JP4414145B2 - Conductive nanoparticle paste - Google Patents

Conductive nanoparticle paste Download PDF

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Publication number
JP4414145B2
JP4414145B2 JP2003060094A JP2003060094A JP4414145B2 JP 4414145 B2 JP4414145 B2 JP 4414145B2 JP 2003060094 A JP2003060094 A JP 2003060094A JP 2003060094 A JP2003060094 A JP 2003060094A JP 4414145 B2 JP4414145 B2 JP 4414145B2
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solvent
metal nanoparticles
paste
metal
dispersion
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JP2004273205A (en
Inventor
雅行 上田
頼重 松葉
憲明 畑
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ハリマ化成株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a conductive metal nanoparticle paste and a method for forming a fine wiring pattern using the same, and more specifically, using a screen printing method, an ink jet printing method, etc., such as a glass substrate, a ceramic substrate, etc. The present invention relates to a conductive metal nanoparticle paste used for forming a fine wiring pattern with low impedance corresponding to digital high-density wiring on a heat-resistant substrate, and a method for forming a fine wiring pattern using the conductive metal nanoparticle paste.
[0002]
[Prior art]
As one method for producing ultrafine metal particles having a very small particle diameter, at least an ultrafine metal particle having an average particle diameter of 100 nm or less, Japanese Patent Application Laid-Open No. 3-34211 is prepared by using a gas evaporation method. A dispersion liquid in which ultrafine metal particles of 10 nm or less are colloidally dispersed in a dispersion solvent and a method for producing the same are disclosed. In addition, in JP-A-11-319538, etc., metal ultrafine particles having an average particle diameter of several nanometers to several tens of nanometers are prepared by a wet process using a reduction precipitation method using an amine compound for reduction, and colloidally formed. Dispersed ones and methods for making them are disclosed. The ultrafine metal particles having an average particle diameter of several nanometers to several tens of nanometers prepared by a wet method disclosed in Japanese Patent Application Laid-Open No. 11-319538, etc. are made of a polymer resin or the like in order to maintain a colloidal state. It is what is covered.
[0003]
In general, ultrafine metal particles having an average particle diameter of several nanometers to several tens of nanometers are sintered at a temperature much lower than the melting point (for example, ultrafine particles having a clean surface at 200 ° C. or lower for silver). It is known. This is because in ultrafine metal particles, if the particle size is sufficiently reduced, the proportion of the high energy state atoms present on the particle surface will increase and the surface diffusion of metal atoms will be so large that it cannot be ignored. As a result, due to this surface diffusion, the interface between the particles is stretched and sintered.
[0004]
When the metal nanoparticles having an average particle diameter of about several nanometers to several tens of nanometers are brought into direct contact with each other, fusion occurs with each other, and ultrafine particles aggregate to lose uniform dispersibility in the dispersion solvent. Therefore, the surface of the metal nanoparticles is uniformly coated with alkylamine or the like, and the surface is provided with a surface-coated molecular layer, so that the metal nanoparticles exhibit high dispersibility. In addition to the metal nanoparticles, metal fine powder having an average particle size of 0.5 to 20 μm is used as a metal filler, and the metal nanoparticles are densely filled in the gaps between the metal fillers having relatively large particle sizes. By forming a packed layer of low-temperature sintered body and bringing the metal fine powders into physical contact with each other by curing shrinkage of the binder resin such as epoxy resin, it is possible to obtain good electrical conduction. Application to a conductive metal paste that can achieve the properties has also been proposed.
[0005]
In the conductive metal paste in which the metal fine powder filler and the metal nanoparticles are used in combination, a surface coating molecule such as an alkylamine that coats and protects the surface of the metal nanoparticles is used at a heating temperature, for example, 250 ° C. In order to react with surface coating molecules such as alkylamines when such a degree is reached and to promote their removal, acid anhydrides, carboxylic acids or their derivatives, which are reactive to amino groups when heated, are pasted. Is incorporated in the binder resin composition constituting Prior to the progress of the low-temperature firing treatment, surface coating molecules such as alkylamines react with the mixed acid anhydrides and leave the surface of the metal nanoparticles, and the surfaces of the metal nanoparticles are in contact with each other and used together. It will be in the state with which it filled with the clearance gap between metal fine powder. Then, along with low-temperature firing, the metal nanoparticles constitute a dense sintered body layer, and as a result of the thermal curing and shrinkage of the epoxy resin used for the binder resin, the gaps between the metal fine powders are compressed. Thus, a conductor layer is formed in which the sintered body layer in which the metal nanoparticles are densely packed is formed in the gaps between the metal fine powders. That is, as a result of the metal nanoparticles forming a dense sintered body layer, there is a reduction in the gap space due to aggregation, but it is balanced with the total volume compression amount caused by the hardening and shrinkage of the binder resin. For example, when using a conductive silver paste in which silver fine powder and silver nanoparticles are used together in a conductive layer in which a sintered metal layer in which metal nanoparticles are dense in the gaps between the obtained metal fine powders is used. The volume resistivity is 5 × 10-6  Ω · cm to 10 × 10-6  Ω · cm is achieved.
[0006]
The conductive metal paste using the metal fine powder and the metal nanoparticles in combination can produce a conductor layer exhibiting much superior conductivity as compared with the conventional conductive metal paste using only the metal fine powder. Although it is possible to use it for the formation of extremely fine wiring patterns, the limit of the drawing accuracy is governed by the average particle diameter of the metal fine powder used, so the conventional conductive metal paste It did not substantially exceed the limit of.
[0007]
For the purpose of forming an extremely fine wiring pattern, a conductive metal paste using only metal nanoparticles as a conductive medium and blended in a binder resin composition has also been proposed. Since this conductive metal paste uses only metal nanoparticles as the conductive medium, the limit of the drawing accuracy is markedly improved. Further, in the obtained fine wiring pattern, the conductor layer made of a sintered body layer of metal nanoparticles, which is solidified by the binder resin and fixed on the substrate surface, has a volume resistivity of 3 × 10.-Five  Ω · cm to 10 × 10-Five  Good electrical conductivity of no particular problem has been achieved in practical use of about Ω · cm.
[0008]
[Patent Document 1]
JP-A-3-34211
[Patent Document 2]
JP-A-11-319538
[0009]
[Problems to be solved by the invention]
At present, with the miniaturization of various electronic devices and electronic components, there is a demand for further miniaturization of circuit wiring patterns formed on a wiring board. Furthermore, a conductive layer using a conductive metal paste is used to form a wiring pattern. For example, a fine wiring pattern with a minimum line width / wiring interval of 20 μm / 20 μm can be obtained with good reproducibility. There is a demand for production with stable energization characteristics.
[0010]
For example, when the minimum line width / wiring interval is about 50 μm / 50 μm, in the conductive metal paste using the above-mentioned metal fine powder filler and metal nanoparticles in combination, for example, a metal fine powder having an average particle diameter of about 1 μm By using the filler, it is possible to achieve the required drawing accuracy. On the other hand, when the minimum line width / wiring interval is a fine wiring pattern reaching 20 μm / 20 μm, use of a conductive metal paste that uses only metal nanoparticles as a conductive medium is necessary to achieve the drawing accuracy required for the wiring pattern. However, when using a conductive metal paste in which the metal nanoparticles described above are blended in the binder resin composition, the volume specific resistivity of the obtained conductor layer is the upper limit of the target current-carrying characteristics, 10x10-Five  Although it is Ω · cm or less, it is a more preferable range for achieving stable energization characteristics with a high yield, 10 × 10-6  The value of Ω · cm or less has not been reached. That is, as the minimum line width decreases, unless the coating thickness of the conductive metal paste suitable for drawing such a fine pattern is also reduced, a reduction in drawing accuracy due to paste bleeding and sagging cannot be avoided. Therefore, the cross-sectional area of the obtained conductor layer shows a decrease in which the decrease in the minimum line width and the decrease in the film thickness synergistically affect each other, so that the volume resistivity is reduced to such an extent that the decrease can be offset. Is more desirable.
[0011]
The present invention solves the above-mentioned problems, and an object of the present invention is to achieve high drawing accuracy that can be used for forming an extremely fine wiring pattern, for example, the minimum line width / wiring interval reaches 20 μm / 20 μm. A conductive metal nanoparticle paste that uses only metal nanoparticles as a conductive medium, can form a wiring pattern, and the volume resistivity of the obtained conductor layer is 10 × 10 with high reproducibility.-6  A conductive metal nanoparticle paste that can be used for forming a fine wiring pattern with a low impedance that can be in a suitable range of Ω · cm or less, and a method for forming a fine wiring pattern using the conductive metal nanoparticle paste It is to provide. More specifically, an object of the present invention is to use a conductive metal nanoparticle paste to heat-treat a coating layer drawn on a fine wiring pattern at a low temperature so that the metal nanoparticles are sintered at a low temperature. When the bonded conductor layer is formed, the volume resistivity of the obtained sintered conductor layer is 10 times the volume resistivity obtained in the bulk state of the metal material constituting the metal nanoparticles. Within 5 times, preferably within 5 times, with high reproducibility, stable and good current carrying characteristics, and the ability to form highly reliable fine wiring. It is in providing a functional nanoparticle paste.
[0012]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors utilize a conductive metal paste in which only the above-mentioned metal nanoparticles are blended in a binder resin composition as a conductive medium in the process of advancing research. In this case, the volume resistivity of the obtained conductor layer is significantly higher than 10 times the volume resistivity obtained in the bulk state of the metal material constituting the metal nanoparticles, and is usually 3 × 10.-Five  Ω · cm to 10 × 10-Five  The factors that were kept in the range of Ω · cm were examined. In the study, in a conductive metal paste containing a metal fine powder filler having an average particle size of about 0.5 μm, the binder resin component usually causes heat curing and shrinkage, thereby causing a gap between these metal fine powder fillers. Although it is an essential component that fulfills the role of close mechanical contact, the binder that condenses the entire conductor layer, and the adhesive resin that adheres to the substrate surface, it is also close in the film thickness direction. When the dense sintered body layers of the metal nanoparticles to be connected are integrally formed, the mechanical contact between the metal nanoparticles located on the surface of each sintered body is made dense in the sintered bodies. It has been found that the binder resin component is no longer an essential component, and it is not necessary to use the function of the binder and the function of the binder that condenses the entire conductor layer. Moreover, in the conductive metal paste which mix | blended only the metal nanoparticle mentioned above in a binder resin composition as a conductive medium, a metal nanoparticle is contained in the organic solvent which hold | maintains binder resin contained in a proper density | concentration. Acid anhydrides, etc., used to remove the surface coating molecular layer are also dissolved, but they are contained at the stage of removal by reacting the coating molecules with acid anhydrides, etc. by proceeding with heat treatment. It was also found that the fluidity of the liquid phase component in the paste coating layer decreases at an accelerated rate as the thermosetting reaction in the binder resin component also proceeds gradually. The decrease in fluidity of the liquid phase component in the paste coating layer is useful for suppressing the sagging and spreading of fine patterns during heating, but is caused by aggregation and volume shrinkage due to low-temperature firing between metal nanoparticles. It has also been found that it becomes a factor that delays the progress of. That is, between the metal nanoparticles that are densely laminated, the coating molecular layer on the surface is removed and the metal surfaces of the fine spherical particles are in direct contact with each other, so that low-temperature sintering proceeds. When the thermosetting reaction of the binder resin composition that fills the gap space of the metal particles proceeds, the fluidity of this liquid phase component decreases, and as a result of the low-temperature sintering, aggregation and volume shrinkage occur. Although it is necessary to squeeze out the liquid phase component which occupies space, the fluidity | liquidity fall of a liquid phase component makes this squeeze difficult. Therefore, since the progress of aggregation and volume shrinkage due to low-temperature firing between metal nanoparticles is interrupted when reaching a certain level, a dense sintered body layer between metal nanoparticles is formed, and a uniform film is formed. Although the thick shape and good conductivity were obtained, it was clarified that the volume resistivity of the obtained conductor layer does not reach a sufficiently low level to the extent that it is comparable to the bulk metal. In addition, the obtained conductor layer is composed of a dense sintered body layer between metal nanoparticles and a binder resin for fixing the same, and the volume ratio of the sintered body metal contained per unit volume is limited. When applying to a fine wiring pattern corresponding to a high current density, it was clarified that there is a limit to the thermal conductivity that contributes to the dissipation of heat generated in the wiring.
[0013]
Based on the above findings, the present inventors proceeded with further studies, and reduced or eliminated factors that interrupt the progress of aggregation and volume shrinkage due to low-temperature firing between metal nanoparticles. Since the dense sintered body layer between the particles becomes denser, a binder for condensing the entire conductor layer is completely unnecessary, and the volume specific resistivity of the obtained conductor layer is greatly reduced. Also found that it would be possible. Specifically, when making a conductive nanoparticle paste comprising metal nanoparticles, the surface of the metal nanoparticles is provided with a coating molecular layer, but the surface density is within an appropriate range, while the dispersion solvent is When heated, these coating molecules elute and function as a free solvent that detaches from the surface.High solubilityIn addition, in a low-temperature firing treatment, the dispersion solvent is heated in a dispersion solvent by using an organic solvent having a structure that does not contain a binder resin component or an acid anhydride that exhibits reactivity with a coating agent molecule. As a result of the dissolution and separation of the coating agent molecules, low temperature firing between the metal nanoparticles starts, and the fluidity of the dispersion solvent does not decrease. It is not a factor to suppress the progress, and the dense sintered body layer formed between the metal nanoparticles becomes denser, so that the volume resistivity of the obtained conductor layer is remarkably reduced. I found. At that time, the dispersion solvent uses a high-boiling liquid organic substance that functions as a free solvent that enables elution and detachment of the coating agent molecules during the heating, and finally ends the low-temperature baking treatment. Then, it was confirmed that it would be possible to gradually evaporate, and the present inventors completed the present invention based on these series of findings.
[0014]
That is, the conductive nanoparticle paste according to the present invention is a conductive nanoparticle paste comprising metal nanoparticles,
The average particle diameter of the metal nanoparticles is selected in the range of 1 to 100 nm,
The conductive nanoparticle paste is a dispersion obtained by uniformly dispersing the metal nanoparticles in a dispersion solvent,
The surface of the metal nanoparticle contains a nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with the metal element contained in the metal nanoparticle, and is coordinated by a lone electron pair possessed by these atoms. Covered with one or more compounds having a group capable of bonding;
The total of one or more compounds having a group containing nitrogen, oxygen, or sulfur atoms with respect to 100 parts by mass of the metal nanoparticles, containing 10 to 30 parts by mass,
When the dispersion solvent is heated to 100 ° C. or more, 50 parts by mass or more of the compound having a group containing nitrogen, oxygen, or sulfur atoms covering the surface of the metal nanoparticles can be dissolved per 100 parts by mass of the dispersion solvent. , An organic solvent having high solubility, or a mixed solvent composed of two or more liquid organic substances,
8 to 220 parts by mass of the dispersion solvent with respect to 100 parts by mass of the metal nanoparticles,
One kind of organic solvent constituting the dispersion solvent or two or more kinds of liquid organic substances react with the compound having a group containing nitrogen, oxygen or sulfur atoms in the temperature range of 20 ° C. to 300 ° C. Without showing sex
The compound having a group containing nitrogen, oxygen, or sulfur atom has a boiling point in the range of 150 ° C. to 300 ° C. and a melting point of 20 ° C. or less,
One kind of the organic solvent constituting the dispersion solvent, or two or more kinds of liquid organic substances each have a boiling point in the range of 150 ° C. to 300 ° C. and a melting point of 20 ° C. or less. Nanoparticle paste. For example, the compound having a group containing nitrogen, oxygen, or sulfur atoms that coats the surface of the metal nanoparticles is preferably a monoalkylamine.
[0015]
In the conductive nanoparticle paste according to the present invention, the average particle size of the metal nanoparticles is more preferably selected in the range of 2 to 10 nm.
[0016]
In addition, as the metal nanoparticles,
From nanoparticles composed of gold, silver, copper, platinum, palladium, nickel, and aluminum metals, or alloys composed of two or more metals selected from gold, silver, copper, platinum, palladium, nickel, and aluminum Nanoparticles can be used.
[0017]
In addition, when the conductive nanoparticle paste according to the present invention is used as a paste for inkjet printing,
The liquid viscosity (20 ° C.) of the paste is selected in the range of 5 mPa · s to 30 mPa · s,
The volume ratio of the dispersion solvent in the paste is more preferably selected in the range of 60 to 80% by volume. In addition, when the conductive nanoparticle paste according to the present invention is a paste for screen printing,
The liquid viscosity (25 ° C.) of the paste is selected in the range of 50 Pa · s to 200 Pa · s,
The volume ratio of the dispersion solvent in the paste is more preferably selected in the range of 25 to 45% by volume.
[0018]
Furthermore, the present invention also provides an invention of a method for forming a fine wiring pattern with good conductivity using the above-described conductive nanoparticle paste according to the present invention,
That is, the method for forming a fine wiring pattern according to the present invention is a method for forming a fine wiring pattern with good conductivity, comprising a sintered body layer of metal nanoparticles on a substrate,
Forming a coating layer of the fine wiring pattern to be drawn on the substrate surface using a paste-like dispersion liquid containing metal nanoparticles selected in an average particle size range of 1 to 100 nm;
A step of firing the metal nanoparticles contained in the coating layer to form a sintered body layer between the metal nanoparticles;
As the paste-like dispersion containing the metal nanoparticles, the conductive nanoparticle paste according to the present invention in any of the above-described forms,
The formation of a sintered body layer between the metal nanoparticles is performed by heating the coating layer to a temperature not exceeding 300 ° C.
When heating in the baking treatment, the compound having a group containing nitrogen, oxygen, and sulfur atoms that coats the surface of the metal nanoparticles is composed of a highly soluble organic solvent, or two or more liquid organic substances. In the dispersion solvent using the mixed solvent, dissociation and elution from the surface of the metal nanoparticles are achieved, and the surface contact between the metal nanoparticles is achieved,
A method for forming a fine wiring pattern, wherein the metal nanoparticles are sintered with each other and the dispersion solvent is removed by evaporation.
[0019]
In the method for forming a fine wiring pattern according to the present invention, it is possible to use a screen printing method or an ink jet printing method when drawing a coating layer of a fine wiring pattern using the paste dispersion liquid. ,
When ink-jet printing is used for drawing, it is desirable to use the ink-jet printing paste according to the present invention, which is prepared as described above, and when screen printing is used for drawing. It is preferable to use the paste for screen printing according to the present invention prepared in the above-described configuration.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0021]
The low-temperature sintered conductive metal nanoparticle paste for ultrafine circuit printing of the present invention is particularly for ultrafine printing used for forming extremely fine circuits with low impedance corresponding to digital high density wiring. The average particle diameter of the metal nanoparticles contained as the conductive medium is selected in the range of 1 to 100 nm according to the target line width of the ultra fine printing and the film thickness after the heat-firing treatment. Preferably, the average particle size is selected in the range of 2 to 10 nm. By selecting the average particle diameter of the contained metal nanoparticles themselves within the above range, application to an extremely fine line width pattern is possible by a known method such as a screen printing method or an ink jet printing method.
[0022]
Thus, when using extremely fine metal nanoparticles, in the form of dry powder, when the particles come into contact with each other, each metal nanoparticle adheres to cause aggregation. The present invention is not suitable for the purpose of high density printing. In order to prevent aggregation of the nanoparticles, a coating layer made of a low molecule is provided on the surface of the metal nanoparticles, and a material dispersed in a liquid is used. That is, in the conductive nanoparticle paste of the present invention, the surface of the metal nanoparticles is oxidized so that the coating film is heat-treated to cause fusion between the metal nanoparticles contained in the contact interface. A film in which the film is substantially absent is used.
[0023]
Specifically, the surface of the metal nanoparticle used as a raw material has a group containing nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with the metal element contained in the metal nanoparticle. It is set as the state coat | covered with 1 or more types of compounds. That is, the metal surface of the metal nanoparticle is uniformly formed by using one or more compounds having a group containing nitrogen, oxygen, or sulfur atom as a group capable of coordinately bonding with the metal element contained in the metal nanoparticle. For example, a dispersion of metal nanoparticles dispersed in one or more organic solvents is used while maintaining a state of being covered with, for example, an amine compound having one or more terminal amino groups.
[0024]
The role of this coating layer is that the metal nanoparticles are not in direct contact with each other until the heat treatment is performed, so that aggregation of the metal nanoparticles contained in the conductive paste is suppressed, The anti-agglomeration resistance is maintained at a high level. In addition, even when it is in contact with water or oxygen molecules in the atmosphere, such as when coating, the surface of the metal nanoparticles is already covered with a coating layer, leading to direct contact with water molecules and oxygen molecules. Therefore, it also has a function of suppressing the formation of a natural oxide film on the surface of the metal ultrafine particles due to moisture and oxygen molecules in the atmosphere.
[0025]
The compound used for the uniform coating of the surface of the metal nanoparticle uses a group having a lone electron pair on a nitrogen, oxygen, or sulfur atom when forming a coordinate bond with the metal element. For example, an amino group is mentioned as a group containing a nitrogen atom. Examples of the group containing a sulfur atom include a sulfanyl group (—SH) and a sulfide type sulfanediyl group (—S—). Examples of the group containing an oxygen atom include a hydroxy group (—OH) and an ether type oxy group (—O—).
[0026]
A representative example of the compound having an amino group that can be used is an alkylamine. Such an alkylamine is preferably one that does not desorb in a normal storage environment, specifically in a range not reaching 40 ° C., in a state in which a coordinate bond is formed with the metal element, and has a boiling point. A range of 60 ° C. or higher, preferably 100 ° C. or higher, and more preferably 150 ° C. or higher is preferable. On the other hand, when conducting the heat treatment of the conductive nanoparticle paste, it is necessary to be able to evaporate together with the dispersion solvent after detachment from the surface of the metal nanoparticles, and at least the boiling point Is preferably in the range not exceeding 300 ° C, usually in the range of 250 ° C or less. For example, as the alkylamine, those having an alkyl group selected in the range of C8 to C18 and having an amino group at the end of the alkyl chain are used. For example, alkylamines in the range of C8 to C18 have thermal stability, and the vapor pressure near room temperature is not so high. When stored at room temperature or the like, the content is maintained within a desired range. It is preferably used in terms of handling properties, such as being easy to control.
[0027]
In general, in forming such a coordination bond, the primary amine type is preferable because it shows a higher binding ability, but secondary amine type and tertiary amine type compounds can also be used. is there. In addition, compounds in which two or more adjacent amino groups are involved in bonding, such as 1,2-diamine type and 1,3-diamine type, can also be used. A chain amine compound containing a polyoxyalkyleneamine type ether type oxy group (—O—) in the chain can also be used. In addition to the terminal amino group, a hydrophilic end group, for example, a hydroxyamine having a hydroxyl group, such as ethanolamine, can also be used.
[0028]
Moreover, alkanethiol can be mentioned as a typical example of a compound having a sulfanyl group (—SH) that can be used. In addition, such alkanethiol is preferably in a state in which a coordinate bond is formed with a metal element and does not desorb in a normal storage environment, specifically, in a range not reaching 40 ° C., and has a boiling point. A range of 60 ° C. or higher, preferably 100 ° C. or higher, and more preferably 150 ° C. or higher is preferable. On the other hand, when conducting the heat treatment of the conductive nanoparticle paste, it is necessary to be able to evaporate together with the dispersion solvent after detachment from the surface of the metal nanoparticles, and at least the boiling point Is preferably in the range not exceeding 300 ° C, usually in the range of 250 ° C or less. For example, as the alkanethiol, C4 to C20 is used as the alkyl group, and more preferably selected within the range of C8 to C18, and an alkyl chain having a sulfanyl group (—SH) is used. For example, alkanethiols in the range of C8 to C18 have thermal stability, and the vapor pressure near room temperature is not so high. When stored at room temperature or the like, the content is maintained and controlled within a desired range. It is preferably used in terms of handling properties, such as being easy to do. In general, primary thiol type compounds are preferred because they exhibit higher binding ability, but secondary thiol type and tertiary thiol type compounds can also be used. In addition, those in which two or more sulfanyl groups (—SH) are involved in binding, such as 1,2-dithiol type, can also be used.
[0029]
Moreover, alkanediol can be mentioned as a representative of the compound which has a hydroxyl group which can be utilized. Examples include glycols such as ethylene glycol, diethylene glycol, and polyethylene glycol. In addition, such alkanediols are preferably those that do not desorb in a normal storage environment, specifically in a range that does not reach 40 ° C., in a state in which a coordinate bond is formed with the metal element. A range of 60 ° C. or higher, usually 100 ° C. or higher, and more preferably 150 ° C. or higher is preferable. On the other hand, when conducting the heat treatment of the conductive nanoparticle paste, it is necessary to be able to evaporate together with the dispersion solvent after detachment from the surface of the metal nanoparticles, and at least the boiling point Is preferably in the range not exceeding 300 ° C, usually in the range of 250 ° C or less. For example, those involving two or more hydroxy groups, such as 1,2-diol type, can be used more suitably.
[0030]
In the conductive metal nanoparticle paste of the present invention, the contained metal nanoparticles contain the above-mentioned nitrogen, oxygen or sulfur atoms, and compounds having groups capable of coordinative bonding by lone electron pairs of these atoms In the state which has 1 or more types as a surface coating layer, it is disperse | distributed in the dispersion solvent. Such a surface coating layer has an appropriate coating ratio so that an excessive amount of coating molecules does not exist as long as it can function to avoid direct contact between the surfaces of the metal nanoparticles during storage. select. That is, when heated and fired at a low temperature, the coating layer molecules can be eluted and separated in the coexisting dispersion solvent, and the content can be achieved and the coating protection function can be achieved. Select the coverage ratio. For example, when the conductive metal nanoparticle paste is prepared, the above-described nitrogen, oxygen, or sulfur atom is contained in 100 parts by mass of the metal nanoparticle, and the coordinated bond by the lone electron pair of these atoms is present. It is preferable to select the coating ratio so that one or more compounds having possible groups generally contain 10 to 30 parts by mass, more preferably 10 to 20 parts by mass as a sum. In addition, with respect to 100 parts by mass of the metal nanoparticle, the surface of the metal nanoparticle includes a nitrogen atom, an oxygen atom, or a sulfur atom, and a group capable of coordinative bonding by a lone electron pair possessed by these atoms. The sum total of one or more compounds also depends on the average particle size of the metal nanoparticles. That is, when the average particle diameter of the metal nanoparticles becomes smaller, the total surface area of the nanoparticle surface per 100 parts by mass of the metal nanoparticles increases in inverse proportion to the average particle diameter. Need a higher ratio. Taking that point into consideration, when the average particle diameter of the metal nanoparticles is selected within the range of 2 to 10 nm, the sum of the coating molecules covering the surface with respect to 100 parts by mass of the metal nanoparticles is: It is preferable to select in the range of 10 to 30 parts by mass.
[0031]
The organic solvent used as a dispersion solvent contained in the conductive metal nanoparticle paste of the present invention has a role of dispersing the metal nanoparticles provided with the above-mentioned surface coating layer at room temperature, but when heated, Exhibits a function as a solvent capable of eluting and releasing the coating layer molecules on the surface of the metal nanoparticles. At that time, in the elution stage of the coating layer molecules in the heated state, a high-boiling liquid organic substance in which transpiration does not proceed remarkably is used. Accordingly, when heated to 100 ° C. or higher, preferably, 50 parts by mass or more of the compound having a group containing nitrogen, oxygen, or sulfur atoms covering the surface of the metal nanoparticles can be dissolved per 100 parts by mass of the dispersion solvent. In addition, one kind of organic solvent having high solubility or a mixed solvent composed of two or more kinds of liquid organic substances is used. In addition, when heated to 100 ° C. or higher, one kind of organic solvent capable of forming a compatible solution of any composition with respect to the compound having a group containing nitrogen, oxygen, or sulfur atoms that coats the surface of the metal nanoparticles, or It is more preferable to use a mixed solvent composed of two or more kinds of liquid organic substances, particularly those exhibiting high compatibility.
[0032]
Specifically, the coating layer molecule contains a nitrogen, oxygen, or sulfur atom, and is coordinated on the surface of the metal nanoparticle by using a group capable of coordinative bonding by a lone electron pair possessed by these atoms. The organic solvent contained in the dispersion solvent can maintain the dispersion state of the metal nanoparticles covered with the coating layer molecules or be compatible with each other by utilizing the affinity for the remaining hydrocarbon chain and skeleton. Demonstrate the ability to achieve The affinity of the coating layer molecules due to coordinate binding to the surface of the metal nanoparticles is stronger than physical adsorption, but rapidly decreases with heating, while accompanying the temperature increase, As a result of the increase in the solubility characteristic of the organic solvent, when the temperature is higher than the equilibrium temperature, the detachment and elution of coating layer molecules are accelerated at an accelerated rate as the temperature rises. Eventually, almost all of the coating layer molecules on the surface of the metal nanoparticles are dissolved in the dispersion solvent present during heating, and substantially no coating layer molecules remain on the surface of the metal nanoparticles. Is achieved.
[0033]
Of course, since the elution process of the coating layer molecules from the surface of the metal nanoparticles and the reattachment process are in a thermal equilibrium relationship, the solubility of the coating layer molecules in the dispersion solvent during heating is sufficiently high. desirable. Even if the coating layer molecules are eluted into the dispersion solvent infiltrating the gaps between the stacked metal nanoparticles, the coating layer molecules are transferred from the inside of the coating layer to the outer edge through the narrow gaps. It takes more time to spread and flow out. In order to effectively suppress the reattachment of the coating layer molecules during the progress of the sintering between the metal nanoparticles, it is desirable to use the organic solvent exhibiting the high solubility described above.
[0034]
That is, the organic solvent used as a dispersion solvent shows affinity for the coating layer molecules on the surface of the metal nanoparticles, but the coating layer molecules on the surface of the metal nanoparticles easily elute into the organic solvent near room temperature. Although it does not occur, the solubility increases with heating, and when the coating layer molecules can be eluted into the organic solvent when heated to 100 ° C. or higher, those are used. For example, a compound that forms a coating layer on the surface of metal nanoparticles, for example, an amine compound such as an alkylamine contains a chain hydrocarbon group that has an affinity with the alkyl group portion, It is preferable to select a nonpolar solvent or a low polarity solvent instead of a solvent having such a high polarity that the solubility of the amine compound is too high and the coating layer on the surface of the metal nanoparticles disappears even at around room temperature. In addition, when the conductive metal nanoparticle paste of the present invention is actually used, it has thermal stability to such an extent that thermal decomposition does not occur even at a temperature at which low-temperature baking treatment is performed, The boiling point is at least 100 ° C. or higher, and preferably 150 ° C. or higher and not exceeding 300 ° C. Also, when forming fine lines, it is necessary to maintain the conductive metal nanoparticle paste in the desired liquid viscosity range in the coating process, and it is easy at around room temperature considering the handling properties. A non-polar solvent or a low-polar solvent exhibiting the above high boiling point that does not evaporate into, for example, a primary alcohol having 10 or more carbon atoms, such as tetradecane, which is an alkane having 10 or more carbon atoms, 1-decanol and the like are preferably used.
[0035]
On the other hand, the conductive metal nanoparticle paste according to the present invention is used for drawing a fine pattern by applying various coating methods such as a screen printing method and an ink jet printing method. Therefore, it is desirable to prepare the conductive metal nanoparticle paste according to the present invention so as to have a liquid viscosity suitable for each of the drawing techniques employed. For example, when a screen printing method is used for drawing a fine wiring pattern, it is desirable that the dispersion containing the nanoparticles has a liquid viscosity of 50 to 200 Pa · s (25 ° C.). . At that time, the volume ratio of the dispersion solvent in the paste is more preferably selected in the range of 25 to 45% by volume. On the other hand, when the ink jet printing method is used, it is desirable to select the liquid viscosity within a range of 5 to 30 mPa · s (20 ° C.). At that time, the volume ratio of the dispersion solvent in the paste is more preferably selected in the range of 60 to 80% by volume. The liquid viscosity of the dispersion containing the nanoparticles is determined depending on the average particle diameter of the nanoparticles to be used, the dispersion concentration, and the type of the dispersion solvent being used. The liquid viscosity can be adjusted.
[0036]
For example, as a dispersion solvent, in addition to the above-mentioned nonpolar solvent or low polarity solvent that exhibits a high boiling point, the liquid viscosity is adjusted, and when heated, it is useful for elution of coating layer molecules, while at around room temperature, A relatively low-polar liquid organic substance that exhibits a function of suppressing the separation of the coating layer molecules and a function of compensating for the separation can be added and blended. Such a low-polarity liquid organic substance added and blended can achieve uniform mixing with the main solvent component, and the boiling point of the liquid organic material should be as high as the main solvent component. desirable. For example, when the main solvent component is 1-decanol or the like, which is a primary alcohol having 10 or more carbon atoms, branched diols such as 2-ethyl-1,3-hexanediol, When the main solvent component is an alkane having 10 or more carbon atoms, such as tetradecane, a dipolar amine having a branch such as bis-2-ethylhexylamine is supplementarily added and blended. It can be used for liquid organic substances.
[0037]
The conductive metal nanoparticle paste according to the present invention contains an acid anhydride that shows reactivity with a binder resin component or a coating agent molecule, such as a thermosetting epoxy resin component that undergoes polymerization and cures when heated. By not adopting the configuration, even in the process of proceeding with the low-temperature baking treatment, there is no generation of a polymer inside, and a factor that significantly reduces the fluidity of the dispersion solvent itself is eliminated.
[0038]
During the heat treatment, the coating layer molecules such as alkylamine coating the surface of the metal nanoparticles are eluted and separated in the dispersion solvent, and the coating layer that has suppressed the aggregation of the metal nanoparticles disappears. Gradually, the metal nanoparticles are fused and agglomerated by fusion, and finally a random chain is formed. At this time, the low-temperature sintering of the metal nanoparticles proceeds, the space between the nanoparticles decreases, the entire volume shrinks, and the random chains achieve close contact with each other. When the gap space between the nanoparticles decreases, the dispersion solvent that occupies this gap space maintains fluidity, so even if the gap between the nanoparticles becomes a bottleneck, it is pushed out to the outside, Volume shrinkage proceeds. In this low-temperature firing process, when the heat treatment temperature is selected within the range of 300 ° C. or less, preferably 250 ° C. or less, the coating layer molecules are eluted and detached from the dispersion solvent described above, and the resulting metal nanoparticles are obtained. The sintered body is smooth and mirror-like with no surface irregularities reflecting non-uniform aggregation of metal nanoparticles, and is more dense and extremely low resistance, for example, volume resistivity is 10 × 10.-6It becomes a conductor layer of Ω · cm or less. On the other hand, as the entire volume shrinks, the dispersion solvent extruded to the outside and the coating layer molecules dissolved in the solvent gradually evaporate while continuing to heat, and finally the resulting metal nanoparticles are sintered. The body has a limited amount of organic matter remaining. Specifically, as a hinder resin component, a thermosetting resin component that remains in the sintered body of the metal nanoparticles obtained and becomes a constituent element of the conductor layer even after the low-temperature firing step is finished. Since it does not contain, the volume occupation rate of the sintered body of the metal nanoparticles in the conductor layer itself is high. As a result, in addition to the low volume resistivity of the sintered body of metal nanoparticles itself, the thermal conductivity of the entire conductor layer is also greatly improved due to the high volume occupancy of the metal body. . Because of both advantages, the formation of the fine wiring pattern using the conductive metal nanoparticle paste according to the present invention is more suitable for forming the fine wiring pattern when the current density flowing is high.
[0039]
In the method for forming a fine wiring pattern according to the present invention, a coating layer having a desired fine pattern is formed using the above-described conductive metal nanoparticle paste with the liquid viscosity optimized according to the coating method. In order to perform fine pattern drawing with high reproducibility and drawing accuracy, it is preferable to apply a screen printing method or an ink jet printing method. Note that, regardless of whether the screen printing method or the inkjet printing method is used, the average thickness of the dispersion coating layer to be drawn is the minimum wiring width with respect to the minimum wiring width of the drawn fine pattern. It is necessary to select the range of 1/5 to 1/1. Accordingly, the average film thickness of the dense metal sintered body layer finally obtained is 1/10 of the minimum wiring width in consideration of evaporation of the dispersion solvent contained in the coating layer and aggregation / shrinkage accompanying sintering. It is more reasonable to select in the range of ~ 1/2. Corresponding to these requirements, it is desirable to select the volume ratio range of the dispersion solvent in the above-mentioned paste in the conductive metal nanoparticle paste compatible with the screen printing method and the ink jet printing method.
[0040]
On the other hand, the fine wiring pattern to be produced is selected from gold, silver, copper, platinum, palladium, nickel, and aluminum for use as circuit wiring when mounting various electronic components on a printed wiring board. It is preferable to do. Or the alloy which consists of 2 or more types of metals selected from gold | metal | money, silver, copper, platinum, palladium, nickel, and aluminum can also be selected. Therefore, the metal nanoparticles used in the conductive metal nanoparticle paste according to the present invention are nanoparticles made of gold, silver, copper, platinum, palladium, nickel, aluminum metal, or gold, silver, copper, platinum, It is desirable to select nanoparticles made of an alloy made of two or more metals selected from palladium, nickel, and aluminum according to the application.
[0041]
In the metal nanoparticles, the heat treatment temperature in the low-temperature firing process is 300 ° C. or lower, preferably 250 ° C. or lower, so that a good sintered body can be obtained as long as a clean metal surface is maintained. Can be formed. Furthermore, even near room temperature, these metal nanoparticles tend to fuse and aggregate with each other when the metal surface is brought into direct contact. Therefore, for example, using a commercially available metal nanoparticle dispersion as a raw material, the dispersion solvent is converted into a desired organic solvent, and the content ratio of the appropriate dispersion solvent and adjustment of the liquid viscosity are adjusted to the present invention. When preparing such a conductive metal nanoparticle paste, for example, it is desirable to use the following procedure.
[0042]
As a metal nanoparticle dispersion used as a raw material, the surface of metal nanoparticles is coated and protected with a surface coating molecule such as alkylamine, and the solubility of the surface coating molecule such as alkylamine is poor and the boiling point is 100 ° C. or less. A non-polar solvent or a material that is uniformly dispersed in a low-polar solvent. First, the dispersion solvent contained in the metal nanoparticle dispersion is removed while suppressing the separation of surface coating molecules such as alkylamine. Removal of the dispersion solvent is suitably performed by distillation under reduced pressure, but during this vacuum distillation, in order to suppress detachment of surface coating molecules on the surface of the metal nanoparticles, A protective solvent component having excellent affinity and having a boiling point significantly higher than that of the dispersion solvent distilled off under reduced pressure is added and mixed, and then distilled off under reduced pressure. For example, when the dispersion solvent to be distilled off under reduced pressure is toluene, and a dodecylamine that is an alkylamine is used as the coating layer molecule of the metal nanoparticles, a diol-based solvent, for example, A small amount of various glycols such as dipropylene glycol, diethylene glycol, propylene glycol, and ethylene glycol are added. In addition, in addition to alkylamine, which is used as a metal nanoparticle coating layer molecule, such as dodecylamine, it can be used as a metal nanoparticle coating layer molecule, and another amine having a higher boiling point should be added. You can also. These other types of amines can also be used for the purpose of substituting a part of the coating layer molecules of the metal nanoparticles present initially when the dispersion solvent is distilled off under reduced pressure. The molecular component of the coating layer to be substituted, such as this different type of amine, has an affinity with a solvent component for protection such as various glycols, and at the same time has a group capable of coordinating bonding such as an amino group. A liquid organic compound having a high boiling point can be used. For example, 2-ethylhexylamine and Jeffamine EDR148 (2,2- (ethylenedioxy) bisethylamine) can be used.
[0043]
Solvent components for protection such as diol solvents used in the process after the dispersion solvent having a low boiling point was distilled off under reduced pressure, which was originally included, or coating layer molecules used for partial replacement of coating layer molecules It becomes a mixture in which the components remain. In order to remove these excessive additives and to remove high-boiling polymer components mixed in the metal nanoparticle dispersion used as a raw material, using a polar solvent having an appropriate polarity, Wash. In addition, although the polar solvent utilized for this washing | cleaning does not reach | release the coating layer molecule | numerator of the metal nanoparticle surface, it shall be able to melt | dissolve an unnecessary organic substance component. In addition, after the washing, the solid-liquid phase can be easily separated from the metal nanoparticles having a coating layer on the surface and the polar solvent. For example, the dispersion is performed on the metal nanoparticles having the coating layer on the surface. It is desirable to use a polar solvent in which the characteristics are not so high, and the metal nanoparticles having a coating layer on the surface thereof are allowed to settle by allowing to stand. Finally, after washing and removing the polar solvent layer by solid-liquid phase separation, the polar solvent infiltrating the sedimented layer of metal nanoparticles is evaporated and removed. However, it is desirable to use a volatile polar solvent that can be easily achieved. Considering these requirements, it is preferable to use low boiling point ketones such as acetone.
[0044]
The removal of unnecessary residual organic substances using the polar solvent is completed, and separation from the polar solvent is performed by solid-liquid phase separation, and the polar solvent infiltrating the sedimented layer of metal nanoparticles is evaporated and removed. The high-boiling point dispersion solvent component described above is added to the metal nanoparticles having the coating layer on the surface after the removal of the solvent and drying, and the paste is re-prepared. In addition, since the paste-like dispersion liquid finally prepared has a relatively low volume ratio of the dispersion solvent component as described above, excessive stirring is required to obtain a uniform dispersion liquid. Necessary. In order to avoid this, a non-polar solvent whose boiling point does not exceed 70 ° C., for example, hexane, which is an alkane having 6 or less carbon atoms, is used as a diluting solvent to achieve uniform dispersion. When removing and drying the solvent, in addition to the metal nanoparticles having a coating layer on the surface, there may be cases where agglomerated metal nanoparticle mass is mixed, using the hexane or the like as a solvent for dilution, The re-dispersed liquid with uniform dispersion is filtered through a filter with a sub-micron pore size, for example, a 0.2 μm membrane filter, to remove the aggregated metal nanoparticle mass. Thereafter, the solvent for low boiling point dilution such as hexane used for uniform dispersion is selectively distilled off under reduced pressure using the difference in boiling point, to the target high boiling point dispersion solvent, A paste-like dispersion liquid in which metal nanoparticles having a coating layer on the surface are uniformly dispersed is prepared.
[0045]
In the conductive metal nanoparticle paste according to the present invention, the dispersion solvent is changed and unnecessary organic substances are removed by the above-described procedure. Therefore, the coating molecular weight covering the surface of the metal nanoparticle is adjusted to an appropriate range and then heated. In this case, a proper amount of the high boiling point dispersion solvent used for elution of the coating molecules is contained. In addition, in the process of removing the initial dispersion solvent, an operation of adding a diol component (dipropylene glycol, diethylene glycol, propylene glycol, ethylene glycol, etc.) to the metal nanoparticle dispersion used as a raw material and stirring with heating is performed. Along with the application, a substantial part such as excess organic matter mixed in the dispersion is once dissolved in the diol component. Thereafter, in the washing with a polar solvent such as acetone, the dissolution of the excess organic substance once dissolved in the diol component and the polar solvent such as acetone together with the diol component is promoted.
[0046]
On the other hand, as a low-polar liquid organic substance that is added and blended in addition to 1-decanol, which is the main dispersion solvent when finally dispersed in the target high-boiling dispersion solvent, 2 -Addition of ethyl-1,3-hexanediol, etc., and use of a diluting solvent such as hexane to achieve uniform dispersion, whereby the amine compound and the coating layer molecules in 1-decanol exhibiting polarity Helps maintain the dispersion of metal nanoparticles. In addition to tetradecane as the main dispersion solvent, bis-2-ethyl-hexylamine or the like is added as a low-polar liquid organic material that is supplementally added and blended, and a dilution solvent such as hexane is used. Thus, uniform dispersion helps to maintain the dispersion of the metal nanoparticles having the amine compound as a coating layer molecule in the nonpolar solvent tetradecane.
[0047]
During the heat treatment, the remaining organic components are concentrated at the interface between the obtained sintered body layer and the underlying substrate surface, and after sintering, the contact between the substrate surface and the sintered body layer is made dense. It performs the function of maintaining. Such close contact also makes a certain contribution to the fixing of the resulting sintered body layer to the substrate surface.
[0048]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. These examples are examples of the best mode of the present invention, but the present invention is not limited by these examples.
[0049]
Example 1
A paste-like dispersion liquid containing silver nanoparticles as a conductive medium and exhibiting a liquid viscosity suitable for screen printing was prepared by the following procedure.
[0050]
As a silver nanoparticle raw material, a commercially available silver ultrafine particle dispersion (trade name: independent dispersed ultrafine particle Ag1T manufactured by vacuum metallurgy), specifically, 35 parts by mass of silver ultrafine particles, alkylamine as dodecylamine (molecular weight) 185.36, boiling point 248 ° C.) 7 parts by mass, As an organic solvent, a dispersion of ultrafine silver particles having an average particle diameter of 3 nm containing 58 parts by mass of toluene was used.
[0051]
  In a 1 L eggplant-shaped flask, the above-mentioned silver ultrafine particle dispersion Ag1T, 500 g (containing 35 wt% of Ag: made by vacuum metallurgy), Jeffamine EDR148 (2,2- (ethylenedioxy) bisethylamine)H 2 N-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -NH 2 : 87.5 g (manufactured by Sun Techno Chemical) (50 wt% with respect to Ag solid content) and 52.5 g of dipropylene glycol (30 wt% with respect to Ag solid content) are added and mixed, and 1 at 80 ° C. Stir for hours. After completion of the stirring, the dispersion solvent toluene contained in Ag1T was removed by concentration under reduced pressure.
[0052]
The solvent-removed mixture was transferred to a 2 L beaker, polar solvent acetone, 1,000 g was added, and the mixture was stirred at room temperature for 3 minutes and allowed to stand. In the treatment, the Ag nanoparticles settled on the bottom of the beaker while adding the polar solvent acetone, stirring, and allowing to stand. On the other hand, unnecessary organic components contained in the mixture were dissolved in the supernatant, and a brown acetone solution was obtained. After removing this supernatant layer, 800 g of acetone was added to the sediment again, and the mixture was stirred and allowed to stand to precipitate Ag nanoparticles, and then the supernatant acetone solution layer was removed. While observing the colored state of the supernatant acetone layer, 500 g of acetone was further added to the sediment, and the same operation was repeated. Next, when 300 g of acetone was added to the sediment in the previous stage, and stirring and standing were performed, no coloration was found in a range visually observed in the supernatant acetone layer.
[0053]
After removing this supernatant acetone layer, the acetone solvent remaining in the Ag nanoparticles settled on the bottom of the beaker was volatilized and dried to obtain a blue fine powder. To the obtained blue fine powder, 16.7 g of calcoal 1098 (1-decanol, melting point 6.88 ° C., boiling point 232 ° C .: manufactured by Kao), 2-ethyl-1,3-hexanediol (boiling point 244 ° C., sum) 7.2 g and 300 g of hexane were added, and the mixture was heated and stirred at 70 ° C. for 30 minutes. By this heating and stirring, the Ag nanoparticles that had been in the form of a blue fine powder were redispersed to form a uniform dispersion. After completion of stirring, the mixture was filtered through a 0.2 μm membrane filter, and then hexane in the filtrate was removed by vacuum concentration.
[0054]
Along with the removal of the solvent hexane, a uniform dark blue colored paste-like nanoparticle dispersion was obtained. The paste-like dispersion (nanoparticle paste) had a liquid viscosity of 150 Pa · s (spiral viscometer, measurement temperature 23 ° C.). The total composition of this nanoparticle paste is 50 parts by mass of organic components as a total with respect to 175 parts by mass of Ag nanoparticles of the conductive medium, specifically, 16.7 masses of 1-decanol as the main dispersion solvent. Part, 2-ethyl-1,3-hexanediol was 7.2 parts by mass, and other organic substances (such as dodecylamine) remained 26.1 parts by mass. Therefore, in this nanoparticle paste, the volume ratio of Ag nanoparticles as a solid component is 22.2% by volume, the volume ratio of the organic component is 77.8% by volume, and the ratio of the dispersion solvent is 36.9%. Corresponds to volume%.
[0055]
Using the obtained nanoparticle paste, a 10 × 50 mm wide pattern was printed on a slide glass by a screen printing method with an average film thickness of 30 μm at the time of application. . After printing, the nanoparticle paste coating layer on the slide glass is subjected to a heat treatment at 250 ° C. for 40 minutes, and the contained silver nanoparticles are baked with each other to form a conductor composed of a sintered layer of silver nanoparticles. A layer pattern was formed. The surface of the conductor layer pattern exhibited a specular gloss, and the average film thickness was 5 μm. Moreover, when the volume resistivity was measured as a uniform conductor layer having the above average film thickness, it was 3.5 μΩ · cm. In addition, the resistivity of the silver bulk is 1.59 μΩ · cm (20 ° C.), and the volume resistivity of the sintered body layer of the obtained silver nanoparticles is compared with the resistivity of the silver bulk, The value was not inferior.
[0056]
(Example 2)
A dispersion containing silver nanoparticles as a conductive medium and exhibiting a liquid viscosity suitable for ink jet printing was prepared by the following procedure.
[0057]
In a 1 L eggplant type flask, 87.5 g of 2-ethylhexylamine (boiling point: 169 ° C .: manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 500 g (containing 35 wt% of Ag: manufactured by Vacuum Metallurgy) of the above silver ultrafine particle dispersion Ag1T. 50 wt% relative to the minute) and 52.5 g of dipropylene glycol (30 wt% relative to the Ag solid content) were added and mixed, followed by heating and stirring at 80 ° C. for 1 hour. After completion of the stirring, the dispersion solvent toluene contained in Ag1T was removed by concentration under reduced pressure.
[0058]
The solvent-removed mixture was transferred to a 2 L beaker, polar solvent acetone, 1,000 g was added, and the mixture was stirred at room temperature for 3 minutes and allowed to stand. In the treatment, the Ag nanoparticles settled on the bottom of the beaker while adding the polar solvent acetone, stirring, and allowing to stand. On the other hand, unnecessary organic components contained in the mixture were dissolved in the supernatant, and a brown acetone solution was obtained. After removing this supernatant layer, 800 g of acetone was added to the sediment again, and the mixture was stirred and allowed to stand to precipitate Ag nanoparticles, and then the supernatant acetone solution layer was removed. While observing the colored state of the supernatant acetone layer, 500 g of acetone was further added to the sediment, and the same operation was repeated. Next, when 300 g of acetone was added to the sediment in the previous stage, and stirring and standing were performed, no coloration was found in a range visually observed in the supernatant acetone layer.
[0059]
After removing this supernatant acetone layer, the acetone solvent remaining in the Ag nanoparticles settled on the bottom of the beaker was volatilized and dried to obtain a blue fine powder. To the obtained blue fine powder, 23.4 g of bis-2-ethylhexylamine (boiling point 263 ° C., manufactured by Tokyo Chemical Industry Co., Ltd.), N14 (tetradecane, melting point 5.86 ° C., boiling point 253.57 ° C., manufactured by Nippon Mining Petrochemical Co., Ltd.) 93.6 g and hexane 300 g were added, and the mixture was heated and stirred at 70 ° C. for 30 minutes. By this heating and stirring, the Ag nanoparticles that had been in the form of a blue fine powder were redispersed to form a uniform dispersion. After completion of stirring, the mixture was filtered through a 0.2 μm membrane filter, and then hexane in the filtrate was removed by vacuum concentration.
[0060]
Along with the removal of the solvent hexane, a uniform dark blue high fluidity paste type nanoparticle dispersion was obtained. The liquid viscosity of this highly fluid paste dispersion (nanoparticle ink) was 10 mPa · s (B-type rotational viscometer, measurement temperature 20 ° C.). The total composition of the nanoparticle dispersion is 152.8 parts by mass of the total amount of organic components with respect to 175 parts by mass of Ag nanoparticles of the conductive medium. Specifically, bis-2-ethylhexylamine is 23.4 parts by mass. Part, 93.6 parts by mass of tetradecane as the main dispersion solvent, and 35.8 parts by mass of other organic substances (such as dodecylamine) remained. Therefore, in this nanoparticle paste, the volume ratio of Ag nanoparticles as a solid component is 7.8% by volume, the volume ratio of the organic component is 92.2% by volume, of which the ratio of the dispersion solvent is 71. It corresponds to 1% by volume.
[0061]
A 10 × 50 mm wide pattern was printed on a slide glass by an inkjet printing method with an average film thickness of 10 μm at the time of coating by inkjet coating using the obtained nanoparticle ink. After printing, the nanoparticle ink coating layer on the slide glass is subjected to a heat treatment at 230 ° C. for 60 minutes, and the contained silver nanoparticles are subjected to a firing process, thereby forming a conductor composed of a sintered layer of silver nanoparticles. A layer pattern was formed. The surface of the conductor layer pattern exhibited a specular gloss, and the average film thickness was 1 μm. Moreover, when the volume resistivity was measured as a uniform conductor layer having the average film thickness, it was 3.0 μΩ · cm.
[0062]
(Comparative Example 1)
A paste-like dispersion liquid containing silver nanoparticles as a conductive medium and showing a liquid viscosity usable for screen printing was prepared by the following procedure.
[0063]
In a 1 L eggplant-shaped flask, 16.7 g of calcoal 1098 (1-decanol: manufactured by Kao) was added to 500 g (containing 35 wt% of Ag: manufactured by Vacuum Metallurgy) of the above silver ultrafine particle dispersion Ag1T, 2-ethyl-1, 7.2 g of 3-hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred with heating at 40 ° C. for 30 minutes. After completion of the stirring, the dispersion solvent toluene derived from Ag1T was removed by vacuum concentration.
[0064]
With the selective solvent removal of toluene, a uniform dark blue paste-like nanoparticle dispersion was obtained. The liquid viscosity of this paste-like dispersion (nanoparticle paste) was 80 Pa · s (spiral viscometer, measurement temperature 23 ° C.). The total composition of the nanoparticle paste is 65 parts by mass of organic components as a total with respect to 175 parts by mass of Ag nanoparticles of the conductive medium, specifically, 16.7 masses of 1-decanol as the main dispersion solvent. Part, 2-ethyl-1,3-hexanediol was 7.2 parts by mass, and other organic matter (dodecylamine) was 41.1 parts by mass. Therefore, in this nanoparticle paste, the volume ratio of Ag nanoparticles as a solid component is 17.9% by volume, the volume ratio of the organic component is 82.1% by volume, and the ratio of the dispersion solvent is 29.9%. Corresponds to volume%. In addition, unlike the nanoparticle paste described in Example 1 described above, the nanoparticle paste of this example is subjected to a selective solvent removal treatment of toluene without performing a cleaning treatment using an acetone solvent. Concomitantly, there is a difference in composition and liquid viscosity between the two.
[0065]
Using the obtained nanoparticle paste, a 10 × 50 mm wide pattern was printed on a slide glass by a screen printing method with an average film thickness of 25 μm at the time of application. . After printing, the nanoparticle paste coating layer on the slide glass is subjected to a heat treatment at 250 ° C. for 40 minutes, and the contained silver nanoparticles are baked with each other to form a conductor composed of a sintered layer of silver nanoparticles. A layer pattern was formed. Although the average film thickness of the conductor layer pattern was 5 μm, many cracks were formed on the surface thereof, and when the volume resistivity was measured, it was used in Example 1 described above. It was impossible to measure under the measurement conditions. That is, the volume resistivity is estimated to exceed 10 μΩ · cm.
[0066]
(Comparative Example 2)
A paste-like dispersion liquid containing silver nanoparticles as a conductive medium and exhibiting a liquid viscosity usable for inkjet printing was prepared by the following procedure.
[0067]
In a 1 L eggplant-shaped flask, 23.4 g of bis-2-ethylhexylamine (manufactured by Tokyo Chemical Industry), N14 (tetradecane, Nippon Oil) 93.6 g of Chemical) was added and stirred with heating at 40 ° C. for 30 minutes. After completion of the stirring, the dispersion solvent toluene derived from Ag1T was removed by vacuum concentration.
[0068]
Along with the selective desolvation of toluene, a uniform dark blue high-fluidity paste-type nanoparticle dispersion was obtained. The liquid viscosity of this highly fluid paste dispersion (nanoparticle ink) was 10 mPa · s (B-type rotational viscometer, measurement temperature 20 ° C.). The total composition of this nanoparticle dispersion is 157 parts by mass of organic components in total with respect to 175 parts by mass of Ag nanoparticles of the conductive medium, specifically, 23.4 parts by mass of bis-2-ethylhexylamine, 93.6 parts by mass of tetradecane as the main dispersion solvent and 40 parts by mass of other organic substances (such as dodecylamine) remained. Therefore, in this nanoparticle paste, the volume ratio of Ag nanoparticles as a solid component is 7.66 vol%, the volume ratio of organic components is 92.34 vol%, of which the ratio of the dispersion solvent is 69.34 vol%. It corresponds to 45% by volume.
[0069]
A 10 × 50 mm wide pattern was printed on a slide glass by an inkjet printing method with an average film thickness of 10 μm at the time of coating by inkjet coating using the obtained nanoparticle ink. After printing, the nanoparticle ink coating layer on the slide glass is subjected to a heat treatment at 230 ° C. for 60 minutes, and the contained silver nanoparticles are subjected to a firing process, thereby forming a conductor composed of a sintered layer of silver nanoparticles. A layer pattern was formed. The surface of the conductor layer pattern exhibited a specular gloss, and the average film thickness was 1.5 μm. Further, when the volume resistivity was measured as a uniform conductor layer having the average film thickness, it was 10 μΩ · cm.
[0070]
【The invention's effect】
In the conductive nanoparticle paste of the present invention, metal nanoparticles having an average particle diameter of 100 nm or less are used as the conductive medium, and the surface can be coordinately bonded to the metal element contained in the metal nanoparticles. One or more compounds containing a nitrogen, oxygen, or sulfur atom as a group and having a group capable of coordinative bonding by a lone pair of these atoms, for example, one or more amine compounds having one or more terminal amino groups The metal nanoparticles are uniformly dispersed in a dispersion solvent containing at least one organic solvent component having an affinity for the amine compound after being coated with the amine compound. Is prevented from agglomeration and sedimentation by a coating layer of a compound containing nitrogen, oxygen or sulfur atoms present on the surface. On the other hand, the compound containing nitrogen, oxygen, or sulfur atoms constituting the coating layer at the stage of proceeding the heat treatment at a low temperature after coating is applied by the action of the compatible organic solvent component contained in the dispersion solvent. As a result of separation and elution, the surface of the metal nanoparticles is exposed, and the metal nanoparticles can be in close contact with each other and fired at a low temperature. Along with this process, the dispersion solvent gradually evaporates, and the volume reduction of the entire paste coating layer also proceeds, so in the sintered body formed by firing metal nanoparticles, the gap space infiltrated with the dispersion solvent is reduced. As a result, the metal nanoparticles are more precisely sintered. Therefore, the conductive nanoparticle paste according to the present invention has a smooth surface shape and can form a low resistance and fine circuit when coated and fired on a substrate, in addition to fine pattern printability. It is used as a low-temperature sintered conductive metal paste for dense circuit printing.

Claims (9)

  1. A conductive nanoparticle paste comprising metal nanoparticles,
    The average particle diameter of the metal nanoparticles is selected in the range of 1 to 100 nm,
    The conductive nanoparticle paste is a dispersion obtained by uniformly dispersing the metal nanoparticles in a dispersion solvent,
    The surface of the metal nanoparticle contains a nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with the metal element contained in the metal nanoparticle, and is coordinated by a lone electron pair possessed by these atoms. Covered with one or more compounds having a group capable of bonding;
    The total of one or more compounds having a group containing nitrogen, oxygen, or sulfur atoms with respect to 100 parts by mass of the metal nanoparticles, containing 10 to 20 parts by mass,
    When the dispersion solvent is heated to 100 ° C. or more, 50 parts by mass or more of the compound having a group containing nitrogen, oxygen, or sulfur atoms covering the surface of the metal nanoparticles can be dissolved per 100 parts by mass of the dispersion solvent. , An organic solvent having high solubility, or a mixed solvent composed of two or more liquid organic substances,
    8 to 220 parts by mass of the dispersion solvent with respect to 100 parts by mass of the metal nanoparticles,
    One kind of organic solvent constituting the dispersion solvent or two or more kinds of liquid organic substances react with the compound having a group containing nitrogen, oxygen or sulfur atoms in the temperature range of 20 ° C. to 300 ° C. Without showing sex
    The compound having a group containing nitrogen, oxygen, or sulfur atom has a boiling point in the range of 150 ° C. to 300 ° C. and a melting point of 20 ° C. or less,
    One of the organic solvents constituting the dispersion solvent, or two or more liquid organic substances each have a boiling point in the range of 150 ° C. to 300 ° C. and a melting point of 20 ° C. or less.
    The compound having a group containing nitrogen, oxygen, or sulfur atoms that coats the surface of the metal nanoparticle may be a terminal amino group (—NH) as a group capable of coordinative bonding with the metal element contained in the metal nanoparticle. 2 ) an amine compound having one or more,
    The organic solvent, or a dispersion solvent composed of two or more liquid organic substances, is selected from the following mixed solvents (a) or (b):
    (A) primary alcohols having 10 or more carbon atoms as a main solvent component,
    A mixed solvent obtained by selecting a branched diol as a low-polar liquid organic material to be supplementally added to and blended with the main solvent component;
    (B) an alkane having 10 or more carbon atoms as a main solvent component,
    A mixed solvent obtained by selecting dialkylamines having a branch as a low-polar liquid organic substance to be added and blended with respect to the main solvent component;
    The conductive nanoparticle paste does not contain a binder resin component and an acid anhydride,
    The conductive nanoparticle paste is a paste for ink jet printing,
    The liquid viscosity (20 ° C.) of the paste is selected in the range of 5 mPa · s to 30 mPa · s,
    The conductive nanoparticle paste, wherein the volume ratio of the dispersion solvent in the paste is selected in the range of 60 to 80% by volume.
  2. A conductive nanoparticle paste comprising metal nanoparticles,
    The average particle diameter of the metal nanoparticles is selected in the range of 1 to 100 nm,
    The conductive nanoparticle paste is a dispersion obtained by uniformly dispersing the metal nanoparticles in a dispersion solvent,
    The surface of the metal nanoparticle contains a nitrogen, oxygen, or sulfur atom as a group capable of coordinative bonding with the metal element contained in the metal nanoparticle, and is coordinated by a lone electron pair possessed by these atoms. Covered with one or more compounds having a group capable of bonding;
    The total of one or more compounds having a group containing nitrogen, oxygen, or sulfur atoms with respect to 100 parts by mass of the metal nanoparticles, containing 10 to 20 parts by mass,
    When the dispersion solvent is heated to 100 ° C. or more, 50 parts by mass or more of the compound having a group containing nitrogen, oxygen, or sulfur atoms covering the surface of the metal nanoparticles can be dissolved per 100 parts by mass of the dispersion solvent. , An organic solvent having high solubility, or a mixed solvent composed of two or more liquid organic substances,
    8 to 220 parts by mass of the dispersion solvent with respect to 100 parts by mass of the metal nanoparticles,
    One kind of organic solvent constituting the dispersion solvent or two or more kinds of liquid organic substances react with the compound having a group containing nitrogen, oxygen or sulfur atoms in the temperature range of 20 ° C. to 300 ° C. Without showing sex
    The compound having a group containing nitrogen, oxygen, or sulfur atom has a boiling point in the range of 150 ° C. to 300 ° C. and a melting point of 20 ° C. or less,
    One of the organic solvents constituting the dispersion solvent, or two or more liquid organic substances each have a boiling point in the range of 150 ° C. to 300 ° C. and a melting point of 20 ° C. or less.
    The compound having a group containing nitrogen, oxygen, or sulfur atoms that coats the surface of the metal nanoparticle may be a terminal amino group (—NH) as a group capable of coordinative bonding with the metal element contained in the metal nanoparticle. 2 ) an amine compound having one or more,
    The organic solvent, or a dispersion solvent composed of two or more liquid organic substances, is selected from the following mixed solvents (a) or (b):
    (A) primary alcohols having 10 or more carbon atoms as a main solvent component,
    A mixed solvent obtained by selecting a branched diol as a low-polar liquid organic material to be supplementally added to and blended with the main solvent component;
    (B) an alkane having 10 or more carbon atoms as a main solvent component,
    A mixed solvent obtained by selecting dialkylamines having a branch as a low-polar liquid organic substance to be added and blended with respect to the main solvent component;
    The conductive nanoparticle paste does not contain a binder resin component and an acid anhydride,
    The conductive nanoparticle paste is a paste for screen printing,
    The liquid viscosity (25 ° C.) of the paste is selected in the range of 50 Pa · s to 200 Pa · s,
    The conductive nanoparticle paste, wherein the volume ratio of the dispersion solvent in the paste is selected in the range of 25 to 45% by volume.
  3. 3. The amine compound having one or more terminal amino groups (—NH 2 ) is a monoalkylamine having a boiling point in a range of 150 ° C. or higher and 250 ° C. or lower. Conductive nanoparticle paste.
  4. The conductive nanoparticle paste according to any one of claims 1 to 3, wherein an average particle diameter of the metal nanoparticles is selected in a range of 2 to 10 nm.
  5. The metal nanoparticles are
    From nanoparticles composed of gold, silver, copper, platinum, palladium, nickel, and aluminum metals, or alloys composed of two or more metals selected from gold, silver, copper, platinum, palladium, nickel, and aluminum The conductive nanoparticle paste according to any one of claims 1 to 4, wherein the nanoparticle is a conductive nanoparticle paste.
  6. The dispersion solvent composed of one kind of organic solvent or two or more kinds of liquid organic substances is selected from the following mixed solvents (a ′) or (b ′): (a ′) 1-decanol is mainly used. As a solvent component,
    A mixed solvent obtained by selecting 2-ethyl-1,3-hexanediol as a low-polar liquid organic substance to be added and blended with respect to the main solvent component;
    (B ′) tetradecane as a main solvent component,
    A mixed solvent in which bis-2-ethylhexylamine is selected as a low-polar liquid organic material to be added and blended with respect to the main solvent component;
    The conductive nanoparticle paste according to any one of claims 1 to 5, wherein
  7. A method of forming a fine wiring pattern with good conductivity, comprising a sintered body layer of metal nanoparticles on a substrate,
    Forming a coating layer of the fine wiring pattern to be drawn on the substrate surface using a paste-like dispersion liquid containing metal nanoparticles selected in an average particle size range of 1 to 100 nm;
    A step of firing the metal nanoparticles contained in the coating layer to form a sintered body layer between the metal nanoparticles;
    As the paste-like dispersion liquid containing the metal nanoparticles, using the conductive nanoparticle paste according to any one of claims 1 to 6,
    The formation of a sintered body layer between the metal nanoparticles is performed by heating the coating layer to a temperature not exceeding 300 ° C.
    When heating in the baking treatment, the compound having a group containing nitrogen, oxygen, and sulfur atoms that coats the surface of the metal nanoparticles is composed of a highly soluble organic solvent, or two or more liquid organic substances. In the dispersion solvent using the mixed solvent, dissociation and elution from the surface of the metal nanoparticles are achieved, and the surface contact between the metal nanoparticles is achieved,
    A method for forming a fine wiring pattern, wherein the metal nanoparticles are sintered together and the dispersion solvent is removed by evaporation.
  8. Drawing of the coating layer of the fine wiring pattern using the paste dispersion liquid,
    Using the conductive nanoparticle paste according to claim 1 ,
    The method for forming a fine wiring pattern according to claim 7, wherein the fine wiring pattern is formed using an ink jet printing method.
  9. Drawing of the coating layer of the fine wiring pattern using the paste dispersion liquid,
    Using the conductive nanoparticle paste according to claim 2 ,
    The method for forming a fine wiring pattern according to claim 7, wherein the fine wiring pattern is formed using a screen printing method.
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Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006057348A1 (en) * 2004-11-29 2006-06-01 Dainippon Ink And Chemicals, Inc. Method for producing surface-treated silver-containing powder and silver paste using surface-treated silver-containing powder
JP4723236B2 (en) * 2004-12-28 2011-07-13 三ツ星ベルト株式会社 Silver thin film production method
JP4774750B2 (en) * 2005-02-03 2011-09-14 住友電気工業株式会社 Conductive paste and wiring board using the same
JP4630683B2 (en) * 2005-02-08 2011-02-09 住友ゴム工業株式会社 Electrode printing method and electrode plate provided with the electrode
JP4247627B2 (en) 2005-02-10 2009-04-02 セイコーエプソン株式会社 Optical element manufacturing method
JP4606191B2 (en) * 2005-02-16 2011-01-05 旭化成イーマテリアルズ株式会社 Manufacturing method of laminate
JP4606192B2 (en) * 2005-02-16 2011-01-05 旭化成イーマテリアルズ株式会社 Circuit board manufacturing method
JP5023506B2 (en) * 2005-02-28 2012-09-12 Dic株式会社 Method for producing conductive paint
JP4660780B2 (en) 2005-03-01 2011-03-30 Dowaエレクトロニクス株式会社 Method for producing silver particle powder
ES2424849T3 (en) 2005-03-04 2013-10-09 Inktec Co., Ltd. Conductive inks and their manufacturing method
KR100653251B1 (en) 2005-03-18 2006-12-01 삼성전기주식회사 Mathod for Manufacturing Wiring Board Using Ag-Pd Alloy Nanoparticles
JP4748158B2 (en) * 2005-04-06 2011-08-17 株式会社村田製作所 Conductive resin cured product and electronic component module
KR101249192B1 (en) 2005-04-12 2013-04-03 아사히 가라스 가부시키가이샤 Ink composition and metallic material
JP5176060B2 (en) * 2005-07-05 2013-04-03 Dowaエレクトロニクス株式会社 Method for producing silver particle dispersion
JP4973830B2 (en) * 2005-07-29 2012-07-11 戸田工業株式会社 Conductive composition, conductive paste and conductive film
JP4906301B2 (en) * 2005-09-29 2012-03-28 東海ゴム工業株式会社 Conductive paste
JP4801958B2 (en) * 2005-09-29 2011-10-26 東海ゴム工業株式会社 Conductive paste
US20070144305A1 (en) * 2005-12-20 2007-06-28 Jablonski Gregory A Synthesis of Metallic Nanoparticle Dispersions
JP2007257869A (en) * 2006-03-20 2007-10-04 Mitsui Mining & Smelting Co Ltd Conductive ink
JP4983150B2 (en) 2006-04-28 2012-07-25 東洋インキScホールディングス株式会社 Method for producing conductive coating
JP5170989B2 (en) * 2006-07-07 2013-03-27 株式会社日本触媒 Method for producing conductive copper coating
FI20060673A0 (en) 2006-07-11 2006-07-11 Keskuslaboratorio Method and apparatus for printing and printing product
WO2008009779A1 (en) 2006-07-21 2008-01-24 Valtion Teknillinen Tutkimuskeskus Method for manufacturing conductors and semiconductors
JP4505825B2 (en) * 2006-09-15 2010-07-21 国立大学法人大阪大学 Method for sintering metal nanoparticles and method for forming wiring on a substrate using the sintering method
JP5252473B2 (en) 2006-10-19 2013-07-31 独立行政法人産業技術総合研究所 Conductive pattern forming film, conductive pattern forming method and conductive pattern forming apparatus therefor
JP2008147618A (en) * 2006-11-13 2008-06-26 Sony Corp Method of manufacturing semiconductor device
JP5096735B2 (en) 2006-12-05 2012-12-12 Jx日鉱日石エネルギー株式会社 Wire grid polarizer and method for manufacturing the same, and retardation film and liquid crystal display device using the same
JP5365006B2 (en) * 2007-01-19 2013-12-11 三菱マテリアル株式会社 Metal film forming method
JP4891846B2 (en) * 2007-06-26 2012-03-07 ハリマ化成株式会社 Ultra fine solder composition
JP4986745B2 (en) * 2007-07-05 2012-07-25 Dowaエレクトロニクス株式会社 Silver paste
US8101231B2 (en) * 2007-12-07 2012-01-24 Cabot Corporation Processes for forming photovoltaic conductive features from multiple inks
KR101247431B1 (en) 2007-12-18 2013-03-26 히타치가세이가부시끼가이샤 Copper conductor film and manufacturing method thereof, conductive substrate and manufacturing method thereof, copper conductor wiring and manufacturing method thereof, and treatment solution
US20170004978A1 (en) * 2007-12-31 2017-01-05 Intel Corporation Methods of forming high density metal wiring for fine line and space packaging applications and structures formed thereby
FI20085229A (en) * 2008-03-18 2009-09-19 Keskuslaboratorio New materials and procedures
JP5463538B2 (en) * 2008-03-18 2014-04-09 国立大学法人 東京大学 Method for producing organic thin film transistor
KR100978671B1 (en) * 2008-08-05 2010-08-30 삼성전기주식회사 Metal nanoparticle dispersion
TWI518036B (en) * 2008-08-11 2016-01-21 地方獨立行政法人 大阪市立工業研究所 Copper-based nanoparticles and method for the production thereof
TWI461470B (en) * 2008-08-11 2014-11-21 Osaka Municipal Tech Res Inst Composite nanoparticles and method for the production thereof
JP5651299B2 (en) * 2008-11-11 2015-01-07 Dic株式会社 Process for producing conductive molded product, conductive molded product, and silver paste used therefor
KR101142416B1 (en) 2008-12-31 2012-05-07 주식회사 잉크테크 Method for manufacturing metal film
TWI421882B (en) 2009-06-08 2014-01-01 Daiken Chemical Co Ltd Barium titanate powder, nickel paste, preparation method and laminated ceramic capacitors
KR101451684B1 (en) * 2009-06-16 2014-10-17 반도 카가쿠 가부시키가이샤 Electrically conductive ink and process for production of base material having electrically conductive coating film attached thereto using same
JP5468885B2 (en) * 2009-12-01 2014-04-09 ハリマ化成株式会社 Conductive aluminum paste
JP5811314B2 (en) * 2010-06-16 2015-11-11 国立研究開発法人物質・材料研究機構 Metal nanoparticle paste, electronic component body using metal nanoparticle paste, led module, and method for forming circuit for printed wiring board
JP5569347B2 (en) * 2010-11-10 2014-08-13 凸版印刷株式会社 RFID label
KR101970373B1 (en) 2011-08-03 2019-04-18 히타치가세이가부시끼가이샤 Composition set, electroconductive substrate and manufacturing method thereof, and electroconductive binding material composition
CN103945961B (en) * 2011-09-06 2017-01-18 汉高知识产权控股有限责任公司 Di-or poly-functional electron deficient olefins coated metal powders for solder pastes
KR20130031414A (en) * 2011-09-21 2013-03-29 삼성전기주식회사 Conductive paste composition for low temperature firing
JP6034090B2 (en) * 2012-08-09 2016-11-30 古河電気工業株式会社 Method for producing metal fine particle dispersion and method for forming conductor
JP6179520B2 (en) * 2012-09-05 2017-08-16 日立化成株式会社 Silver paste composition and semiconductor device using the same
EP3049202A1 (en) * 2013-09-24 2016-08-03 Heraeus Deutschland GmbH & Co. KG Process for producing a shiny laminate structure at low temperatures
JP6315669B2 (en) * 2014-02-28 2018-04-25 ハリマ化成株式会社 Method for preparing silver fine particles

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