step to form an organic molecular thin film pattern crystal in Examples 14 and 15 of the present invention.

FIG. 14 shows a second step of forming an organic molecular thin film pattern on a KCl substrate which has been subjected to rectangular processing by adjusting the direction with respect to the substrate crystal axis direction in the first step in Examples 14 and 15 of the present invention. It is a schematic diagram which shows the state which performs.

FIG. 15 is a view showing an organic molecule thin film pattern formed by controlling the orientation in a second step on a substrate on which a convex pattern having a higher adhesion rate of organic molecules than a substrate is formed in a first step in Examples 16 to 18 of the present invention. FIG. 4 is a schematic view showing a state in which is formed.

FIG. 16 is a schematic sectional view of a transistor element in Examples 16 to 18 of the present invention.

FIG. 17 is a schematic diagram showing a state in which an organic molecular thin film pattern is formed in a second step on a substrate finely processed by a fine probe in a first step in Examples 19 and 20 of the present invention.

FIG. 18 shows a state in which an organic molecular thin film pattern is formed in a second step on a substrate finely processed by a fine probe in a first step after applying PMMA in Examples 19 and 20 of the present invention. FIG.

[Explanation of symbols]

1 substrate, 2 particles, 3 convex pattern, 4 concave pattern, 5 organic molecules, 6 heterogeneous or discontinuous organic molecular thin film, 7 homogeneous or continuous organic molecular thin film, 8 organic molecular thin film composed of large single crystal, 9 particles, 10 organometallic molecules or organic molecules, 11 bonds formed after photochemical reaction, 12 reactive species, 13 organic molecules, 14 vacuum chamber, 15 reactive species generator, 16, 17 cell,
18 magnets, 19 liquid crystal molecules, 20 organic molecules, 2
1 organic thin film pattern, 22 single crystal substrate, 23 organic molecular crystal thin film pattern, 24 KCl single crystal substrate, 25,
26 resist pattern, 27 molecular crystal thin film pattern, 28 convex pattern, 28a Au pattern, 29
Organic thin film pattern, 30 substrates, 31 gate electrode, 3
2 gate insulating film, 33 probe, 34 concave pattern, 3
5 Thin-film micropattern, 36 PMMA spin-coated film.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Hamano, Inventor, Materials and Devices Research Laboratory 8-1-1 Tsukaguchi Honmachi, Amagasaki City (72) Inventor Shigeru Kubota 8-1-1, Tsukaguchi Honcho, Amagasaki City (56) References JP-A-1-291224 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 14/00-14/58 C23C 16/00-16/56 JICST file (JOIS)

Claims (10)

(57) [Claims] A first step of subjecting the surface of the substrate to a processing involving a change in shape such that the adsorptivity of organic molecules evaporated in a vacuum is higher than that of a smooth substrate surface; Supplying organic molecules to the substrate in a vacuum to form a thin film on the surface of the substrate. 2. As a first step, atoms or molecules evaporated in a vacuum are attached to form particles made of the deposit on a substrate surface. As a second step,
2. The method according to claim 1, wherein the thin film is formed by growing organic molecules around the particles by adjusting a supply rate of the organic molecules evaporated in a vacuum and / or a substrate temperature. Method for manufacturing organic molecule thin film. 3. The method according to claim 2, wherein the vapor deposition material constituting the particles in the first step is different from the organic molecules forming the film in the second step. Method. 4. The method according to claim 1, wherein the first step is to give light or light and a magnetic field to give a photochemical reaction to form particles, or to give light or light and a magnetic field to the formed particles to give a photochemical reaction. The method for producing a thin film of organic molecules according to claim 2. 5. The organic molecule according to claim 2, wherein at least one evaporant supplied to form particles on the substrate surface in the first step is a radical atom or a radical molecule. Thin film manufacturing method. 6. As a first step, a liquid crystal compound is oriented in a specific direction by applying a magnetic field to a compound having a thermotropic liquid crystal property attached on a substrate surface. 2. The method according to claim 1, wherein the orientation or crystal orientation of the organic molecules is oriented in a desired direction by forming a thin film of the organic molecules on the liquid crystalline compound. 7. A first step of performing processing with a change in shape at a desired position on a smooth substrate surface, an adhesion rate of organic molecules on a substrate surface in an initial stage of thin film formation, and a selectively processed portion of organic molecules. And adjusting the organic molecule supply rate and / or the substrate temperature or both so that the difference in the adhesion rate becomes large, and including a second step of controlling the arrangement and shape of the organic thin film pattern on the substrate. A method for producing a thin film pattern of an organic molecule. 8. As a first step, an uneven portion is formed by etching a smooth substrate surface, or a thin film is formed on a smooth substrate surface, and the thin film is patterned to form an uneven portion. 8. The method according to claim 7, wherein in the step (c), the organic molecule supply rate and / or the substrate temperature are adjusted so that the organic molecules grow in a specific direction from the side surface of the convex portion of the concave / convex portion. A method for producing a thin film pattern of a molecule. 9. As a first step, a thin film made of a material different from that of the substrate is formed on a smooth substrate surface, and the thin film is patterned to form a convex portion. Adjusting the speed or the substrate temperature or both to selectively attach organic molecules to the convex side walls,
The method for producing a thin film pattern of an organic molecule according to claim 7, wherein the molecular orientation is controlled. 10. As a first step, a micropattern having a size of 1 μm or less is formed by a fine probe used in a scanning tunneling microscope or an atomic force microscope. 8. The method according to claim 7, wherein a fine organic crystal having a size of 1 [mu] m or less is formed at a specific position by adjusting the supply speed and / or the substrate temperature.