JP2004158805A - Process for fabricating organic semiconductor element and organic semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for fabricating an organic semiconductor element capable of forming a low resistance electrode conveniently, and to provide an organic semiconductor element having a low resistance electrode. <P>SOLUTION: After a gate electrode pattern is formed of a catalyst 2 using a print method at a part on a substrate 1 for forming a gate electrode 3A, the gate electrode 3A is formed by touching a plating agent causing electroless plating to the gate electrode pattern on the substrate 1 through action of the catalyst 2. After a source/drain electrode pattern is formed of the similar catalyst 2 at a part for forming a source/drain electrode 3B on an insulating layer 4 formed on the upper surface of the gate electrode 3A, similar plating agent is touched to the source/drain electrode pattern on the insulating layer 4 thus forming the source/drain electrode 3B. Finally, an organic semiconductor layer 5 is formed on the source/drain electrode 3B thus completing an organic semiconductor element. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an organic semiconductor device used for electronics, photonics, bioelectronics, and the like, and a method for manufacturing the same, and particularly relates to a technique effective for easily forming a low-resistance electrode.
[0002]
[Prior art]
Devices using organic semiconductors have milder film forming conditions than conventional inorganic semiconductor devices, and can be used to form semiconductor thin films on various substrates or at room temperature, reducing costs. In addition, flexibility is expected by forming a thin film on a polymer film or the like.
[0003]
As organic semiconductor materials, conjugated polymers and oligomers such as polyphenylenevinylene, polypyrrole, polythiophene and oligothiophene, as well as polyacene compounds such as anthracene, tetracene and pentacene have been studied.
In particular, it has been reported that polyacene compounds have high crystallinity due to strong intermolecular cohesion, and exhibit high carrier mobility and thereby excellent semiconductor device characteristics (for example, Non-Patent References 1 to 5).
[0004]
On the other hand, the conjugated polymer can form a thin film by applying this solution, so that it is expected to form a pattern by printing and to produce an element at low cost (for example, non-patented). Reference 6).
[0005]
[Non-patent document 1]
Sean et al., Science, 2000, 289, p. 559
[Non-patent document 2]
Sean et al., Science, 2000, 287, p1022
[Non-Patent Document 3]
"Journal of Applied Physics" by Jimitrakopouras et al., 1996, 80, p2501
[Non-patent document 4]
Shaun et al., Nature, 2000, 403, p408
[Non-Patent Document 5]
Cloak et al., IEEE Transactions on Electron Devices, 1999, 46, 1258.
[Non-Patent Document 6]
"Science" by Schilling House et al., 2000, 290, p2123
[0006]
[Problems to be solved by the invention]
By the way, as a method of forming an electrode of the above-mentioned organic semiconductor element, a method of forming an electrode pattern by etching or lift-off of a uniformly formed metal thin film (first method) or a method of printing a paint containing a metal filler is used. A method of forming an electrode pattern (second method), a method of forming an electrode pattern by printing a conductive polymer solution (third method), and the like have been proposed.
[0007]
However, in the first method, it is necessary to form a resist layer for forming a pattern and to remove the resist layer, so that there is a problem that a pattern forming process is complicated.
Further, in the second and third methods, there is a problem that the resistance of the electrode increases due to the effect of the contained binder.
Therefore, the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for manufacturing an organic semiconductor element capable of easily forming a low-resistance electrode and an organic semiconductor element having a low-resistance electrode. I have.
[0008]
[Means for Solving the Problems]
In order to solve such a problem, the present inventors have conducted intensive studies, and as a result, a catalyst and a plating agent that act on a plating agent to generate electroless plating act on a portion where an electrode of an organic semiconductor element is provided. It has been found that the above problem can be solved by providing electrodes by performing electroless plating and disposing one of the catalyst and the plating agent by a printing method.
[0009]
That is, in the method for manufacturing an organic semiconductor device according to claim 1 of the present invention, when manufacturing an organic semiconductor device including a substrate, an organic semiconductor layer, an insulating layer, and an electrode, the substrate, the organic semiconductor layer, and the After a catalyst that acts on a plating agent to cause electroless plating is provided by a printing method on at least one of the insulating layers where the electrode is to be provided, the plating agent is provided on the portion, and a non-conductive material is provided on the portion. It is characterized in that the electrode is provided by performing electrolytic plating.
[0010]
In the method for manufacturing an organic semiconductor device according to claim 2 of the present invention, when manufacturing an organic semiconductor device including a substrate, an organic semiconductor layer, an insulating layer, and an electrode, the substrate, the organic semiconductor layer, and the After arranging a catalyst that acts on a plating agent to cause electroless plating in a region including a portion where the electrode is provided in at least one of the insulating layers, the plating agent is arranged on the portion by a printing method, The electrode is provided by applying electroless plating to a portion.
[0011]
Further, in the method for manufacturing an organic semiconductor device according to claim 3 of the present invention, when manufacturing an organic semiconductor device including a substrate, an organic semiconductor layer, an insulating layer, and an electrode, the substrate, the organic semiconductor layer, and After a plating agent is disposed on at least one of the insulating layers where the electrode is to be provided by a printing method, a catalyst that acts on the plating agent to cause electroless plating is disposed on the portion, and a non-electrode is disposed on the portion. It is characterized in that the electrode is provided by performing electrolytic plating.
[0012]
Furthermore, the method for manufacturing an organic semiconductor device according to claim 4 of the present invention is a method for manufacturing an organic semiconductor device including a substrate, an organic semiconductor layer, an insulating layer, and an electrode. After arranging a plating agent in a region including a portion where the electrode is provided in at least one of the insulating layers, a catalyst that acts on the plating agent to cause electroless plating is arranged in the portion by a printing method, The electrode is provided by applying electroless plating to a portion.
[0013]
Further, in the method of manufacturing an organic semiconductor device according to claim 5 of the present invention, in the method of manufacturing an organic semiconductor device according to any one of claims 1 to 4, the plating agent includes a metal salt component and a reducing agent. And the reducing agent component is disposed after the metal salt component is disposed.
Furthermore, in the method of manufacturing an organic semiconductor device according to claim 6 of the present invention, in the method of manufacturing an organic semiconductor device according to any one of claims 1 to 4, the plating agent includes a metal salt component and a reducing agent. And the metal salt component is disposed after disposing the reducing agent component.
[0014]
Furthermore, in the method for manufacturing an organic semiconductor device according to claim 7 of the present invention, in the method for manufacturing an organic semiconductor device according to any one of claims 1 to 6, the catalyst may be Pd, Rh, Pt, It is characterized by comprising at least one compound selected from Ru, Os, and Ir, ions, or metal fine particles.
Furthermore, in the method for manufacturing an organic semiconductor device according to claim 8 of the present invention, in the method for manufacturing an organic semiconductor device according to any one of claims 1 to 7, the electrodes are made of Au, Cu, Ni, It is characterized by being made of at least one metal selected from Co and Fe or an alloy thereof.
[0015]
Further, according to a method for manufacturing an organic semiconductor device according to claim 9 of the present invention, in the method for manufacturing an organic semiconductor device according to any one of claims 1 to 8, the substrate is made of a ceramic material, a semiconductor material, It is characterized by being made of at least one selected from resin materials.
Furthermore, an organic semiconductor device according to a tenth aspect of the present invention provides a gate electrode, a source / drain electrode, an emitter electrode, and a collector electrode by the method of manufacturing an organic semiconductor device according to any one of the first to ninth aspects. , And at least one of the grid electrodes is formed.
[0016]
According to the method for manufacturing an organic semiconductor device of the present invention, after a catalyst that acts on a plating agent and causes electroless plating is disposed on a portion where an electrode is to be provided by a printing method, the plating agent is brought into contact with the portion where the electrode is to be provided. . Then, since the catalyst and the plating agent come into contact with each other, electroless plating is performed on the portion to form an electrode pattern. Therefore, it is possible to easily form an electrode pattern without performing a complicated process such as etching or lift-off which is necessary for forming a conventional electrode pattern.
[0017]
Further, according to the method for manufacturing an organic semiconductor element of the present invention, after arranging a catalyst which acts on a plating agent to cause electroless plating in a region including a portion where an electrode is provided, a plating agent is applied to a portion where an electrode is provided. Contact by printing method. Then, as described above, it is possible to easily form the electrode pattern without performing a complicated process such as etching or lift-off, which is required for forming with the conventional electrode pattern.
[0018]
Furthermore, according to the method for manufacturing an organic semiconductor element of the present invention, after a plating agent is disposed on a portion where an electrode is to be provided by a printing method, a catalyst which acts on the plating agent to cause electroless plating is provided on a portion where the electrode is provided. Make contact. Then, since the plating agent and the catalyst come into contact with each other, electroless plating is performed on the portion to form an electrode pattern. Therefore, it is possible to easily form an electrode pattern without performing a complicated process such as etching or lift-off which is necessary for forming a conventional electrode pattern.
[0019]
Further, according to the method of manufacturing an organic semiconductor element of the present invention, after a plating agent is provided in a region including a portion where an electrode is provided, a catalyst which acts on the plating agent and causes electroless plating to provide an electrode is provided. Is contacted by a printing method. Then, as described above, it is possible to easily form the electrode pattern without performing a complicated process such as etching or lift-off, which is required for forming with the conventional electrode pattern.
[0020]
Furthermore, according to the method for manufacturing an organic semiconductor device of the present invention, since an electrode pattern is formed by bringing a catalyst and a plating agent into contact with each other, conductive filler printing or conductive polymer, which is a conventional electrode pattern printing method, is used. It is possible to reduce the resistance of the electrode, which has been regarded as a problem in printing.
The method for manufacturing an organic semiconductor device of the present invention can be used for various electrodes of the organic semiconductor device and wiring of the device. Further, the present invention can be applied to interlayer bonding of a stacked body in which these elements and wirings are stacked.
[0021]
Further, according to the organic semiconductor device of the present invention, at least one of the gate electrode, the source / drain electrode, the emitter electrode, the collector electrode, and the grid electrode is formed by the method of manufacturing an organic semiconductor device of the present invention. It becomes possible to form a low-resistance electrode.
[About organic semiconductor elements]
Organic semiconductor devices are beneficially applicable in electronics, photonics, bioelectronics, and the like.
[0022]
Examples of such organic semiconductor devices include diodes, transistors, thin film transistors, memories, photodiodes, light emitting diodes, light emitting transistors, gas sensors, biosensors, blood sensors, immune sensors, artificial retinas, taste sensors, and the like.
[About the catalyst]
The catalyst that acts on the plating agent to cause electroless plating is composed of at least one compound selected from Pd, Rh, Pt, Ru, Os, and Ir, and ions thereof, or metal fine particles.
[0023]
Specifically, halides such as chlorides, bromides, and fluorides of the above elements, inorganic salts or composite salts such as sulfates, nitrates, phosphates, borates, and cyanides, carboxylate salts, and organic sulfones Alone or a mixture thereof selected from organic complex salts such as acid salts, organic phosphates, alkyl complexes, alkane complexes, alkene complexes, cyclopentadiene complexes, porphyrins and phthalocyanines, ions of these elements, metal fine particles of these elements Is applicable. In addition, it is also possible to apply a solution or a dispersion in which a surfactant or a resin binder is contained in a catalyst composed of an organic complex salt.
[About plating agent]
As the plating agent, for example, a solution in which metal ions to be deposited as electrodes are uniformly dissolved is used, and a reducing agent is contained together with a metal salt. Here, a solution is usually used, but the present invention is not limited to this as long as it causes electroless plating, and a gaseous or powdery plating agent can be applied.
[0024]
Specifically, as the metal salt, metal halides, nitrates, sulfates, phosphates, borates, acetates, tartrates, citrates and the like can be applied. As the reducing agent, hydrazine, hydrazine salt, borohalide salt, hypophosphite, hyposulfite, alcohol, aldehyde, carboxylic acid, carboxylate and the like can be applied. Elements such as boron, phosphorus, and nitrogen contained in these reducing agents may be contained in the electrode to be deposited.
[0025]
As the plating agent, a mixture of the metal salt and the reducing agent may be used, or the metal salt and the reducing agent may be separately applied. Here, in order to form the electrode pattern more clearly, it is preferable to use a mixture of a metal salt and a reducing agent. When a metal salt and a reducing agent are separately applied, a more stable electrode pattern can be formed by arranging the metal salt on the portion where the electrode is to be provided first and then arranging the reducing agent.
[0026]
If necessary, the plating agent may contain additives such as a buffer for pH adjustment and a surfactant. In addition, as a solvent used for the solution, an organic solvent such as alcohol, ketone, or ester may be added in addition to water.
Furthermore, the composition of the plating agent is composed of a metal salt of the metal to be deposited, a reducing agent, and an additive and an organic solvent as required, and the concentration and composition are adjusted according to the deposition rate. Can be. Also, the deposition rate can be adjusted by adjusting the temperature of the plating agent. Examples of the method of adjusting the temperature include a method of adjusting the temperature of the plating agent and a method of heating and cooling the substrate before immersion to adjust the temperature. Further, the thickness of the deposited metal thin film can be adjusted by the time of immersion in the plating agent.
[About printing method of catalyst or plating agent]
The printing method of the catalyst or the plating agent is not particularly limited. For example, various methods such as screen printing, letterpress, planographic printing, intaglio printing, ink jet printing, soft contact printing, and spray printing through a mask can be applied.
[About the method of contacting the plating agent to the catalyst arranged by the printing method, or the method of contacting the catalyst to the plating agent arranged by the printing method]
The method of bringing the plating agent (or the catalyst) into contact with the catalyst (or the plating agent) disposed by the printing method is not particularly limited. For example, immersion in the plating agent (or the catalyst) or the plating agent (or the catalyst) is performed. Spray spraying, or an ink jet method, screen printing, intaglio, planographic printing, letterpress printing or the like can be applied. Here, if the solute contained in the plating agent adheres to the substrate surface after the electrode pattern is deposited, it can be cleaned if necessary.
[About electrodes provided by electroless plating]
The electrode provided by performing electroless plating is made of at least one metal selected from Au, Ag, Cu, Ni, Co, and Fe, or an alloy thereof. Here, the metal includes an intermetallic compound.
[About organic semiconductor layer]
As a material constituting the organic semiconductor layer, various condensed polycyclic aromatic compounds and conjugated compounds can be applied.
[0027]
Examples of the condensed polycyclic aromatic compound include, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluminene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circum anthracene, bisantene, zethrene, heptasethrene , Pyranthrene, biolanthene, isobiolanthene, sarcobiphenyl, phthalocyanine, porphyrin and the like, and derivatives thereof.
[0028]
Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylenevinylene and its oligomer, polythienylenevinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, and quinone Examples include compounds, cyano compounds such as tetracyanoquinodimethane, fullerene, and derivatives or mixtures thereof.
[0029]
These organic semiconductor elements can be formed by a known method, for example, vacuum evaporation, MBE (Molecular Beam Epitaxy), sputtering, CVD (Chemical Vapor Deposition), laser evaporation, electron beam evaporation, Examples of the method include electrodeposition, spin coating, dip coating, screen printing, inkjet printing, and blade coating.
[About the board]
Various materials can be used as the material constituting the substrate, for example, ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, and silicon carbide, silicon, germanium, gallium arsenide, gallium phosphide, and gallium. A semiconductor substrate such as nitrogen, a resin substrate such as polyethylene terephthalate, polyester such as polynaphthalene terephthalate, polyethylene, polypropylene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, a cyclic polyolefin, polyimide, polyamide, polystyrene, etc. it can.
[0030]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view illustrating an example of the organic semiconductor device according to the present embodiment. FIG. 2 is a cross-sectional view showing one manufacturing step of the organic semiconductor device shown in FIG. Note that the present embodiment is an example of the present invention, and the present invention is not limited to the present embodiment.
[Example 1]
First, a hydrochloric acid solution of palladium (1% by mass of palladium chloride, 10% by mass of hydrochloric acid, and 20% by mass of isopropyl alcohol in water) is screen-printed as a catalyst 2 for generating electroless plating on a glass substrate as a substrate 1 and has a width of 50 μm. A gate electrode pattern was formed.
[0031]
Next, the glass substrate on which the gate electrode pattern was printed was dissolved in a nickel electroless plating bath (nickel chloride 0.1 mol / l, sodium hyposulfite 0.1 mol / l, tartaric acid 0.1 mol / l). Electroless plating was performed by immersion in a uniform solution) to form a gate electrode 3A made of a nickel thin film having a thickness of 130 nm on the surface of the glass substrate.
[0032]
Next, the surface of the glass substrate is sufficiently washed and dried with pure water, and then an N-methylpyrrolidone solution of polyacrylonitrile (2% by mass) is applied by spin coating, followed by drying. A polyacrylonitrile thin film was formed.
Next, a hydrochloric acid solution of palladium chloride is used as the catalyst 2 as described above, avoiding the gate electrode 3A printed on the glass substrate, and forming a dot pattern (a 200 μm × 500 μm strip pattern is formed adjacently at an interval of 30 μm width). Was screen printed to form source / drain electrode patterns.
[0033]
Next, the glass substrate having the source / drain electrode pattern formed on the surface was immersed in the same electroless nickel plating bath as described above to form a 110 nm thick nickel thin film source / drain electrode 3B. Here, the surface resistance of the nickel thin film after sufficiently washing and drying the surface of the glass substrate with pure water was 0.5Ω.
Next, on this glass substrate, a pentacene thin film was grown as the organic semiconductor layer 5 so as to have an average film thickness of 150 nm (film thickness measured by a quartz oscillator) at a substrate temperature of 50 ° C.
[0034]
As a result of evaluating a current-voltage characteristic by bringing a prober probe into contact with the gate electrode 3A and the source / drain electrode 3B of the field effect transistor thus configured, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained from the drain current saturation region is 0.6 cm. ² / Vsec.
[Example 2]
First, a rhodium chloride solution (1% by mass of rhodium chloride, 12 mol / l aqueous solution of hydrochloric acid 10% by mass) is used as a catalyst 2 for producing an electroless plating on a polyimide film (Kapton, manufactured by Toray DuPont) as a substrate 1 on a flexographic plate. Printing was performed to form a gate electrode pattern (a structure in which a 200 μm square pad was connected to the end of a line pattern having an electrode width of 20 μm and a length of 700 μm) in the same manner as in Example 1.
[0035]
Next, the polyimide film on which the gate electrode pattern was formed was immersed in the same electroless nickel plating bath as in Example 1 to form a gate electrode 3A made of a nickel thin film having a thickness of 80 nm on the surface of the polyimide film.
Next, after thoroughly washing and drying the surface of the polyimide film with pure water, a 200 nm-thick SiO 2 film is formed on the surface of the polyimide film as an insulating layer 4. ₂ The thin film was formed using a sputtering method.
[0036]
Next, this SiO ₂ On the surface of the thin film, a rhodium chloride solution was printed as a catalyst 2 as described above on a flexo plate to form a source / drain electrode pattern (width 200 μm, length 500 μm, gap 20 μm).
Next, the polyimide film having the source / drain electrode pattern formed on the surface was immersed in the electroless nickel plating bath used in Example 1 to form a 220 nm thick nickel thin film source / drain electrode 3B. Here, the surface resistance of the nickel thin film after sufficiently washing and drying the polyimide film with pure water was 0.2Ω.
[0037]
Next, a 1% by mass solution of regioregular polyhexylthiophene (manufactured by Aldrich) in toluene was applied as an organic semiconductor layer 5 to the surface of the polyimide film, and heated at 100 ° C. for 1 hour to evaporate and dry toluene. did.
As a result of evaluating the current-voltage characteristics of the gate electrode 3A and the source / drain electrodes 3B of the field-effect transistor thus configured as in Example 1, transistor characteristics were observed. At this time, the mobility of the polyhexylthiophene thin film obtained from the drain current saturation region was 0.008 cm. ² / Vsec.
[Example 3]
In Example 1, a rhodium chloride solution was used instead of the palladium chloride solution used as the catalyst 2 for causing electroless plating, and a gate electrode 3A made of a 230 nm-thick nickel thin film was formed in the same manner as in Example 1. Here, the surface resistance of the nickel thin film after sufficiently washing and drying the surface of the glass substrate with pure water was 0.5Ω.
[0038]
Next, through the same steps as in Example 1, a pentacene thin film deposited film and a source / drain electrode 3B were formed as the organic semiconductor layer 5.
As a result of evaluating the current-voltage characteristics of the gate electrode 3A and the source / drain electrodes 3B of the field effect transistor thus configured in the same manner as in Example 1, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained from the drain current saturation region was 0.5 cm. ² / Vsec.
[Example 4]
First, a hydrochloric acid solution of ruthenium chloride (aqueous solution of 1% by mass of ruthenium chloride, 10% by mass of hydrochloric acid, and 20% by mass of isopropyl alcohol) was screen-printed as a catalyst 2 for causing electroless plating on a polyester film as a substrate 1 and a width of 50 μm. Was formed.
[0039]
Next, the polyester film on which the gate electrode pattern was formed was placed in an electroless cobalt plating bath (0.1 mol / L of cobalt chloride, 0.1 mol / L of sodium hypophosphite, 0.1 mol / L of sodium potassium tartrate). (A dissolved homogeneous solution) to form a gate electrode 3A made of a 180 nm-thick cobalt thin film on the polyester film surface.
[0040]
Next, after thoroughly washing and drying the surface of the polyester film with pure water, a 200 nm-thick SiO 2 film is formed on the polyester film as an insulating layer 4. ₂ The film was formed using a sputtering method.
Next, avoiding the gate electrode pattern, ruthenium chloride was screen-printed as a catalyst 2 similar to the above into a dot pattern (a strip-shaped pattern of 200 μm × 500 μ was formed adjacently at an interval of 30 μm) to form a gate electrode pattern. Formed.
[0041]
Next, the polyester film on which the gate electrode pattern was formed was immersed in the same electroless cobalt plating bath as described above to form a source / drain electrode 3B made of a 210 nm-thick cobalt thin film. Here, the surface resistance of the cobalt thin film after sufficiently washing and drying the surface of the polyester film was 0.2Ω.
[0042]
Next, on the polyester film on which the source / drain electrode patterns were formed, a pentacene thin film was formed as the organic semiconductor layer 5 at a substrate temperature of 50 ° C. and an average film thickness of 150 nm (a film measured with a quartz oscillator) in the same manner as in Example 1. (Thickness).
As a result of evaluating the current-voltage characteristics of the gate electrode and the source / drain electrodes of the field effect transistor thus configured in the same manner as in Example 1, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained from the drain current saturation region was 0.6 cm. ² / Vsec.
[Example 5]
First, as in Example 1, a hydrochloric acid solution of palladium chloride (1% by mass of palladium chloride, 10% by mass of hydrochloric acid, 20% by mass of isopropyl alcohol, polyvinyl alcohol) as a catalyst 2 for causing electroless plating on a glass substrate as a substrate 1 An alcohol (1% by mass aqueous solution) was screen-printed to form a gate electrode pattern having a width of 50 μm.
[0043]
Next, an electroless gold plating bath (0.1 mol / L of potassium dicyanogold, 0.1 mol / L of sodium oxalate, 0.1 mol / L of sodium potassium tartrate) is dissolved in the glass substrate on which the gate electrode pattern is formed. To form a gate electrode 3A made of a gold thin film having a thickness of 90 nm on the surface of the glass substrate.
[0044]
Next, the surface of the glass substrate is sufficiently washed and dried with pure water, and then a 200 nm-thick SiO 2 is formed as the insulating layer 4. ₂ A thin film was formed using a sputtering method.
Next, a hydrochloric acid solution of palladium chloride was screen-printed as a catalyst 2 similar to that described above in a dot pattern (a strip pattern of 200 μm × 500 μ formed adjacently at a width of 30 μm), avoiding the gate electrode pattern. / Drain electrode pattern was formed.
[0045]
Next, the glass substrate on which the source / drain electrode pattern was formed was immersed in the same electroless gold plating bath as described above to form a source / drain electrode 3B made of a gold thin film having a thickness of 90 nm. Here, the surface resistance of the gold thin film after sufficiently washing and drying the surface of the glass substrate was 1.1Ω.
Next, on this glass substrate, a pentacene thin film was grown as the organic semiconductor layer 5 so as to have an average thickness of 150 nm (thickness measured by a quartz oscillator) at a substrate temperature of 50 ° C., as in Example 1. Was.
[0046]
As a result of evaluating the current-voltage characteristics of the gate electrode 3A and the source / drain electrodes 3B of the field-effect transistor thus configured in the same manner as in Example 1, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained from the drain current saturation region was 0.5 cm. ² / Vsec.
[Example 6]
First, as in Example 4, a hydrochloric acid solution of ruthenium chloride (1% by mass of ruthenium chloride, hydrochloric acid) was used as a catalyst 2 for producing electroless plating on a wholly aromatic polyamide film (Aramika, manufactured by Asahi Kasei Corporation) as a substrate 1. A 10% by mass, 20% by mass aqueous solution of isopropyl alcohol) was screen-printed to form a gate electrode pattern having a width of 50 μm.
[0047]
Next, the polyamide film on which the gate electrode pattern was formed was placed in an electroless platinum plating bath (potassium chloroplatinate 0.02 mol / l, hydrazine hydrochloride 0.05 mol / l, sodium potassium tartrate 0.1 mol / l). Was dissolved in a uniform solution) to form a gate electrode 3A made of a platinum thin film having a thickness of 100 nm on the surface of the polyamide film. Here, after sufficiently washing and drying the surface of this polyamide film with pure water, the surface resistance of the obtained platinum thin film was 0.2Ω.
[0048]
Next, on this polyamide film, a 200 nm-thick SiO ₂ The thin film was formed using a sputtering method.
Next, avoiding the gate electrode pattern, screen-printing a dot pattern (a strip-shaped pattern of 200 μm × 500 μ is formed adjacently at an interval of 30 μm) with a hydrochloric acid solution of ruthenium chloride as the same catalyst 2 as described above, Source / drain electrode patterns were formed.
[0049]
Next, the polyamide film on which the source / drain electrodes are formed is immersed in an electroless silver plating bath (silver nitrate 0.05 mol / l, sodium oxalate 0.1 mol / l, formaldehyde 0.05 mol / l). Then, a source / drain electrode 3B made of a silver thin film having a thickness of 250 nm was formed by patterning by electroless plating. Here, after sufficiently washing and drying the surface of the polyamide film with pure water, the surface resistance of the obtained silver film was 0.1Ω.
[0050]
Next, on this polyamide film, a pentacene thin film was grown as the organic semiconductor layer 5 at a substrate temperature of 50 ° C. to have an average film thickness of 150 nm (film thickness measured by a quartz oscillator), as in Example 1. Was.
As a result of evaluating the current-voltage characteristics of the gate electrode 3A and the source / drain electrodes 3B of the field-effect transistor thus configured in the same manner as in Example 1, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained from the drain current saturation region was 0.7 cm. ² / Vsec.
[Example 7]
First, a hydrochloric acid solution of osmium chloride (0.1% by mass of osmium chloride, 10% by mass of hydrochloric acid, and a 20% by mass aqueous solution of isopropyl alcohol) is screen-printed as a catalyst 2 for causing electroless plating on a polycarbonate film as a substrate 1, A gate electrode pattern having a width of 50 μm was formed.
[0051]
Next, the polycarbonate film on which the gate electrode pattern was formed was dissolved in an electroless copper plating bath (copper sulfate 0.1 mol / l, hydrazine hydrochloride 0.5 mol / l, sodium citrate 0.1 mol / l). (A uniform solution), and subjected to electroless plating to form a gate electrode 3A made of a copper thin film having a thickness of 250 nm on the surface of the polycarbonate film. Here, the surface resistance of the obtained copper thin film was 0.1Ω.
[0052]
Next, after sufficiently washing and drying the surface of the polycarbonate film with pure water, a 200 nm-thick SiO ₂ The thin film was formed using a sputtering method.
Next, a screen pattern of a hydrochloric acid solution of osmium chloride as a catalyst 2 similar to the above is printed on a dot pattern (a strip pattern of 200 μm × 500 μ is formed adjacently at a width of 30 μm), avoiding the gate electrode pattern. Source / drain electrode patterns were formed.
[0053]
Next, the polycarbonate film on which the source / drain electrode pattern was formed was subjected to the same electroless silver plating bath as in Example 6 (silver nitrate 0.05 mol / l, sodium oxalate 0.1 mol / l, formaldehyde 0.05 Mol / liter) and subjected to electroless plating to form a source / drain electrode 3B made of a silver thin film having a thickness of 250 nm. Here, after sufficiently washing and drying the surface of the polycarbonate film with pure water, the surface resistance of the obtained silver thin film was 0.1Ω.
[0054]
Next, a pentacene thin film was grown as an organic semiconductor layer 5 on the polycarbonate film at a substrate temperature of 50 ° C. with an average thickness of 150 nm (thickness measured by a quartz oscillator) as in Example 1.
As a result of evaluating the current-voltage characteristics of the gate electrode 3A and the source / drain electrodes 3B of the field effect transistor thus configured in the same manner as in Example 1, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained in the drain current saturation region was 0.5 cm. ² / Vsec.
Example 8
First, in the same manner as in Example 4, on a polyester film as the substrate 1, a hydrochloric acid solution of ruthenium chloride (1% by mass of ruthenium chloride, 10% by mass of hydrochloric acid, and 20% by mass of isopropyl alcohol) was screen-printed, and a gate having a width of 50 μm was formed. An electrode pattern was formed.
[0055]
Next, the polyester film on which the gate electrode pattern was formed was placed in an iron-cobalt electroless plating bath (ferrous chloride 0.1 mol / l, cobalt chloride 0.05 mol / l, sodium borohydride 0.1 mol). / Liter, a uniform solution in which 0.1 mol / liter of sodium potassium tartrate is dissolved), and subjected to electroless plating to form a gate electrode 3A made of a 300 nm-thick iron-cobalt thin film on the polyester film surface. Here, after sufficiently washing the polyester film surface with ethanol and drying, the surface resistance of the obtained iron-cobalt thin film was 2Ω.
[0056]
Next, a 200 nm-thick SiO 2 film was formed as an insulating layer 4 on the polyester film. ₂ The thin film was formed by a sputtering method.
Next, avoiding the gate electrode pattern, screen-printing a dot pattern (a strip-shaped pattern of 200 μm × 500 μ is formed adjacently at an interval of 30 μm) with a hydrochloric acid solution of ruthenium chloride as the same catalyst 2 as described above, Source / drain electrode patterns were formed.
[0057]
Next, this polyester film was immersed in the same electroless nickel plating bath as in Example 1 and subjected to electroless plating to form a source / drain electrode 3B made of a nickel thin film having a thickness of 210 nm. Here, after sufficiently washing and drying the surface of the polyester film with pure water, the obtained nickel thin film had a surface resistance of 0.2Ω.
[0058]
Next, on this glass substrate, a pentacene thin film was grown as the organic semiconductor layer 5 at a substrate temperature of 50 ° C. to an average film thickness of 150 nm (film thickness measured by a quartz oscillator) as in Example 1.
As a result of evaluating the current-voltage characteristics of the gate electrode 3A and the source / drain electrodes 3B of the field-effect transistor thus configured in the same manner as in Example 1, good transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained in the drain current saturation region was 0.5 cm. ² / Vsec.
[Example 9]
FIG. 3 is a cross-sectional view illustrating another manufacturing process of the organic semiconductor device of the present invention. In FIG. 3, the same parts as those in FIG.
[0059]
First, as shown in FIG. 3, a pentacene thin film is vacuum-deposited as an organic semiconductor layer 5 on a silicon substrate (n-type, oxide layer thickness 200 nm, oxide layer is not shown) whose surface is oxidized as the substrate 1. It was formed uniformly to a film thickness of 150 nm by the method.
Next, on the surface of the pentacene thin film, a hydrochloric acid solution of palladium chloride (1% by mass of palladium chloride, 10% by mass of hydrochloric acid, and 20% by mass of isopropyl alcohol) as a catalyst 2 for causing electroless plating in the same manner as in Example 1 Was screen-printed to form strip-shaped source / drain electrode patterns having a width of 50 μm.
[0060]
Next, the silicon substrate on which the source / drain electrode pattern was formed was placed in the same nickel electroless plating bath as in Example 1 (nickel chloride 0.1 mol / l, sodium hypochlorite 0.1 mol / l, tartaric acid 0). .1 mol / liter in a uniform solution) and subjected to electroless plating to form a source / drain electrode 3B made of a 430-nm-thick nickel thin film on the surface of the silicon substrate. Here, the surface resistance of the obtained nickel thin film was 0.3Ω.
[0061]
As a result of evaluating current-voltage characteristics using a prober probe for the source / drain electrodes 3B and the field-effect transistor using the silicon substrate as the gate electrode 3A, favorable transistor characteristics were observed. At this time, the mobility of the pentacene thin film obtained from the drain current saturation region was 0.9 cm. ² / Vsec.
[Example 10]
First, in the same manner as in Example 9, a tetracene thin film was uniformly formed as the organic semiconductor layer 5 to have a thickness of 200 nm on the surface silicon oxide substrate as the substrate 1 by using a vacuum evaporation method.
[0062]
Next, a source / drain electrode 3B made of a nickel thin film having a thickness of about 660 nm was formed in the same steps as in Example 9. Here, the surface resistance of the obtained nickel thin film was 0.1Ω.
Here, as in Example 9, the current-voltage characteristics were evaluated. As a result, the mobility of the tetracene thin film obtained from the drain current saturation region was 0.3 cm. ² / Vsec.
[0063]
【The invention's effect】
As described above, according to the method for manufacturing an organic semiconductor element of the present invention, after a catalyst that acts on a plating agent and causes electroless plating is disposed on a portion where an electrode is provided by a printing method, the plating agent is removed. By performing electroless plating while making contact with the portion, it is possible to easily form an electrode by electroless plating.
[0064]
Further, according to the method for manufacturing an organic semiconductor element of the present invention, after arranging a catalyst which acts on a plating agent to cause electroless plating in a region including a portion where an electrode is provided, a plating agent is applied to a portion where an electrode is provided. By performing the electroless plating in contact with a printing method, it is possible to easily form an electrode by the electroless plating.
Furthermore, according to the method of manufacturing an organic semiconductor device of the present invention, after a plating agent is disposed on a portion where an electrode is to be provided by a printing method, a catalyst that acts on the plating agent to cause electroless plating is contacted with this portion. By performing the electroless plating in this way, it is possible to easily form the electrode by the electroless plating.
[0065]
Further, according to the method of manufacturing an organic semiconductor device of the present invention, after a plating agent is provided in a region including a portion where an electrode is provided, a catalyst which acts on the plating agent and causes electroless plating to provide an electrode is provided. By performing electroless plating by contacting the electrodes with a printing method, it is possible to easily form electrodes by electroless plating.
Furthermore, according to the method for manufacturing an organic semiconductor device of the present invention, since a catalyst that acts on a plating agent to cause electroless plating and reacts with the plating agent to form an electrode by electroless plating, It is possible to reduce the resistance of the electrode.
Since the organic semiconductor element of the present invention is obtained by the above-described manufacturing method, it is possible to realize a reduction in the resistance of the electrode.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing one configuration example of an organic semiconductor device of the present invention.
FIG. 2 is a cross-sectional view showing one manufacturing step of the organic semiconductor device of the present invention.
FIG. 3 is a cross-sectional view showing another manufacturing process of the organic semiconductor device of the present invention.
[Explanation of symbols]
1 substrate
2 catalyst
3A Gate electrode
3B source / drain electrode
4 Insulating layer
5 Organic semiconductor layer

Claims (10)

When manufacturing an organic semiconductor element including a substrate, an organic semiconductor layer, an insulating layer, and an electrode,
The substrate, the organic semiconductor layer, and a portion of at least one of the insulating layers where the electrodes are to be provided, after disposing a catalyst that acts on a plating agent to cause electroless plating by a printing method, A method for manufacturing an organic semiconductor device, comprising: arranging an electrode by electroless plating on the portion; When manufacturing an organic semiconductor element including a substrate, an organic semiconductor layer, an insulating layer, and an electrode,
The substrate, the organic semiconductor layer, and a region including a portion where the electrode is provided in at least one of the insulating layers, after disposing a catalyst that acts on a plating agent to cause electroless plating, the plating agent is A method for producing an organic semiconductor device, comprising: arranging portions by printing, applying electroless plating to the portions, and providing the electrodes. When manufacturing an organic semiconductor element including a substrate, an organic semiconductor layer, an insulating layer, and an electrode,
The substrate, the organic semiconductor layer, and a portion of the at least one of the insulating layers where the electrodes are provided, after disposing a plating agent by a printing method, a catalyst that acts on the plating agent to cause electroless plating. A method for manufacturing an organic semiconductor device, comprising: arranging an electrode by electroless plating on the portion; When manufacturing an organic semiconductor element including a substrate, an organic semiconductor layer, an insulating layer, and an electrode,
The substrate, the organic semiconductor layer, and a region including at least one of the insulating layers provided with the electrode, after disposing a plating agent, a catalyst that acts on the plating agent to cause electroless plating, A method for producing an organic semiconductor device, comprising: arranging portions by printing, applying electroless plating to the portions, and providing the electrodes. The plating agent according to any one of claims 1 to 4, wherein the plating agent comprises a metal salt component and a reducing agent component, and after the metal salt component is arranged, the reducing agent component is arranged. A method for manufacturing an organic semiconductor device. 5. The plating method according to claim 1, wherein the plating agent includes a metal salt component and a reducing agent component, and the metal salt component is disposed after disposing the reducing agent component. 6. A method for manufacturing an organic semiconductor device. The organic catalyst according to any one of claims 1 to 6, wherein the catalyst comprises at least one compound selected from Pd, Rh, Pt, Ru, Os, and Ir, ions, or metal fine particles. A method for manufacturing a semiconductor element. 8. The organic semiconductor device according to claim 1, wherein the electrode is made of at least one metal selected from Au, Cu, Ni, Co, and Fe, or an alloy thereof. 9. Method. 9. The method according to claim 1, wherein the substrate is made of at least one selected from a ceramic material, a semiconductor material, and a resin material. 10. 10. A method of manufacturing an organic semiconductor device according to claim 1, wherein at least one of a gate electrode, a source / drain electrode, an emitter electrode, a collector electrode, and a grid electrode is formed. Organic semiconductor device.

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