JP2010027663A - Apparatus for manufacturing organic thin film for semiconductor device, and method for manufacturing organic thin film for semiconductor device using the device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for manufacturing an organic thin film for a semiconductor device that efficiently obtains the organic thin film of high quality, and a method for manufacturing the organic thin film for the semiconductor device using the apparatus. <P>SOLUTION: The apparatus for manufacturing the organic thin film for the semiconductor device forms the organic thin film by laminating at least one monomolecular layer formed of an organic molecule on a surface of a substrate 30 to be filmed through a chemical bonding. The apparatus includes a substrate stage 311 for holding the substrate 30 to be filmed, a means 33 of introducing a fluid containing the organic molecule into the apparatus, a means 322 of removing by-products produced when the chemical bond is formed from the apparatus, and a means 34 of discharging the fluid from the apparatus. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an apparatus for producing an organic thin film for a semiconductor device that forms an organic thin film suitable for a semiconductor device such as a thin film transistor, a light emitting element, and a solar cell by a chemical reaction, and a method for producing an organic thin film for a semiconductor device using the apparatus.

2. Description of the Related Art In recent years, so-called organic devices using organic thin films as components of electronic devices have attracted attention as new semiconductor devices that replace conventional inorganic semiconductor devices centered on silicon.
This is because a printing process such as ink jet, which is difficult to use for manufacturing an inorganic semiconductor device, and a solution process such as a spin coating method and a casting method can be used for manufacturing an organic device. Therefore, attempts have been made to fabricate elements on a large area substrate or to fabricate elements on a flexible substrate.

  However, while the development of organic devices has progressed, characteristics such as lifetime and carrier mobility have not yet been solved. This is because it is difficult to align the molecules in the organic thin film in the conventional vacuum deposition method or the above-described solution process, and the molecules in the organic thin film are randomly oriented. It is considered to be.

It is known that such a film is in an amorphous state or a polycrystalline state, and its characteristics are inferior to those of a single crystal state film in which organic molecules are regularly aligned.
For example, pentacene, which is known as an organic semiconductor material, exhibits a high mobility of 1.4 cm ² / V · s in a single crystal state (Non-patent Document 1), but an amorphous material produced by a coating method has a thickness of 0.45 cm ^2. / V · s (Non-Patent Document 2), which is lower than the single crystal state.

  In addition, the reason for the short lifetime is that the materials of substrates and electrodes generally used in organic devices are inorganic materials, and the interaction between inorganic materials and organic molecules is generally low. It is thought that this is caused by the migration of organic molecules caused by the heat generated by, causing degradation.

  In order to solve these problems, Patent Document 1 discloses an organic thin film having a multilayer structure of organic molecules in which organic molecule layers (organic molecular layers) are bonded by a covalent bond in a direction perpendicular to the substrate from the surface of the substrate or electrode. Proposed. There, the substrate and electrode surface are covalently bonded to the organic molecular layer, and the organic molecular layers are also covalently bonded to each other. Therefore, the durability is high, and the organic molecules in the organic thin film are oriented in the vertical direction. Therefore, organic devices with high carrier mobility and high light emission have been devised.

In addition, as a method for forming a multilayer structure of organic molecules described in Patent Document 1, a covalent bond is formed between a substrate surface and an organic molecule by a chemical reaction, an organic molecular layer is stacked, and the surface of the organic molecular layer is further formed. And organic molecules are formed into covalent bonds by chemical reaction. That is, organic molecules are sequentially stacked from the substrate by a chemical reaction to form a multilayer structure as described above.
However, Patent Document 1 only describes a general manufacturing method, and does not specifically describe a manufacturing apparatus for industrialization.

  On the other hand, Patent Document 2 devises an apparatus for producing an organic thin film in which organic molecules are sequentially stacked as described above. Patent Document 2 discloses an apparatus for producing an organic thin film in which organic molecules are sequentially laminated by alternately immersing a substrate in a polymer solution charged with a cation and a polymer solution charged with an anion.

JP 2004-103547 A JP 2001-62286 A Applied Physics Letter 90, (2007) 092104 W. L. Kalb et al. Synthetic Metals 153, (2005) 1, T. Minakata et al.

However, in the production methods and production apparatuses such as Patent Document 1 and Patent Document 2, the reaction yield of a chemical reaction when organic molecules are sequentially stacked is low, and it is difficult to produce a high-quality organic thin film.
More specifically, it is generally known that when a chemical reaction proceeds from a raw material system to a production system, a by-product is generated with chemical equilibrium in many cases including the production of an intermediate.
When organic molecules are stacked from a substrate by a chemical reaction as in Patent Document 1, if the concentration of by-products in the container that performs the chemical reaction increases, the reaction that proceeds to the generation system is suppressed due to chemical equilibrium (Lechatrier's principle) ), An organic thin film cannot be obtained with a high reaction yield.

Therefore, it is difficult to obtain a high-quality organic thin film when stacked using a chemical reaction with a low reaction yield.
In addition, when the production apparatus disclosed in Patent Document 2 is used for industrialization, a high-quality organic thin film with a low reaction yield is obtained because the by-product is structured to stay in the reaction tank. Is difficult to get.
In general, as the number of stacked layers increases, the yield of the entire stacked organic thin film is greatly reduced when the stacking yield when stacking one layer is low.

More specifically, when the number of stacks is n (n ≧ 1) and the stacking yield when stacking one layer is x (0 ≦ x <1), the yield of the whole organic thin film can be expressed as y = ^xn. it can.
That is, the overall yield of the laminated organic thin film is the nth power of the laminated yield x when the organic thin film is laminated, and the yield of the whole organic thin film is affected. When the multilayer organic thin film structure is formed by this method, the overall yield of the laminated organic thin film is greatly reduced, and not only the production efficiency is lowered, but also the organic molecular layer cannot be uniformly formed on the surface of the substrate to be deposited. This can cause serious defects in the membrane quality.
Therefore, an object of the present invention is to efficiently obtain a high-quality organic thin film.

  As a result of diligent research, the inventors of the present invention can efficiently produce a high-quality organic thin film for a semiconductor device, and an organic thin film for a semiconductor device using the same. A method was developed to complete the present invention.

However, according to the present invention, a semiconductor having at least an airtight reaction chamber for forming an organic thin film by laminating at least one monomolecular layer composed of organic molecules via a chemical bond on the surface of a substrate to be deposited. An apparatus for producing an organic thin film for a device,
The reaction chamber is
An introduction part for introducing a gaseous or solution-like fluid containing the organic molecules into the reaction chamber;
A substrate stage for holding the deposition substrate;
A discharge part for discharging the fluid from the reaction chamber;
With
Furthermore, a means for removing a by-product generated when a chemical bond is formed is provided at least in the reaction chamber or in a by-product removal chamber connected to the reaction chamber and provided separately from the reaction chamber. An apparatus for producing an organic thin film for a semiconductor device is provided.

More specifically, according to the present invention, the device is
Comprising the gas tight reaction chamber and the byproduct removal chamber,
An apparatus for producing an organic thin film for a semiconductor device is provided in which means for removing the byproduct is provided in the byproduct removal chamber.

Also according to the invention, the device comprises:
Comprising the airtight reaction chamber,
An apparatus for producing an organic thin film for a semiconductor device is provided in which means for removing the by-product is provided in the reaction chamber.

Also according to the invention, the device comprises:
Comprising the gas tight reaction chamber and the byproduct removal chamber,
An apparatus for producing an organic thin film for a semiconductor device is provided in which means for removing the byproduct is provided in the reaction chamber and the byproduct removal chamber.

  Moreover, according to this invention, the preparation apparatus of the said organic thin film for semiconductor devices provided with the sensor for detecting the film-forming state of an organic thin film in the said reaction chamber is provided.

  In addition, according to the present invention, there is provided an apparatus for producing an organic thin film for a semiconductor device, wherein at least the reaction chamber, the fluid introduced into the reaction chamber, or the substrate stage further includes a heating unit.

  Further, according to the present invention, there is provided an apparatus for producing an organic thin film for a semiconductor device, wherein the means for removing the by-product is adsorption of a by-product by a packed molecular sieve or an ion exchange resin.

Furthermore, according to the present invention, any one of the above devices is used,
A first step of forming a first organic molecule layer by forming a chemical bond between a binding site on the surface of the substrate to be deposited and a binding site of a first organic molecule having one or more binding sites; There is provided a method for producing an organic thin film for a semiconductor device, comprising a step of removing a by-product generated in the first step.

  More specifically, according to the present invention, when the first organic molecule has two or more binding sites, the first organic molecule layer is formed after the first step. A chemical bond is formed between an unreacted binding site on the opposite side of the substrate to be deposited, which the organic molecule has, and a binding site of a second organic molecule having one or more binding sites, and further a second There is provided a method for producing an organic thin film for a semiconductor device, wherein the second step of forming the organic molecular layer includes a step of removing a by-product generated in the second step.

  According to the invention, when the second organic molecule has two or more binding sites, the second organic molecule forming the second organic molecule layer after the second step has. A chemical bond is formed between an unreacted binding site on the opposite side of the film-forming substrate side and a binding site of the third organic molecule having two or more binding sites to form a third organic There is provided a method for producing an organic thin film for a semiconductor device, wherein a third step of laminating a molecular layer includes a step of removing a by-product generated in the third step.

  According to the present invention, after the third step, the third organic molecule forming the third organic molecular layer has an unreacted binding site on the side opposite to the film-forming substrate, There is provided a method for producing an organic thin film for a semiconductor device, wherein the step of forming a second organic molecular layer and a third organic molecular layer is repeated at least once.

  Moreover, according to this invention, the manufacturing method of the said organic thin film for semiconductor devices whose by-product produced in the process in any one of said 1st-3rd process is water is provided.

  Further, according to the present invention, the organic thin film for a semiconductor device, wherein the water is removed by an adsorbent selected from the group consisting of silica gel, activated alumina, calcium chloride, magnesium sulfate, molecular sieve, ion exchange resin, and zeolite. Is provided.

  According to the present invention, the binding site on the surface of the film-forming substrate is a hydroxy group, and the binding site of the first organic molecule is any of a carboxy group, a phosphonic acid group, a silyl group, or a chloride thereof. A method for producing the organic thin film for a semiconductor device is provided.

  According to the present invention, when the first to third organic molecules have two or more binding sites, the binding sites of the same organic molecule are the same or different from each other, and a hydroxy group, an amino group, a formyl group Alternatively, a method for producing the organic thin film for a semiconductor device, which is a carboxy group or a protected derivative thereof, is provided.

  Moreover, according to this invention, the manufacturing method of the said organic thin film for semiconductor devices whose by-product produced in the process in any one of said 1st-3rd process is hydrochloric acid is provided.

  Moreover, according to this invention, the manufacturing method of the said organic thin film for semiconductor devices by which the said hydrochloric acid is removed by the neutralizing agent selected from an alkaline solution, a granular or powdery alkali, or an ion exchange resin is provided.

  Further, according to the present invention, there is provided the organic thin film for a semiconductor device, wherein a binding site on the surface of the substrate to be deposited is a hydroxy group, and a binding site of the first organic molecule is a silyl chloride group or a carboxylic acid chloride group. A method of making is provided.

According to the manufacturing apparatus of the organic thin film for semiconductor devices of the present invention and the manufacturing method of the organic thin film for semiconductor devices using the same,
By-products generated during any one of the first to third steps can be removed in the gastight reaction chamber and / or the by-product removal chamber, so that a single molecule of an organic molecule through a chemical bond A stacking reaction of organic molecular layers (hereinafter also referred to as simply “stacking reaction”) in which at least one layer is stacked proceeds to the production system, and the reaction yield of the stacking reaction (hereinafter referred to as “stacking yield”) is improved, resulting in high quality. An organic thin film for a semiconductor device can be efficiently produced.

Furthermore, by performing the second step, a two-layer organic thin film can be produced with high quality, and a high quality organic thin film for a semiconductor device having two or more functions can be produced.
Moreover, the organic thin film for semiconductor devices which has a high-quality three-layer film structure can be produced by performing a 3rd process.

Furthermore, by repeating the second step and the third step after the third step, it is possible to produce a high-quality organic thin film for a semiconductor device having a multilayer structure in which a large number of organic molecular layers are stacked. it can.
In each of the above steps according to the present invention, the by-product generated in each step is removed, and the stacking yield when the organic molecular layer of the monomolecular layer of organic molecules via the bond is stacked is high. Even when a film structure is produced, a high-quality organic thin film can be obtained.

  Further, in the first step, the binding site on the surface of the film formation substrate is a hydroxy group, and the binding site of the first organic molecule is a hydroxy group, a carboxy group, a phosphonic acid group and a silyl group or their reactivity. In the case of any one of the derivatives, generally, a substrate of an inorganic material having a low interaction and the organic thin film can be strongly bonded by a covalent bond, so that an organic thin film having high thermal stability and high durability can be produced. .

  In the case where the second step and / or the third step are any of a reaction of an amino group and a formyl group, a reaction of an amino group and a carboxy group, and a reaction of a hydroxy group and a carboxy group, Water is produced as a by-product with a chemical equilibrium in the process of a chemical reaction progressing from the system to the production system, or in the process of generating an intermediate from the raw material system. Therefore, by removing the water generated as a by-product by the following method, the chemical equilibrium proceeds to the production system, so that the stacking yield is improved and a high-quality organic thin film can be obtained.

That is, when water is generated as a by-product in any of the first to third steps, water can be easily and selectively removed by distillation or column chromatography.
In addition, water generated as a by-product can be selected without heat treatment by removing it through an adsorbent selected from silica gel, activated alumina, calcium chloride, magnesium sulfate, molecular sieve, ion exchange resin, and zeolite. Water can be removed.

In the first step, when the binding site on the surface of the film formation substrate is a hydroxy group, and the binding site of the first organic molecule is a silyl chloride group or a carboxylic acid chloride group, generally the interaction Therefore, an organic thin film having high thermal stability and high durability can be manufactured.
In this case, hydrochloric acid is generated as a by-product. Therefore, the removal of this hydrochloric acid by the following method not only promotes the formation of the organic molecular layer, but also suppresses the corrosion of the organic thin film, substrate and electrode material by hydrochloric acid. You can also
That is, by removing hydrochloric acid generated as a by-product through an alkali solution, particulate or powdered alkali or ion exchange resin, hydrochloric acid can be easily and selectively removed without heat treatment. it can.

  In addition, when the second step and / or the third step combines an amino group and a carboxylic acid chloride group or a hydroxy group and a carboxylic acid chloride group, hydrochloric acid is generated as a by-product. Thus, by removing hydrochloric acid, corrosion of the organic thin film, the substrate, and the electrode material by hydrochloric acid can be suppressed.

  In addition, by providing a sensor for detecting the organic thin film formation process in the reaction chamber, the end point of the lamination reaction can be detected, and one lamination can be completed in the shortest lamination time. The production time of the thin film can be shortened.

In addition, since any one of the reaction chamber, the fluid introduced into the reaction chamber, and the substrate stage in the reaction can be heated, the reaction rate of the stacking reaction is improved, so that the time for manufacturing the organic thin film can be shortened.
In addition, since the by-product removing means in the by-product removing chamber is column chromatography, the by-product removing process is quick and the by-product can be removed without the need for heating.

A material, a manufacturing apparatus, and a manufacturing method for manufacturing the organic thin film for a semiconductor device of the present invention will be described.
First, materials will be described in the order of a film formation substrate, a first organic molecule, a second organic molecule, and a third organic molecule.

  As a film formation substrate on which the organic thin film used in the present invention is formed, a silicon substrate, a quartz substrate, a glass substrate, a resin substrate made of a material such as polycarbonate, polyetheretherketone, polyimide, polyester, polyethersulfone, or the like. Can be mentioned.

The substrate surface is not necessarily the same material as the substrate. For example, gold (Au), silver (Ag), copper (for example) can be easily reacted with the first organic molecules formed on the substrate. Cu), platinum (Pt), palladium (Pd), iron (Fe), aluminum (Al), tantalum (Ta), indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO) ) And tin oxide (SnO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), tantalum oxide (Ta ₂ O ₅ ), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ) ₂ ) and a film formation substrate on which a component different from the substrate material such as an insulating material such as silicon nitride (Si ₃ N ₄ ) is deposited may be used.
Examples of the deposition method include sputtering, vacuum deposition, ion plating, and chemical vapor deposition (CVD) well known to those skilled in the art. For example, the surface of the material deposited by the above-described method may be treated with oxygen plasma treatment or UV. -The method of making it an oxide using techniques, such as ozone oxidation treatment and anodization treatment, can be used.

As the bonding site on the substrate surface used in the present invention, among the above-listed substrate materials or substrate surface materials, those having a hydroxy group on the surface are preferable, and specific bonding sites include Si—OH (silicon, Glass, quartz, silicon oxide), Al-OH (aluminum, aluminum oxide), Ta-OH (tantalum oxide), In-OH (ITO, IZO), Zn-OH (zinc oxide), Sn- OH (derived from tin oxide), Zr—OH (derived from zirconium oxide), Ti—OH (derived from titanium oxide), C—OH (derived from resin material) and the like can be mentioned.
These binding sites having a hydroxy group are preferable because they form a covalent bond via the binding site of the first organic molecule via oxygen, and thus an organic thin film with high thermal stability and little deterioration can be produced.

  Oxygen plasma treatment, UV-ozone treatment, anodization treatment, sulfuric acid-hydrogen peroxide treatment, steam heating treatment well known to those skilled in the art as a method for introducing hydroxy groups into the substrate material to be deposited or the surface of the deposition substrate Such a method can be used.

In addition to those having a hydroxy group on the surface of the substrate to be deposited, those in which the metal atom itself becomes a binding site are preferable, and specifically include Au, Ag, and Pt.
Those having a metal atom as a binding site are preferable because they form a chemical bond directly with the binding site of the first organic molecule, and carrier injection into the organic thin film reduces resistance.

Next, the binding site of the first organic molecule that can be used in the first step will be described.
When the bonding site on the surface of the film formation substrate is a hydroxy group, the bonding site of the first organic molecule is a silyl hydroxy group (Si—OH), a carboxy group (—COOH), a phosphonic acid group (—PO ₃ H). ₂ ), silylalkoxy group (Si-OR), silyl chloride group (Si-Cl), carboxylic acid chloride group (-COCl) and the like.

Since these binding sites and the binding sites on the surface of the film-forming substrate are bonded to form a covalent bond, generally an inorganic material with low interaction and an organic thin film can be strongly bonded, so that thermal stability is improved. It is possible to produce an organic thin film of a monomolecular layer of organic molecules through bonding of an excellent and highly durable organic molecular layer to the surface of the film formation substrate.
In particular, when the substrate surface binding site is a combination of Si-OH and a silylhydroxy group, silylalkoxy group, or silylchloride group, the substrate and the first organic molecule are bonded by the same atom (equivalent atom) via oxygen ( Siloxane bonds (Si—O—Si)), thermal stability, and durability can be improved, which is preferable.

  Further, water reacts as a by-product in the reaction with silylhydroxy group, carboxy group and phosphonic acid group, and hydrochloric acid as a by-product in the reaction with silyl chloride group and carboxylic acid chloride group.

  In the case of the former, by using an adsorbent selected from silica gel, activated alumina, calcium chloride, magnesium sulfate, molecular sieve, ion exchange resin, and zeolite, it is relatively possible to use column chromatography or the like without requiring heat treatment. Water can be easily removed.

  In the latter case, hydrochloric acid can be removed relatively easily by column chromatography or the like via a neutralizing agent such as an alkaline solution, a solid alkaline material, or an ion exchange resin, without requiring heat treatment. Further, by removing hydrochloric acid, corrosion of the organic thin film, the substrate and the substrate surface material can be suppressed.

  As the alkaline solution, an aqueous solution of pH 9 to 14 such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, or calcium carbonate, or an amine aqueous solution such as ammonia or tetramethylamine can be used.

  In addition, as the solid alkali material, particles such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and calcium carbonate can be used.

  Examples of the molecular sieve include Molecular Sieve 3A, 4A, 5A, and 13X. Among these, 3A or 4A type purchased from GL Sciences, for example, is preferable from the viewpoint of dehydration efficiency.

  Examples of the ion exchange resin include weakly basic anion exchange resins. Among these, from the viewpoint of adsorption efficiency of hydrochloric acid, for example, styrene polyamine type Diaion WA20 manufactured by Mitsubishi Chemical Corporation is preferable.

When the reaction for generating hydrochloric acid as a by-product is performed in the gas phase, a method of bubbling a carrier gas into an alkali solution or a method of passing through a column filled with a solid alkali material can be used.
In addition, when the reaction for generating hydrochloric acid as a by-product is performed in a liquid phase, a method of passing the solution through a column filled with a solid alkali material can be used.
Specific solid alkali materials include sodium hydroxide, potassium hydroxide and calcium hydroxide beads, magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), barium oxide (BaO), and alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ) and other metal oxides.

  When the binding site on the substrate surface is a metal atom, the binding site of the first organic molecule is preferably a thiol group (—SH), a dithiol group (—S—SH), or the like. Since the bonding site of the first organic molecule and the metal atom of the electrode directly form a chemical bond, it is preferable to inject carriers into the organic thin film because resistance decreases.

Next, the skeleton of the first organic molecule will be described.
Examples of the first organic molecule used in the present invention include aliphatic skeletons and aromatic skeletons.
When the organic thin film is used as an insulating thin film such as an insulating layer of a thin film transistor, an interlayer insulating film of a device, or a passivation film, an aliphatic skeleton is preferably used.

  When organic thin films are used as semiconducting or conductive thin films such as transistor semiconductor layers, organic EL carrier transport layers, light emitting layers, solar cell n layers, p layers, i layers, and electrode films of devices. It is preferable to use an aromatic skeleton.

Examples of the aliphatic skeleton include linear or branched C ₁ -C ₂₀ alkyl compounds which may have an unsaturated bond. Among these, a linear alkyl compound is preferable in consideration of self-organizing arrangement on the substrate.

  In addition, the aromatic skeleton includes a monocyclic aromatic compound such as benzene, a skeleton in which benzene such as biphenyl and p-terphenyl is bonded to each other in a para position, and a condensation such as naphthalene, anthracene, naphthacene, and pentacene. A polycyclic aromatic skeleton may be mentioned. In addition, a heterocyclic compound having a π-conjugated structure is also preferable. Specifically, examples of the 5-membered ring structure include thiophene, pyrrole, furan, imidazole, and selenophene, and examples of the 6-membered ring structure include pyridine, pyrimidine, and pyrazine. . Further, a skeleton linked at the 2,5-position or para-position (for example, bithiophene, terthiophene, bipyridine, etc.) or a condensed polycyclic skeleton may be used.

  Among these, in consideration of the solubility of molecules, the sublimation temperature, and the boiling point when sequentially laminating, a low molecular weight body is preferable, and one having 1 to 3 aromatic rings or heterocyclic rings linked is preferable.

Next, the skeletons of the second organic molecule and the third organic molecule will be described.
Examples of the skeleton of the second organic molecule and the third organic molecule used in the present invention include a skeleton composed of aliphatic and a skeleton composed of aromatic, like the skeleton of the first organic molecule.
When using an organic thin film as an insulating thin film, it is preferable to use an aliphatic skeleton for any of the first to third organic molecules, and also when using an organic thin film as a semiconducting or conductive thin film. It is preferred to use an aromatic skeleton for any of the molecules.

Next, the combination of the binding site of the first organic molecule and the binding site of the second organic molecule to be subjected to the second step, and the binding site of the second organic molecule to be subjected to the second step The combination of the binding sites of the third organic molecule will be described.
The combination of the unreacted binding site of the first organic molecule and the binding site of the second organic molecule used in the present invention, and the unreacted binding site of the second organic molecule and the third organic molecule The combinations when the binding sites react include amino group (—NH ₂ ) and formyl group (—CHO), amino group and carboxy group (—COOH), hydroxy group and carboxy group, hydroxy groups to each other, amino group and carboxylic group. Acid chloride group (—COCl), hydroxy group and carboxylic acid chloride group, terminal acetylene (≡C—H) and aryl bromide (Ar—Br), formyl group and phosphorus ylide (R ₂ C—PR ₃ ) and terminal ethylene (= CH-H) and aryl bromide. (Ar means an aromatic skeleton, and R means a hydrocarbon skeleton).

  In the reaction between an amino group and a formyl group, an amino group and a carboxy group, a hydroxy group and a carboxy group, and a hydroxy group, an azomethine bond (—CH═N—), an amide bond (—CO—NH—), an ester bond ( -COO-) and ether bond (-O-) are given, and these reactions generate water as a by-product when the chemical reaction proceeds from the raw material system to the production system, and by removing this water, a chemical equilibrium is generated. Since the process proceeds to the system, the stacking yield is improved, and a high-quality organic thin film can be obtained.

  In particular, the azomethine bond resulting from the reaction of the amino group and formyl group of the aromatic organic molecule forms a π-conjugated bond, and the molecules before and after the azomethine bond are connected by the π-conjugated bond, extending the π-conjugate. Can do. Therefore, it is preferable when the organic thin film is used as a conductive or semiconductive thin film.

  From the viewpoint of using an organic thin film as a conductive or semiconducting thin film, an acetylene bond (-C≡C-) generated from terminal acetylene and aryl bromide, an ethylene bond (-C = C-) generated from formyl group and phosphorus ylide, terminal An ethylene bond (-C = C-) generated from ethylene and aryl bromide is also preferable because the preceding and succeeding molecules can be linked by a π-conjugated bond.

  In addition, the reaction of amino group and carboxylic acid chloride group and hydroxy group and carboxylic acid chloride group give amide bond and ester bond, respectively, which may corrode organic thin film, substrate and substrate surface material. Although hydrochloric acid is by-produced, according to the present invention, corrosion of the organic thin film and the substrate can be suppressed by removing the hydrochloric acid.

  In particular, the amide bond resulting from the reaction of an amino group and a carboxy group, or an amino group and a carboxylic acid chloride group causes cross-linking due to hydrogen bonding between adjacent amide bonds in the parallel direction, resulting in an organic thin film with few pinholes. Since it can form, it is preferable when using an organic thin film as an insulating thin film.

  In the reaction of the amino group and the carboxy group, a condensing agent such as dicyclohexylcarbodiimide (DCC) can be used. In this case, water is not by-produced, but a urea derivative of DCC is by-produced. Since this DCC derivative is a compound that is hardly soluble in general solvents, there is a risk of inhibiting the reaction of organic molecules when it is physically adsorbed on the substrate. Preferably it is done.

  For removal of water or hydrochloric acid generated in each of the above steps, the adsorbent and neutralizing agent used in the first step can be used. Organic by-products generated by other reactions can be effectively removed by using activated carbon as an adsorbent.

  Next, the number of binding sites of the first to third organic molecules will be described.

  When the first organic molecule has a single-layer structure consisting of only the first organic molecular layer, it may have one or more binding sites for binding to the binding sites on the substrate surface. In the case of a two-layer structure or a multilayer structure composed of the organic molecular layer and the second organic molecular layer, two or more binding sites are required.

Similarly, the second organic molecule also binds to an unreacted binding site of the first organic molecular layer in the case of a two-layer structure composed of the first organic molecular layer and one second organic molecular layer. It is sufficient to have one or more binding sites for the three-layer structure composed of the first organic molecular layer, the second organic molecular layer and the third organic molecular layer, or the first In the case of a multilayer structure in which the second organic molecular layer and the third organic molecular layer are repeatedly laminated in addition to the organic molecular layer, two or more binding sites are required. In addition, the second organic molecule that is the termination of the organic molecular layer stacking reaction may have one or more binding sites.
Further, the third organic molecule has a three-layer structure composed of the first organic molecular layer, the second organic molecular layer, and the third organic molecular layer, or the second organic molecular layer, In order to construct a multilayer structure in which the organic molecular layer and the third organic molecular layer are repeatedly laminated, two or more binding sites are required.

Next, the position of the binding site in each organic molecule of the first to third organic molecules will be described.
In the stacking reaction in each of the above steps, it is preferable that the molecules are stacked in a direction substantially perpendicular to the substrate. Therefore, the binding sites of the molecules are located at positions separated from each other on the long axis in the organic molecule. Is preferred.
Specifically, the 6-membered aromatic compound is para-positioned, the naphthalene compound which is a bicyclic aromatic compound having 10 carbon atoms is 1,5-position or 2,6-position, and the 5-membered-ring heterocyclic compound is 2, In the 5-position, linear alkyl compounds, α- and ω-positions are preferred.

  In addition, the position of the binding site of the first organic molecule in the case of a single-layer structure consisting of only the first organic molecular layer and the second organic molecule that terminates the stacking reaction is in the long axis direction of each molecule. It is preferable to have one at the end. In addition, the end opposite to the end having the binding site is preferably an inactive alkyl group or phenyl group from the viewpoint of the stability of the organic thin film.

As a specific example of the first organic molecule, when an organic thin film for a semiconductor device having one organic molecular layer is produced, n-octadecyltrichlorosilane (C ₁₈ ) is used as an alkyl group-terminated one. C ₄ -C ₂₂ linear alkyl silanes such as those having a toluene skeleton such as p-tolyltrichlorosilane, and those having a phenyl group terminal include phenyl trichlorosilane, benzyltrichlorosilane, phenethyltrichlorosilane, Examples include phenylpropyltrichlorosilane, phenylbutyltrichlorosilane, N-phenylaminopropyltrimethoxysilane, and the like.

  Specific examples of the first organic molecule in the case of producing an organic thin film for a semiconductor device having two or more organic molecular layers include those having an amino group such as 3-aminopropyltrimethoxysilane, 11-amino. Undecyltriethoxysilane, p-aminophenylmethoxysilane, those having a formyl group, triethoxysilylundecanal, those having a carboxy group, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4, 5,6-epoxyhexyltriethoxysilane, (3-glycidoxypropyl) trimethoxy, such as 5,8-naphthalenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and those having an epoxy group As silane or an isocyanate group, 3-isocyanatopropyltrimethoate Shishiran, and the like.

  Specific examples of the second organic molecule include benzaldehyde, aniline, 2-naphthaldehyde, 1-naphthaldehyde, 2-naphthylamine when an organic thin film for a semiconductor device having two organic molecular layers is prepared. 1-naphthylamine, 2,2 ′: 5′2 ″ -terthiophene-5-carboxaldehyde and the like. When an organic thin film for a semiconductor device having an organic molecular layer having a three-layer structure or a multilayer structure is prepared, terephthalaldehyde, 2,2 ′: 5′2 ″ -terthiophene-5,5′-dicarboxyl is used. Examples include aldehyde, p-phenylenediamine, 1,5-naphthalenediamine, 4,4′-diaminostilbene, and the like.

  As a specific example of the third organic molecule, a specific example in the case of producing an organic thin film for a semiconductor device having an organic molecular layer having a three-layer structure and a multilayer structure in the specific example of the second organic molecule described above. Can be used.

Next, the manufacturing apparatus in this invention is demonstrated using FIGS. 1-3.
FIG. 1 shows an organic thin film production apparatus according to the present invention.
This apparatus includes an airtight reaction chamber 11 for performing a stacking reaction, a substrate stage 111 for holding a film forming substrate provided in the reaction chamber, and a byproduct removal chamber 12. It is an organic thin film production apparatus.

  In such a separation type configuration, the reaction chamber and the by-product removal chamber are separated from each other, so that the stacking reaction performed in the reaction chamber, such as the adsorbent flying to the substrate and the pH change of the reaction chamber, is not performed. A means for removing the product is preferred because it has no effect. Moreover, since a by-product removal chamber can be easily added, two or more types of by-products can be removed.

  As a means for introducing the first to third organic molecules (hereinafter referred to as laminated molecules) that are the raw materials for the organic thin film, a fluid mixed or dissolved in a carrier gas or a solvent is introduced into the reaction chamber. It can be introduced through the provided inlet 13.

The carrier gas is an inert gas that does not participate in the stacking reaction, and is preferably a gas that is well mixed with the organic molecules and by-products of the raw material.
Specific examples include nitrogen, argon, supercritical carbon dioxide, and air, and it is preferable to adjust the pressure so that the stacked molecules and by-products are vaporized.
Among these, nitrogen gas, argon gas, or supercritical carbon dioxide is preferable from the viewpoint of providing a stable mixture.

Moreover, as said solvent, when water or hydrochloric acid byproduces, the polar organic solvent which melt | dissolves them is preferable, Specifically, alcohol, such as methanol, ethanol, 2-propanol, tetrahydrofuran, a dioxane, etc. And high boiling polar solvents such as dimethyl sulfoxide and dimethylformamide.
From the viewpoint of removing water, these anhydrous solvents are preferably used as the solvent. Moreover, when a hydroxy group is a binding site, it is preferable to use a solvent excluding alcohols.
A solvent immiscible with water, such as benzene or toluene, can also be used.

  The mixing ratio (partial pressure ratio) of the above-mentioned laminated molecules and carrier gas is in the range of 0.0001: 1 to 1: 1, and the concentration when the above-mentioned laminated molecules are dissolved in the solvent is 0.1 mmol. The range of / L to 1 mol / L is preferable from the viewpoint of the minimum supply amount to the reaction chamber and the saturation solubility (miscibility) in the fluid.

Further, as a means for discharging the by-product generated by the stacking reaction, the above-described fluid is discharged into the by-product removal chamber through the discharge port 14 using the pressure when the fluid is introduced into the reaction chamber. The fluid is pumped from the reaction chamber by a liquid pump or a diaphragm pump manufactured by Buchi, etc., which has high durability against a corrosive gas, or the by-product removal chamber is discharged from the reaction chamber. Then, after removing the by-product, it can be circulated into the reaction chamber through the reintroduction port 15.
In order not to increase the concentration of by-products in the reaction chamber and to remove the by-products and advance the lamination reaction, fluid is circulated between the reaction chamber and the by-product removal chamber during the lamination reaction. Preferably it is.

  Further, in FIG. 1, from the viewpoint of the airtightness of the reaction chamber, one introduction port, one discharge port, and one reintroduction port are provided. However, the type of stacked molecules, the type of by-products, and the type of discharge ( The number of introduction ports, discharge ports, and reintroduction ports may be increased by transporting to the byproduct removal chamber or discarding the fluid.

  A stacking reaction is performed in the reaction chamber of such a manufacturing apparatus, and a by-product generated in the reaction chamber is removed in the by-product removal chamber and introduced into the reaction chamber again. Proceeds to the production system, and a high-quality organic thin film can be obtained with a high lamination yield.

  It is also preferred that a sensor 112 for detecting the organic thin film forming process is provided in the reaction chamber, the end point of the stacking reaction can be detected, and one stacking can be completed in the shortest stacking time. Therefore, the production time of the organic thin film can be shortened. Examples of sensors include measurement of weight change with a quartz resonator, measurement of film thickness change with a spectroscopic ellipsometer, measurement of change in dielectric constant of the substrate surface by surface plasmon resonance, measurement of change in substrate absorbance by UV-visible spectrum. However, the quartz resonator is preferable because it does not use an optical method and can perform stable measurement regardless of the fluid medium.

In addition, it is preferable to provide means for heating the fluid containing the layered molecules to be introduced, the reaction chamber, or the substrate stage. Since the reaction rate is improved by heating, the time for producing the organic thin film can be shortened.
In the case of heating, it is preferable to heat to a temperature of 150 ° C. or less in consideration of the thermal strength of the organic thin film and environmental load.

In the byproduct removal chamber, a filler can be used as a means for removing byproducts.
As said filler, the said neutralizing agent or adsorption agent is used.

Moreover, when performing the lamination reaction which produces | generates hydrochloric acid in a by-product in a liquid phase, the method of passing a solution through the column filled with the solid alkali material is mentioned.
For other by-products, it is preferable to use activated carbon capable of adsorbing various organic substances.
In addition, before removing the by-products by column chromatography, the solid substance can be removed by filtration in order to prevent clogging by solids generated in the reaction chamber or the like.

In addition to the column chromatography described above, when the boiling point of the stacked molecule and the fluid carrying the stacked molecule and the by-product are greatly different, the by-product can be removed by distillation.
The difference in boiling point at this time is preferably ± 25 ° C. or more. For example, when benzene that is immiscible with water is used as a solvent, dean-stark apparatus is used, and benzene (bp 80 ° C.) is used. A method of removing water by azeotropically boiling water (bp 100 ° C.) as a by-product (azeotropic point 69 ° C.) and utilizing the specific gravity of benzene and water and the property of phase separation. it can.

FIG. 2 shows an organic thin film manufacturing apparatus according to another embodiment of the present invention.
This apparatus includes an airtight reaction chamber 21 for performing a lamination reaction, a substrate stage 211 for holding a film formation substrate provided in the reaction chamber, a sensor 212 for detecting a film formation process of an organic thin film, and a by-product. This is an apparatus for producing an organic thin film for a semiconductor device of the same type, which comprises an object removing means 22, a means 23 for introducing stacked molecules, and a means 24 for discharging a fluid.

  In the same type of configuration, a by-product generated in the stacking reaction can be quickly removed, so that the reaction rate of the stacking reaction is improved.

The means for introducing the laminated molecules, the means for discharging the fluid, the sensor for detecting the film forming process of the organic thin film, the fluid to be introduced, the means for heating the reaction chamber or the substrate stage are the same as those of the organic thin film for the above-mentioned separation type semiconductor device A device similar to a manufacturing device can be used.
Further, as a means for removing by-products, adsorption with an adsorbent, distillation, sublimation, recrystallization, reprecipitation, and separation membrane can be used.

Among these, distillation is preferable because by-products can be removed while heating the reaction chamber, so that the reaction rate of the lamination reaction is improved. Further, a reaction chamber equipped with a Dean-Stark device (not shown) is also preferable, and by-product water can be removed using benzene or toluene as a solvent.
In addition, when performing adsorption with an adsorbent, the same adsorbent as that for the organic thin film production apparatus for a separation type semiconductor device can be used, but it is allowed to settle in order to prevent the adsorbent from flying to the substrate. Preferably, it is preferable not to select an alkaline solution, a solid alkaline material, or the like that dissolves in a solvent and affects the pH in the reaction chamber and inhibits the lamination reaction.

FIG. 3 shows an organic thin film manufacturing apparatus according to another embodiment of the present invention.
This apparatus includes an airtight reaction chamber 31 for performing a lamination reaction and a by-product removal chamber 322. A substrate stage 311 for holding a substrate to be formed in the reaction chamber, and a process for forming an organic thin film. This is an apparatus for producing an organic thin film for a mixed semiconductor device, which includes a sensor 312 to detect and a by-product removing unit 321.

  In such a mixed-type configuration, by-products are removed in the reaction chamber and by-product removal chamber, so that an organic thin film for the same type semiconductor device capable of removing two or more types of by-products can be produced. It has two effects, that is, the effect of the apparatus and the effect of the apparatus for producing an organic thin film for a separation type semiconductor device capable of quickly removing the by-product generated by the stacking reaction.

  Means for removing by-products, means for introducing stacked molecules, means for discharging fluid, sensors for detecting the process of forming an organic thin film, means for introducing fluid, means for heating reaction chamber or substrate stage are separate types Or the thing similar to the preparation apparatus of the organic thin film for identical type semiconductor devices can be used.

Next, a manufacturing method will be described with reference to FIGS.
In the first step of the present invention, a first organic molecule layer is formed by a chemical reaction between the surface binding site of the substrate and the first organic molecule.

First, the above-described substrate 40 is fixed to the substrate stage 411 of the reaction chamber 41, and a carrier gas or solution containing the first organic molecule is introduced into the reaction chamber. The first organic molecule layer 401L is formed by the first step with the binding site of the first organic molecule 401 in contact with the binding site on the substrate surface, and a by-product 421 is generated. The resulting by-product is immediately transported to the by-product removal chamber 42 where it is removed. The fluid from which by-products have been removed is again introduced into the reaction chamber (FIG. 4a).
In order not to increase the concentration of by-products in the reaction chamber, it is preferable that the fluid containing the stacked molecules circulate between the reaction chamber and the by-product removal chamber during the stacking reaction.
Also in the following second step and third step, it is preferable to circulate a fluid containing laminated molecules during the lamination reaction.

  According to the method for producing an organic thin film of the present invention, reaction by-products are removed as needed, so that the lamination reaction proceeds to the production system based on the Le Chatelier's principle, and a high-quality organic thin film having a high lamination yield is obtained. be able to.

Next, in the second step, the second organic molecular layer is formed by the unreacted binding site of the first organic molecular layer, the binding site of the second organic molecule, and the second step.
First, in order to remove the first organic molecules remaining in the reaction chamber, it is preferable that the reaction chamber is filled with a fluid in which the first organic molecules can be mixed or dissolved and washed well.

  Next, a fluid containing the second organic molecule 402 is introduced into the reaction chamber. The unreacted binding site of the first organic molecular layer 401L formed by the above-described method and the binding site of the second organic molecule in contact with each other chemically react to form the second organic molecular layer 402L. Product 422 is produced.

  The resulting by-product is immediately transported to the by-product removal chamber 42 where it is removed and again introduced into the reaction chamber (FIG. 4b)).

  By such a method, a two-layer structure of the first organic molecular layer and the second organic molecular layer can be formed. In such an organic thin film having a two-layer structure, for example, an organic thin film having different functions such as an insulating layer and a semiconductor layer of a transistor, a p layer and an n layer of a solar cell, a carrier transport layer and a light emitting layer of an organic EL can be easily formed. It is possible to make it, and it is possible to give diversity to the function of the organic thin film.

  In addition, when different by-products are generated in the first step, the second step, and the following third step, two or more by-product removal chambers are provided, or a by-product is provided for each stacking reaction. It is preferred to replace the product removal chamber.

  Next, in the third step, an unreacted binding site of the second organic molecular layer and a binding site of the third organic molecule can be further bonded to form a third organic molecular layer.

  First, as in the second step, it is preferable to fill the reaction chamber with a fluid in which the second organic molecules can be mixed or dissolved in order to remove the remaining second organic molecules, and to wash well. Thereafter, a fluid containing the third organic molecule 403 is introduced into the reaction chamber. The third organic molecular layer 403L is formed by a chemical reaction between the unreacted binding site of the second organic molecular layer 402L formed by the above-described method and the binding site of the third organic molecule in contact therewith. The by-product 422 generated in this process is immediately transported to the by-product chamber 42 where it is removed and introduced again into the reaction chamber (FIG. 4c)).

By such a technique, an organic thin film having a three-layer structure in which the second and third organic molecular layers are laminated on the first organic molecular layer can be formed (FIG. 4d).
In addition, by repeating the second step and the third step on the third organic molecular layer, organic molecules can be sequentially laminated to produce an organic thin film for a semiconductor device having a multilayer structure. .

  With the increase in the number of layers, there is a concern that the film quality of the entire organic thin film may be deteriorated when the stacking yield is low when stacking one layer. According to the present invention, by-products are successively formed during the stacking reaction. Since it is removed and the stacking yield when stacking one layer is high, high quality film quality can be maintained even if the number of stacks increases.

  Furthermore, a specific method of sequentially stacking organic molecules by repeating the second step and the third step will be described with reference to FIG.

  As a method of sequentially laminating the second organic molecule and the third organic molecule, the protection and desorption of the second organic molecule and the third organic molecule having a combination binding site that causes a laminating reaction in the molecule. Of the combined binding sites that cause the stacking reaction in the molecule (AB type (Fig. 5a)) and the method of laminating and stacking repeatedly, the second organic molecule having one binding site and the other binding A method (AA-BB type (FIG. 5b)) in which two types of third organic molecules having sites are prepared and alternately stacked is mentioned.

  That is, when the stacked molecule has two or more binding sites, the binding sites of the same organic molecule are the same or different from each other, and are a hydroxy group, an amino group, a formyl group, a carboxyl group, or a protected derivative thereof. .

  In the AB type, after using a molecule AB ′ (B ′ is a protected binding site B) in which the functional group B is protected for the purpose of preventing self-reaction between molecules, the AB ′ is laminated. Although it is necessary to perform deprotection, it is preferable because one kind of organic molecule is prepared.

On the other hand, in the AA + B-B type, it is necessary to prepare two kinds of organic molecules, but this is preferable because there is no treatment for protecting and deprotecting the binding site B as in the AB type.
By the above method, an organic thin film for a semiconductor device having a multilayer structure in which organic molecules are laminated by a covalent bond one by one from the substrate surface can be produced.

The following examples and comparative examples illustrate the present invention, and the present invention is not limited to the following examples and comparative examples.
The manufacturers of the processing equipment, measuring equipment and reagents used in the examples and comparative examples are described below.
apparatus:
UV ozone treatment equipment: SAMCO (UV-1)
Contact angle meter: Rycobel (PG-X)
Spectroscopic ellipsometer: A. Woollam (M-2000U)
UV-visible spectrophotometer: Shimadzu Corporation (UV-3600)

reagent:
Acetone: Sigma Aldrich Japan (special grade)
Octadecyltrichlorosilane: Gelest (97%)
Anhydrous tetrahydrofuran: Kanto Chemical (water content 0.005% or less)
p-aminophenyltrimethoxysilane: Gelest (90%)
Absolute ethanol: Kanto Chemical (water content 0.005% or less)
Terephthalaldehyde: Tokyo Chemical Industry (98%)
Diaminostilbene dihydrochloride: Aldrich (95%)
Purification of diaminostilbene Diaminostilbene dihydrochloride was dissolved in water and neutralized by adding a small amount of aqueous sodium hydroxide. Further dichloromethane was added and the organic phase was extracted. The organic phase was dried and purified by recrystallization from a dichloromethane / hexane system.

Example 1
6a) to 6d) schematically show a method for producing the organic transistor of the present invention.
A glass substrate obtained by sputtering ITO at 60 nm was used as a film-forming substrate (25 mm square) 60.
First, after removing organic deposits on the surface of the substrate by ultrasonic cleaning with acetone, hydroxy groups (In—OH) were exposed on the surface of the substrate by UV ozone treatment (room temperature, 10 minutes). The substrate was fixed to the substrate stage 611 in the reaction chamber 61. Further, in order to adsorb hydrochloric acid generated as a by-product, ion exchange resin (Diaion WA20 manufactured by Mitsubishi Chemical Corporation) 62 was spread in the reaction chamber (FIG. 6a).

Next, n-octadecyltrichlorosilane 601 (OTS) (FIG. 6d)) was stacked as the first organic molecule using the same type manufacturing apparatus.
First, the reaction chamber 61 was held with a vacuum pump at a reduced pressure of 10 Pa or less for 10 minutes, and the operation of filling nitrogen gas was repeated three times to remove moisture and oxygen in the reaction chamber (this operation is hereinafter referred to as nitrogen replacement). To do). Next, an anhydrous tetrahydrofuran solution (1 mmol / L) of OTS was prepared, and 200 ml was introduced from the inlet 63 into the reaction chamber at room temperature. The depth from the solution surface to the film formation substrate surface at this time was 3 cm.
In addition, hydrochloric acid 621 generated as a by-product by the reaction between the substrate surface hydroxy group and the trichlorosilyl group of OTS was adsorbed by the ion exchange resin 62 spread in the reaction chamber (FIG. 6b)).

  After 3 hours, an anhydrous tetrahydrofuran solution of OTS was discharged from the discharge port 64 into the reaction chamber. Further, anhydrous tetrahydrofuran was introduced, the substrate was thoroughly washed, and then the anhydrous tetrahydrofuran used for cleaning was discharged from the discharge port 64. The washing process by introducing and discharging anhydrous tetrahydrofuran was further repeated twice to remove OTS physically adsorbed on the substrate (FIG. 6c)).

Next, the substrate was taken out of the reaction chamber, and when the static contact angle of water was measured, it showed a high water repellency of 109 °.
The contact angle was calculated by a so-called θ / 2 method in which a water droplet was dropped on the substrate surface and calculated from an angle formed by a straight line connecting the left and right end points and the vertex of the dropped droplet and the substrate surface.
Moreover, when the film thickness of the organic thin film was measured with the spectroscopic ellipsometer, it was almost equal to the molecular length calculated from the molecular orbital calculation, and was 2.9 nm. Therefore, the formation of the OTS monomolecular film could be confirmed.

Comparative Example 1
An experiment was conducted using the same substrate to be formed and the first organic molecule as in Example 1 without removing the by-product using the ion exchange resin.
Specifically, a glass substrate on which ITO (50 nm) was sputtered and an OTS anhydrous tetrahydrofuran solution (1 mmol / L) were sealed in the manufacturing apparatus used in Example 1, and OTS was stacked on the ITO surface.
After washing with tetrahydrofuran after 3 hours, the substrate was taken out and the static contact angle of water was measured. As a result, it was 40 °, which was lower than that of Example 1. Further, it was observed with naked eyes that the ITO on the glass substrate was peeled off, and when the electrical resistance value of the ITO electrode was measured with a tester, a value larger than the measurement limit (5 MΩ or more) was shown. That is, the ITO on the substrate surface was eroded by the by-produced hydrochloric acid.

Examples 2 and 3
A quartz substrate (Example 2) and a silicon substrate (Example 3) were used as the film-forming substrate 70, respectively (substrate size is 25 mm square). First, both substrates were treated in the same manner as in Example 1 to expose the hydroxy group (Si—OH) on the substrate surface, and then fixed to the substrate stage 711 in the reaction chamber 71, The inside of the piping and by-product removal chamber (also referred to as a column) 72 was replaced with nitrogen. In addition, as shown in FIG. 7a), the lamination reaction was performed with a separation type manufacturing apparatus.

Next, p-aminophenyltrimethoxysilane 701 (APhS) (FIG. 7j)) was stacked as the first organic molecule.
APhS is heated to 100 ° C., and the vaporized gas is mixed with nitrogen as a carrier gas (partial pressure ratio APhS: nitrogen = 0.0005: 1) and introduced into a reaction chamber heated to 100 ° C. at a flow rate of 0.5 L / min. 73 (FIG. 7a)). In addition, nitrogen initially charged and the introduced carrier gas were discharged from the discharge port 76, and purged with nitrogen gas containing APhS for 5 minutes so that the concentration in the reaction chamber became uniform. After the introduction, the introduction port 73 and the discharge port 76 are closed, and the reaction product is circulated between the reaction chamber 71 and a by-product removal chamber consisting of a column packed with 4A type molecular sieve (purchased from GL Sciences) with high methanol adsorption capacity. In the first step, APhS was laminated with a siloxane bond.

Further, methanol 721 produced as a by-product was adsorbed in the column 72 (FIG. 7b)).
The film formation process was detected by the quartz crystal resonator 712, and it was observed that the increase in the weight of the molecule covalently bonded to the substrate with respect to the reaction time stopped in a self-organized manner about 2.5 hours after the reaction started. After the chamber, piping, and byproduct removal chamber were purged with nitrogen, the reaction chamber was filled with absolute ethanol, and the substrate was thoroughly cleaned. The absolute ethanol used for the cleaning was discarded from the discharge port 76, and APhS physically adsorbed on the reaction chamber and the substrate was removed by repeating the above cleaning process two more times.
Thus, the first organic molecular layer 701L (first layer) was formed (FIG. 7c)).

Next, terephthalaldehyde 702 (TPAld) (FIG. 7k)) was laminated as a second organic molecular layer.
First, 3A type molecular sieve (purchased from GL Sciences Inc.) with high water adsorption capacity was filled as an adsorbent in the by-product removal chamber 72, and nitrogen substitution in the reaction chamber, piping, and by-product removal chamber was performed. .
Next, an absolute ethanol solution of TPAld (1 mmol / L) was prepared, and this solution was introduced from the introduction port 73 of the reaction chamber 71 with a liquid feed pump to fill the reaction chamber, piping, and byproduct removal chamber 72 ( FIG. 7 d)). The introduced absolute ethanol solution was circulated between the reaction chamber and the by-product removal chamber, and TPAld was laminated with an azomethine bond in the second step.

  Further, water 722 generated as a by-product was adsorbed in the column 72 (FIG. 7e)). The film-forming process was detected by a quartz oscillator, and it was observed that the increase in the weight of the molecules covalently bonded to the substrate with respect to the reaction time stopped self-organized 6 hours after the start of the reaction. And the byproduct removal chamber was filled with absolute ethanol for cleaning, the remaining TPAld was dissolved, and the substrate, reaction chamber, piping and byproducts were thoroughly cleaned. The absolute ethanol used for washing was discarded from the outlet 76, and the washing process was repeated twice more. A second organic molecular layer 702L (second layer) was thus formed (FIG. 7f)).

Further, 4,4′-diaminostilbene 703 (StDA) (FIG. 7l)) was laminated as a third organic molecular layer.
First, an absolute ethanol solution (1 mmol / L) of StDA was prepared, and this solution was introduced from the introduction port 73 of the reaction chamber 71 with a liquid feed pump to fill the reaction chamber, piping, and byproduct removal chamber 72 (see FIG. 7g)). At this time, as the adsorbent in the by-product removal chamber, the same adsorbent as in the TPAld lamination was used. Next, the introduced absolute ethanol solution was circulated between the reaction chamber and the byproduct removal chamber, and StDA was laminated with an azomethine bond in the third step.
Further, water 722 generated as a by-product was adsorbed in the column 72 (FIG. 7h)). The film-forming process was detected by a quartz oscillator, and it was observed that the increase in the weight of the molecules covalently bonded to the substrate with respect to the reaction time stopped self-organized 6 hours after the start of the reaction. Then, the byproduct removal chamber was filled with absolute ethanol for cleaning, the remaining StDA was dissolved, and the substrate, reaction chamber, piping, and byproducts were thoroughly cleaned. The absolute ethanol used for washing was discarded from the outlet 76, and the washing process was repeated twice more. Thus, a third organic molecular layer 703L (third layer) was formed (FIG. 7i) m)).

  As the evaluation of the produced organic thin film, FIG. 8 shows the results of measuring the film thickness with a spectroscopic ellipsometer when laminated on a silicon substrate and the change in absorption due to the ultraviolet-visible light spectrum when laminated on a quartz substrate. The film thickness shows a monotonous increase with the increase in the number of layers, and the increase is almost equal to the molecular length obtained from the molecular orbital calculation, so the stacked molecules are oriented in a direction substantially perpendicular to the substrate, It was confirmed that it was formed (FIG. 8a)). Further, in the absorption spectrum, an increase in absorption near 300 to 500 nm and a long wavelength shift at the absorption edge were confirmed with an increase in the number of layers (FIG. 8b)). From these, it was confirmed that the organic molecular layers were laminated one by one from the substrate by a chemical reaction, and a high-quality organic thin film could be obtained.

Comparative Examples 2 and 3
Without removing the by-products, experiments were performed using the same substrate to be formed as in Examples 2 and 3 and the first to third organic molecules.
Specifically, using the same film-formed substrate as in Examples 2 and 3, the hydroxy group (Si—OH) was exposed on the substrate surface by the same treatment.

Next, APhS was laminated as the first organic molecule.
In a Teflon (registered trademark) container that can be sealed, a film-forming substrate and APhS were added in a nitrogen atmosphere, and heated in an oven at 100 ° C. for 3 hours. Next, the substrate was taken out and subjected to ultrasonic cleaning with acetone to remove the physically adsorbed APhS, thereby forming a first organic molecular layer (first layer).

Next, TPAld was stacked as the second organic molecule.
In a glass container that can be sealed, an APhS-laminated substrate and an aqueous solution of TPAld in dichloromethane (1 mmol / L) were added and stirred for 20 hours at room temperature. Next, the substrate was taken out and subjected to ultrasonic cleaning with absolute ethanol to remove the physically adsorbed TPAld, thereby forming a second organic molecular layer (second layer).

Further, StDA was stacked as the third organic molecule.
In a glass container that can be sealed, a TPAld-laminated substrate and StDA in anhydrous dichloromethane (1 mmol / L) were added and stirred at room temperature for 20 hours. Next, the substrate was taken out and subjected to ultrasonic cleaning with absolute ethanol to remove the physically adsorbed StDA, thereby forming a third organic molecular layer (third layer).

  As the evaluation of the produced organic thin film, the results of film thickness measurement using a spectroscopic ellipsometer and absorption spectrum measurement using an ultraviolet-visible light spectrum as in Examples 2 and 3 are shown in FIG. The film thickness increased monotonically up to the second layer, but no increase was observed in the third layer (FIG. 9a)). Further, in the absorption spectrum, a long wavelength shift of the absorption edge was observed with an increase in the number of layers, but the increase in absorption near 300 to 500 nm was compared with Example 2 in which by-products were removed, It was observed to be small (FIG. 9b)). From these facts, it was confirmed that when a lamination reaction was performed in an atmosphere in which a by-product remained in a sealed container, the lamination yield decreased due to chemical equilibrium, and a high-quality organic thin film could not be produced. .

  According to the apparatus for producing an organic thin film for a semiconductor device and the method for producing an organic thin film for a semiconductor device using the same according to the present invention, the by-product generated in any of the first to third steps is airtight. Since it can be removed in the sex reaction chamber and / or the byproduct removal chamber, a stacking reaction of an organic molecular layer in which at least one monomolecular layer of organic molecules via a chemical bond is stacked (hereinafter also simply referred to as a stacking reaction). Advances to the production system, the reaction yield of the stacking reaction (hereinafter referred to as stacking yield) is improved, and a high-quality organic thin film for semiconductor devices can be efficiently produced.

It is the schematic of the organic thin film preparation apparatus of this invention. It is the schematic of the organic thin film preparation apparatus of this invention. It is the schematic of the organic thin film preparation apparatus of this invention. It is the schematic which shows the preparation process of the organic thin film of this invention. It is the schematic which shows the preparation process of the organic thin film of this invention. It is the schematic which shows the preparation process of the organic thin film of this invention. It is the schematic which shows the preparation process of the organic thin film of this invention. It is a figure which shows the preparation results of the organic thin film of this invention and Example 2 and 3. FIG. It is a figure which shows the preparation results of the organic thin film of the comparative examples 2 and 3.

Explanation of symbols

10: Substrate 11: Reaction chamber 111: Substrate stage 112: Sensor 12: Byproduct removal chamber 13: Introduction port 14: Discharge port 15: Reintroduction port

20: Substrate 21: Reaction chamber 211: Substrate stage 212: Sensor 22: Byproduct remover 23: Inlet 24: Discharge port 30: Substrate 31: Reaction chamber 311: Substrate stage 312: Sensor 321: Byproduct remover 322: Byproduct removal chamber 33: Introduction port 34: Discharge port 35: Reintroduction port 40: Substrate

401: First organic molecule (first layer)
402: Second organic molecule (second layer)
403: Third organic molecule (third layer)
401L: First organic molecular layer (first layer)
402L: Second organic molecular layer (second layer)
403L: third organic molecular layer (third layer)
41: Reaction chamber 411: Substrate stage

412: Sensor 42: By-product removal chamber 421: By-product generated in the first step 422: By-product generated in the second and third steps 43: Inlet 44: Outlet 45: Reinlet 60: Substrate

601: First organic molecule (OTS)
601L: First organic molecular layer (first layer)
61: Reaction chamber 611: Substrate stage 612: Sensor 62: By-product removing agent 621: By-product (hydrochloric acid) generated in the first step
63: Introduction port

64: Discharge port 70: Substrate 701: First organic molecule (APhS)
702: Second organic molecule (TPAld)
703: Third organic molecule (StDA)
701L: First organic molecular layer (first layer)
702L: Second organic molecular layer (second layer)
703L: Third organic molecular layer (third layer)

71: Reaction chamber 711: Substrate stage 712: Sensor 72: Byproduct removal chamber (column)
721: By-product (methanol) generated in the first step
722: By-product (water) generated in the second and third steps
73: Introduction port 74: Discharge port 75: Reintroduction port 76: Discharge port

Claims (18)

An apparatus for producing an organic thin film for a semiconductor device comprising at least one monolayer composed of organic molecules on the surface of a substrate to be deposited via a chemical bond and having at least an airtight reaction chamber to form an organic thin film. There,
The reaction chamber is
An introduction part for introducing a gaseous or solution-like fluid containing the organic molecules into the reaction chamber;
A substrate stage for holding the deposition substrate;
A discharge part for discharging the fluid from the reaction chamber;
With
Furthermore, a means for removing a by-product generated when a chemical bond is formed is provided at least in the reaction chamber or in a by-product removal chamber connected to the reaction chamber and provided separately from the reaction chamber. An apparatus for producing an organic thin film for a semiconductor device. The device is
Comprising the gas tight reaction chamber and the byproduct removal chamber,
The apparatus for producing an organic thin film for a semiconductor device according to claim 1, wherein means for removing the by-product is provided in the by-product removal chamber. The device is
Comprising the airtight reaction chamber,
The apparatus for producing an organic thin film for a semiconductor device according to claim 1, wherein means for removing the by-product is provided in the reaction chamber. The device is
Comprising the gas tight reaction chamber and the byproduct removal chamber,
The apparatus for producing an organic thin film for a semiconductor device according to claim 1, wherein means for removing the by-product is provided in the reaction chamber and the by-product removal chamber.   The apparatus for producing an organic thin film for a semiconductor device according to any one of claims 1 to 4, further comprising a sensor for detecting a film forming state of the organic thin film in the reaction chamber.   The apparatus for producing an organic thin film for a semiconductor device according to claim 1, wherein at least the reaction chamber, the fluid introduced into the reaction chamber, or the substrate stage further includes a heating unit.   The apparatus for producing an organic thin film for a semiconductor device according to any one of claims 1 to 6, wherein the means for removing the by-product is adsorption of a by-product by a packed molecular sieve or an ion exchange resin. Using the device according to any one of claims 1 to 7,
A first step of forming a first organic molecule layer by forming a chemical bond between a binding site on the surface of the substrate to be deposited and a binding site of a first organic molecule having one or more binding sites; A method for producing an organic thin film for a semiconductor device, comprising a step of removing a by-product generated in the first step.   When the first organic molecule has two or more binding sites, the first organic molecule that forms the first organic molecular layer after the first step is opposite to the film formation substrate. A second step of forming a second organic molecule layer by forming a chemical bond between the unreacted binding site on the side and the binding site of the second organic molecule having one or more binding sites. The manufacturing method of the organic thin film for semiconductor devices of Claim 8 including the process of removing the byproduct produced in the case of this 2nd process.   When the second organic molecule has two or more binding sites, the second organic molecule forming the second organic molecule layer after the second step has the film-forming substrate side, A third organic layer is laminated by forming a chemical bond between the unreacted binding site on the opposite side and the binding site of the third organic molecule having two or more binding sites. The manufacturing method of the organic thin film for semiconductor devices of Claim 9 in which a process includes the process of removing the by-product produced in this 3rd process.   After the third step, the third organic molecule forming the third organic molecule layer has an unreacted binding site on the side opposite to the substrate to be deposited, and further the second organic molecule layer and the first organic molecule layer. The method for producing an organic thin film for a semiconductor device according to claim 10, wherein the step of forming the third organic molecular layer is repeated at least once.   The method for producing an organic thin film for a semiconductor device according to any one of claims 8 to 11, wherein a by-product generated in any one of the first to third steps is water.   The method for producing an organic thin film for a semiconductor device according to claim 12, wherein the water is removed by an adsorbent selected from the group consisting of silica gel, activated alumina, calcium chloride, magnesium sulfate, molecular sieve, ion exchange resin, and zeolite. .   The binding site on the surface of the film-forming substrate is a hydroxy group, and the binding site of the first organic molecule is any one of a carboxy group, a phosphonic acid group, a silyl group, or a chloride thereof. The manufacturing method of the organic thin film for semiconductor devices as described in any one of these.   In the case where the first to third organic molecules have two or more binding sites, the binding sites of the same organic molecule are the same or different from each other, and the hydroxy group, amino group, formyl group, carboxy group or their protected groups are protected. The method for producing an organic thin film for a semiconductor device according to claim 8, wherein the organic thin film is a derivative.   The method for producing an organic thin film for a semiconductor device according to any one of claims 8 to 11, wherein a by-product generated in any one of the first to third steps is hydrochloric acid.   The method for producing an organic thin film for a semiconductor device according to claim 16, wherein the hydrochloric acid is removed by a neutralizing agent selected from an alkali solution, granular or powdery alkali, or an ion exchange resin.   18. The semiconductor device according to claim 8, wherein a bonding site on the surface of the film formation substrate is a hydroxy group, and a bonding site of the first organic molecule is a silyl chloride group or a carboxylic acid chloride group. A method for producing an organic thin film.

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