WO2023058656A1 - インク、インクの製造方法および積層セラミックコンデンサの製造方法 - Google Patents
インク、インクの製造方法および積層セラミックコンデンサの製造方法 Download PDFInfo
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- WO2023058656A1 WO2023058656A1 PCT/JP2022/037140 JP2022037140W WO2023058656A1 WO 2023058656 A1 WO2023058656 A1 WO 2023058656A1 JP 2022037140 W JP2022037140 W JP 2022037140W WO 2023058656 A1 WO2023058656 A1 WO 2023058656A1
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- ink
- metal nanoparticles
- hydroxycarboxylic acid
- nanoparticles
- ligand
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- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 20
- 239000003985 ceramic capacitor Substances 0.000 title claims description 16
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 127
- 239000003446 ligand Substances 0.000 claims abstract description 119
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 141
- 229910052759 nickel Inorganic materials 0.000 claims description 70
- 239000002105 nanoparticle Substances 0.000 claims description 67
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
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- 238000005245 sintering Methods 0.000 claims description 12
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- 239000011521 glass Substances 0.000 claims description 4
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- 230000015572 biosynthetic process Effects 0.000 description 10
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 8
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 7
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- 230000005540 biological transmission Effects 0.000 description 4
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- 229940074391 gallic acid Drugs 0.000 description 4
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- 238000003917 TEM image Methods 0.000 description 3
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Definitions
- the present invention relates to an ink, a method for producing the ink, and a method for producing a multilayer ceramic capacitor.
- Multilayer ceramic capacitors can utilize metal layers formed from sintered metal nanoparticles.
- Metal nanoparticles may also be used in a variety of other contexts.
- Non-Patent Document 1 describes a method for producing nickel nanoparticles.
- the conductive layer of the MLCC may be formed from metal nanoparticles.
- One possible method for depositing metal nanoparticles in the MLCC manufacturing process is inkjet printing an ink containing metal nanoparticles onto a substrate such as a ceramic tape. Such inks may also be used to deposit metal nanoparticles in any other suitable circumstances to form any other suitable product.
- metal nanoparticle inks for inkjet deposition poses various challenges.
- many metal nanoparticles in their as-synthesized form are not dispersible and/or stable in common inkjet solvent systems such as propylene glycol butyl ether (PGBE).
- PGBE propylene glycol butyl ether
- Organic polymers and/or ligands can be introduced as stabilizers during metal nanoparticle synthesis to help disperse the metal nanoparticles in the solvent.
- the use of such organic moieties can increase the viscosity of the ink to values unsuitable for inkjet printing.
- Polymers and other stabilizers can also increase the organic carbon content of metal nanoparticles to inappropriate levels.
- a layer of metal nanoparticles may be sintered after deposition to bind the metal nanoparticles together as a film.
- Inappropriate levels of organic stabilizers on metal nanoparticles can result in the formation of insulating carbonaceous marks from the sintering process. This can degrade the performance of the resulting capacitor.
- an object of the present invention is to provide an ink in which metal nanoparticles are dispersed and which is suitable for inkjet printing.
- An ink according to an embodiment of the present invention is An ink comprising metal nanoparticles and a solvent, at least a portion of the surface of the metal nanoparticles are coordinated by hydroxycarboxylic acid ligands;
- the hydroxycarboxylic acid ligands contain a carboxyl group and at least one hydroxyl group.
- a method for producing an ink according to an embodiment of the present invention includes: a step of synthesizing metal nanoparticles; After synthesizing the metal nanoparticles, performing a ligand exchange/introduction reaction to bind hydroxycarboxylic acid ligands to at least a portion of the surface of the metal nanoparticles; dispersing the metal nanoparticles with the hydroxycarboxylic acid ligands attached to at least a portion of their surfaces in an ink solvent system; has The hydroxycarboxylic acid ligands contain a carboxyl group and at least one hydroxyl group.
- a method for manufacturing a multilayer ceramic capacitor according to an embodiment of the present invention includes: A method for manufacturing a multilayer ceramic capacitor having a plurality of layers, inkjet printing an ink comprising metal nanoparticles onto at least a portion of a substrate to obtain a layer of ink; sintering the ink layer to form an electrode layer; has at least a portion of the surface of the metal nanoparticles are coordinated by hydroxycarboxylic acid ligands; At least a part of the layer is formed from the ink containing the metal nanoparticles.
- FIG. 1 is a flow diagram illustrating an exemplary method for producing an ink containing metal nanoparticles.
- FIG. 2A shows an example of a transmission electron microscope (TEM) image of as-synthesized nickel nanoparticles.
- FIG. 2B shows an example of a transmission electron microscope (TEM) image of as-synthesized nickel nanoparticles.
- FIG. 2C shows an example of a transmission electron microscope (TEM) image of nickel nanoparticles after ligand exchange/introduction.
- FIG. 3 shows as-synthesized metal nanoparticles in propylene glycol butyl ether (PGBE).
- FIG. 4 is a graph showing thermogravimetric analysis (TGA) results for as-synthesized metal nanoparticles.
- TGA thermogravimetric analysis
- FIG. 5 is a graph showing TGA results for metal nanoparticles after ligand exchange/introduction.
- FIG. 6 is an image showing an example dispersion of metal nanoparticles in PGBE after ligand exchange/introduction.
- FIG. 7A shows a microscopic image of an ink-jet printed metal nanoparticle film printed with an example ink prepared with metal nanoparticles after ligand exchange/introduction.
- FIG. 7B shows a microscope image of an ink-jet printed metal nanoparticle film printed with the ink of the example prepared with metal nanoparticles after ligand exchange/introduction.
- FIG. 8 is a profilometer scan of the inkjet printed film shown in FIGS. 7A and 7B.
- An example is disclosed of an ink containing a dispersion of metal nanoparticles and having a low viscosity suitable for inkjet printing.
- One example provides an ink comprising metal nanoparticles with hydroxycarboxylic acid ligands coordinated to a portion of their surface, and a solvent.
- a hydroxycarboxylic acid ligand contains at least one phenyl moiety, and at least one phenyl moiety contains at least one hydroxyl group.
- Another example provides a method for producing an ink containing metal nanoparticles.
- the method includes synthesizing metal nanoparticles, and after synthesizing the metal nanoparticles, performing a ligand exchange/introduction reaction to bind hydroxycarboxylic acid ligands to at least a portion of the metal nanoparticle surface.
- a hydroxycarboxylic acid ligand contains at least one phenyl moiety, and at least one phenyl moiety contains at least one hydroxyl group.
- the method further comprises dispersing the metal nanoparticles with hydroxycarboxylic acid ligands attached to a portion of their surface in an ink solvent system to produce an ink comprising the metal nanoparticles.
- the ink of the present invention contains metal nanoparticles.
- a hydroxycarboxylic acid ligand is coordinated to at least part of the surface of the metal nanoparticles.
- a hydroxycarboxylic acid ligand contains a carboxyl group and at least one hydroxyl group. Including at least one hydroxyl group in the hydroxycarboxylic acid ligand can impart dispersibility to the metal nanoparticles.
- said hydroxycarboxylic acid ligand contains at least one phenyl moiety, which preferably contains at least one hydroxyl group.
- Such ligands may also be referred to as hydroxyphenylcarboxylic acids.
- Examples of hydroxycarboxylic acid ligands containing at least one phenyl moiety, wherein the phenyl moiety contains at least one hydroxyl group include gallic acid, 4-hydroxybenzoic acid or 3-(4-hydroxyphenyl)propionic acid.
- a hydroxycarboxylic acid ligand as a ligand, the dispersibility of metal nanoparticles can be improved and dispersion stability can be imparted.
- a hydroxycarboxylic acid ligand containing at least one phenyl moiety, and the phenyl moiety contains at least one hydroxyl group the dispersion stability of the metal nanoparticles is further improved, and the metal nanoparticles are dispersed in the ink solvent system.
- Ink suitable for inkjet can be obtained by dispersing in
- embodiments are disclosed relating to the manufacture, use, and formed films of inks comprising metal nanoparticles having hydroxycarboxylic acid ligands coordinated to at least a portion of their surface.
- the hydroxycarboxylic acid ligand comprises at least one phenyl moiety, and at least one phenyl moiety comprises at least one hydroxyl group.
- Metal nanoparticles bound by hydroxycarboxylic acid ligands according to the disclosed examples can have high dispersibility in one or more inkjet printing solvent systems.
- metal nanoparticles may include nickel nanoparticles. By including nickel nanoparticles, it is possible to obtain an ink suitable for forming a conductive layer of an MLCC.
- the metal nanoparticles preferably have a diameter of 2 nm to 80 nm.
- the diameter of the metal nanoparticles can be obtained by calculating the approximate circle equivalent diameter of at least 50 particles using a transmission electron microscope (TEM) image, and determining the diameter of the particles.
- inks according to the present disclosure can have low viscosities suitable for inkjet printing.
- the metal nanoparticles can also contain a relatively low organic carbon content, thereby avoiding the formation of inadequate amounts of carbon residue during sintering of the printed metal layer. .
- the ink of the present invention contains a solvent (dispersion medium).
- the solvent may be a solvent commonly used for conductive pastes, or a solvent commonly used for inkjet inks. Examples thereof include alcohol-based, ether-based, ester-based, hydrocarbon-based solvents, and mixed solvents thereof.
- the inkjet ink preferably contains propylene glycol butyl ether, propylene glycol methyl ether, terpineol, and dihydroterpineol acetate.
- FIG. 1 illustrates in flow an exemplary method 100 for producing inks containing metal nanoparticles according to the present disclosure.
- the method 100 includes at 102 synthesizing metal nanoparticles.
- the metal nanoparticles may include nickel nanoparticles, as shown at 104 .
- the metal nanoparticles can include any other suitable metal.
- nickel nanoparticles were synthesized via decomposition of nickel(acetylacetonate) 2 precursor by oleylamine and trioctylphosphine (TOP) at 220 °C. More specifically, first, nickel (acetylacetonate) 2 , oleylamine, and TOP were mixed, degassed at 100°C, and then heated at 220°C for 2 hours in an inert atmosphere. A method for synthesizing such nickel nanoparticles is described in more detail in Chem. modified to yield metal nanoparticles that are at least 35 nm). In some examples, metal nanoparticles were produced with diameters in the range of 40 nm to 50 nm. This synthesis yields nickel nanoparticles bound by oleylamine and TOP ligands.
- TOP trioctylphosphine
- FIGS. 2A and 2B show TEM images of as-synthesized nickel nanoparticles. TEM analysis confirmed monodisperse nickel nanoparticles of about 45 nm.
- Figure 2C shows a TEM image of nickel nanoparticles after ligand exchange/introduction with 4-hydroxybenzoic acid. As explained in more detail below, the dispersity of the nickel nanoparticles after ligand exchange/introduction increased relative to the nickel nanoparticles shown in FIGS. 2A and 2B.
- the nickel nanoparticles after ligand exchange/introduction tended to cluster either by agglomeration or agglomeration on the TEM grid compared to the as-synthesized nickel nanoparticles shown in FIGS. 2A and 2B. few.
- the as-obtained metal nanoparticles settle out of both polar and non-polar solvents within minutes.
- Such metal nanoparticle solutions are not suitable for use as inkjet inks due to the instability of the dispersion.
- as-obtained nickel nanoparticles synthesized as described above could not be dispersed in ethanol and settled in less than 2 minutes.
- the resulting nickel nanoparticles were slightly soluble in common glycol ether ink solvents such as PGBE.
- a PGBE formulation containing 10% by weight of as-synthesized nickel nanoparticles was sonicated, resulting in a somewhat dark solution with undissolved particles, but completely sedimented in less than 30 minutes.
- FIG. 3 shows the state of the PGBE formulation containing 10% by weight of as-synthesized nickel nanoparticles after 7 days.
- PGBE containing 30% by weight of as-synthesized nickel nanoparticles formed an unstable paste with a viscosity of 3,000 cP, which is too high for inkjet printing.
- the method 100 includes performing a partial ligand exchange/introduction reaction at 106 after synthesizing the metal nanoparticles.
- Ligand exchange reactions exchange the ligands used during the synthesis of the metal nanoparticles (e.g., oleylamine and/or TOP, for example) with different ligands or bind to available empty surfaces of the metal nanoparticles.
- the ligands are chosen to stabilize the metal nanoparticles in the ink solvent system and provide suitable viscosities for inkjet printing.
- the ligand may also provide a suitably low organic carbon content (e.g., less than 5 wt%) for the metal nanoparticles, which may help during sintering compared to other organic additives. Helps reduce carbon residue formation.
- a ligand may comprise any suitable compound.
- suitable ligands include phosphines, amines, thiols, alcohols, and carboxylic acids, including phenolic acids.
- carboxylic acids are particularly well suited for use as ligands in ligand exchange/introduction.
- carboxylic acids may bind less strongly to metal nanoparticles than other ligands and are therefore easier to remove during sintering without affecting the electronic properties of films formed by metal nanoparticles. may be.
- thiols can bind more strongly to metal nanoparticles, and sintering can result in the formation of residual metal sulfide phases that affect the electrical conductivity of the formed film.
- hydroxycarboxylic acid ligands can be used, as shown at 107 in FIG.
- Such ligands may contain at least one phenyl moiety with a substituted hydroxyl group.
- ligands can provide suitable dispersibility in inkjet solvent systems, and suitable low viscosity for inkjet printing, while leaving deleterious amounts of residue after sintering. It can provide a sufficiently low organic carbon content to avoid carbon residue.
- FIG. 2C shows a TEM image of ligand-exchanged/introduced nickel nanoparticles.
- the ligand-exchanged/introduced nickel nanoparticles have greater dispersibility and are consequently more uniformly distributed in FIG. 2C. It was shown that
- Table 1 lists the results of ligand exchange/introduction. 4-Hydroxybenzoic acid, 3-(4-hydroxyphenyl)propionic acid, gallic acid, citric acid, and hexanoic acid were screened as ligands for ligand exchange/introduction (Table 1).
- the PGBE formulation containing 10 wt% nickel nanoparticles after ligand exchange/introduction was A nickel nanoparticle dispersion liquid in which the nickel nanoparticles were well dispersed was obtained.
- the 4-hydroxybenzoic acid sample provided the best dispersion and stability among the ligands tested (over 1 week). It has been found that the use of hydroxycarboxylic acid ligands containing at least one phenyl moiety, where the phenyl moiety contains at least one hydroxyl group, further improves the dispersion stability of the nickel nanoparticles. Although the mechanism is not clear, it is speculated that the inclusion of a phenyl moiety in the hydroxycarboxylic acid increases the steric hindrance effect of the ligand on the nanoparticles.
- the PGBE preparation containing 10% by weight of nickel nanoparticles after ligand exchange/introduction was sonicated to give a somewhat dark solution with undissolved particles. but completely precipitated in less than 30 minutes. It was confirmed that the dispersibility of PGBE, which is a polar solvent, is lowered by using hexanoic acid having a non-polar tail as a ligand. Furthermore, as described in more detail below, Ni films have been successfully deposited by inkjet printing an ink comprising nickel nanoparticles with 4-hydroxybenzoic acid coordinated to at least a portion of the surface.
- FIG. 4 shows a TGA of an example of as-synthesized nickel nanoparticles.
- FIG. 5 shows a TGA of an example of nickel nanoparticles after ligand exchange/introduction.
- the gentle slope at the beginning of each TGA graph is due to residual solvent leaving the sample.
- the first peak in the gravimetric first derivative is attributed to oleylamine and its derivatives, indistinguishable from ligands.
- a second peak in the weight first derivative is attributed to TOP.
- the second peak of the weight first derivative did not appear without TOP. Therefore, the first peak in the weight first derivative at about 200-300° C. was attributed to oleylamine and the second peak at about 500° C. was attributed to TOP. It has also been suggested by Chem. ing.
- FIG. 6 shows a PGBE formulation containing about 10 wt % nickel nanoparticles after ligand exchange/introduction after more than 7 days.
- the nickel nanoparticles are dispersible and stable (7 days or more), while the viscosity of the ink is suitable for inkjet printing (eg, about 8 cP). Furthermore, it was found that the resulting nickel nanoparticles after ligand exchange/introduction have a low organic carbon content (eg, less than 5 wt%) suitable for MLCC manufacturing processes.
- the metal nanoparticles can be dispersed in an ink solvent system to produce an ink, as shown at 108 in FIG.
- the viscosity of the former is too high to be inkjet printed and the latter is suitable for inkjet printing.
- inks containing ligand-exchanged metal nanoparticles as disclosed can have any other suitable viscosity. Suitable viscosities include viscosities within the range of 7 cP to 20 cP.
- the printing applicability was evaluated for inks using the ligand species and solvents listed in Table 2.
- the resolution was set to 1200 dpi
- the ink discharge frequency was varied between 236 Hz and 4724 Hz
- the effective coating time was 3 minutes to apply the ink onto the printed glass substrate.
- nozzle-out frequently occurred particularly in a region where the ink ejection frequency was low. When the nozzle was out, the print applicability was evaluated while cleaning the nozzle.
- FIG. 7A shows a microscope image of a nickel nanoparticle film formed by inkjet printing an ink containing nickel nanoparticles after ligand exchange/introduction.
- FIG. 7B shows a close-up image of the nickel nanoparticle film of FIG. 7A.
- the ink contained nickel nanoparticle after ligand exchange/introduction with 4-hydroxybenzoic acid ligands coordinated to at least a portion of the surface in a PGBE ink solvent system with 1% polyvinyl butyral (PVB) additive (8 cP viscosity). One containing 30% by weight of particles was used.
- PVB polyvinyl butyral
- FIG. 8 shows a profilometer scan of the inkjet printed nickel nanoparticle film shown in FIGS. 7A and 7B.
- a nickel nanoparticle film formed by inkjet printing with nickel nanoparticles after ligand exchange/introduction has a nickel density of 0.84 mg/cm 2 and a green density of 4.9 g/cm 3 by profilometry analysis. , the membrane height was found to be about 1.9 ⁇ m.
- Inks containing ligand-exchanged/introduced metal nanoparticles for films formed by inkjet printing may be suitable for the fabrication of electrode layers of MLCCs.
- a method for manufacturing a multilayer ceramic capacitor according to an embodiment of the present invention is a method for manufacturing a multilayer ceramic capacitor having a plurality of layers, wherein an ink containing metal nanoparticles is inkjet printed on at least a part of a substrate. It has the steps of obtaining a layer of ink and sintering the layer of ink to form an electrode layer.
- the sintering temperature may be a temperature at which the metal nanoparticles are sintered together and the resulting electrode layer has conductivity, and is preferably 200° C. or higher, more preferably 300° C. or higher, and still more preferably 400° C. or higher.
- a multilayer ceramic capacitor of a desired size can be obtained by stacking a plurality of substrates and appropriately cutting them as required.
- the step of stacking a plurality of substrates may be performed either before or after sintering the ink layer.
- An ink, a method for producing the ink, and a method for producing a multilayer ceramic capacitor according to embodiments of the present invention include the following configurations.
- An ink containing metal nanoparticles and a solvent, at least a portion of the surface of the metal nanoparticles are coordinated by hydroxycarboxylic acid ligands; said hydroxycarboxylic acid ligand comprises a carboxyl group and at least one hydroxyl group; ink.
- said hydroxycarboxylic acid ligand comprises at least one phenyl moiety;
- the step of performing the ligand exchange/introduction reaction includes binding at least one of 4-hydroxybenzoic acid and 3-(4-(hydroxyphenyl)propionic acid to at least a portion of the surface of the metal nanoparticles;
- Any one of (12) to (17) above, wherein the step of dispersing the metal nanoparticles in the ink solvent system comprises dispersing the metal nanoparticles in a solvent system containing propylene glycol butyl ether. 1.
- Dispersing the metal nanoparticles in the ink solvent system comprises dispersing sufficient metal nanoparticles to provide a viscosity of 7 cP to 20 cP, (12) to (18) above.
- Any of (12) to (19) above, wherein the step of dispersing the metal nanoparticles in the ink solvent system comprises dispersing 30% by weight or more of the metal nanoparticles in the ink solvent system.
- a method for manufacturing a multilayer ceramic capacitor having a plurality of layers inkjet printing an ink comprising metal nanoparticles onto at least a portion of a substrate to obtain a layer of ink; sintering the ink layer to form an electrode layer; has at least a portion of the surface of the metal nanoparticles are coordinated by hydroxycarboxylic acid ligands; At least part of the layer is formed from the ink containing the metal nanoparticles, A manufacturing method for a multilayer ceramic capacitor.
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Abstract
Description
本出願は、2021年10月6日出願の米国仮出願第63/262,177号に基づく優先権を主張する出願であり、前記米国仮出願の内容は参照することにより本明細書に組み込まれる。
例えば、非特許文献1にはニッケルナノ粒子の製造方法が記載されている。
金属ナノ粒子および溶媒を含むインクであって、
前記金属ナノ粒子の表面の少なくとも一部は、ヒドロキシカルボン酸リガンドによって配位されており、
前記ヒドロキシカルボン酸リガンドは、カルボキシル基および少なくとも1つのヒドロキシル基を含む。
金属ナノ粒子を合成する工程と、
前記金属ナノ粒子を合成した後、リガンド交換/導入反応を行って、ヒドロキシカルボン酸リガンドを前記金属ナノ粒子の表面の少なくとも一部に結合させる工程と、
前記ヒドロキシカルボン酸リガンドが表面の少なくとも一部に結合した前記金属ナノ粒子をインク溶媒系に分散させる工程と、
を有し、
前記ヒドロキシカルボン酸リガンドは、カルボキシル基および少なくとも1つのヒドロキシル基を含む。
複数の層を有する積層セラミックコンデンサの製造方法であって、
金属ナノ粒子を含むインクを少なくとも一部の基板上にインクジェット印刷してインクの層を得る工程と、
前記インクの層を焼結して電極層を形成する工程と、
を有し、
前記金属ナノ粒子の表面の少なくとも一部は、ヒドロキシカルボン酸リガンドによって配位されており、
少なくとも一部の層が前記金属ナノ粒子を含むインクより形成されている。
本発明において、金属ナノ粒子はニッケルナノ粒子を含み得る。ニッケルナノ粒子を含むことで、MLCCの導電層を形成するのに好適なインクを得ることができる。金属ナノ粒子の直径は2nm~80nmであることが好ましい。金属ナノ粒子の直径は透過型電子顕微鏡(TEM)像を用いて、少なくとも50個以上の粒子について近似円相当径を算出し、粒子の直径とすることができる。
さらに、本開示によるインクは、インクジェット印刷に適した低粘度を有することができる。本開示によれば、金属ナノ粒子はまた、比較的低い有機炭素含有量を含むことができ、それによって、印刷された金属層の焼結中の不適切な量の炭素残渣の形成を回避する。
このようなニッケルナノ粒子の合成方法は、非特許文献1(Chem.Mater,2010,22,1340)に、より詳細に記載されている(ただし、本開示においては、前駆体量は、直径が少なくとも35nmである金属ナノ粒子を生じるように改変した)。いくつかの例では、40nm~50nmの範囲の直径を有する金属ナノ粒子が生成された。この合成は、オレイルアミンおよびTOPリガンドによって結合されたニッケルナノ粒子を生じる。
例えば、カルボン酸は他のリガンドほど強く金属ナノ粒子に結合しない場合があり、したがって、金属ナノ粒子によって形成された膜の電子特性に影響を及ぼすことなく、焼結中に除去することがより容易である場合がある。対照的に、チオールはより強く金属ナノ粒子に結合し得、そして焼結は形成されたフィルムの導電性に影響を及ぼす残留金属硫化物相の形成を生じ得る。より具体的な例として、図1の107に示すように、ヒドロキシカルボン酸リガンドを使用することができる。このようなリガンドは、置換基ヒドロキシル基を有する少なくとも1つのフェニル部分を含み得る。以下においてより詳細に記載されるように、このようなリガンドはインクジェット溶媒系における適切な分散性、およびインクジェット印刷のための適切な低粘度を提供し得、同時に、焼結後に有害な量の残留炭素を残すことを回避するために十分に低い有機炭素含有量を提供し得る。
リガンド交換/導入を行った結果を表1に記載する。リガンド交換/導入するためのリガンドとして、4-ヒドロキシ安息香酸、3-(4-ヒドロキシフェニル)プロピオン酸、没食子酸、クエン酸、およびヘキサン酸をスクリーニングした(表1)。
ヒドロキシカルボン酸リガンドであるクエン酸、4-ヒドロキシ安息香酸、3-(4-ヒドロキシフェニル)プロピオン酸および没食子酸については、リガンド交換/導入後のニッケルナノ粒子を10重量%含有するPGBE調合液はニッケルナノ粒子が良好に分散したニッケルナノ粒子分散液が得られた。極性溶媒であるPGBEには極性の基を有するリガンドを用いることで分散性が得られることが確認された。しかし、クエン酸をリガンドとした分散液は、1日程度でニッケルナノ粒子の沈降が観察された。少なくとも1つのフェニル部分を含み、当該フェニル部分が少なくとも1つのヒドロキシル基で置換されているヒドロキシカルボン酸リガンドである没食子酸サンプルは、分散液調整後、2日未満でニッケルナノ粒子が沈降した。3-(4-ヒドロキシフェニル)プロピオン酸サンプルは、分散液調整後、約1週間後にニッケルナノ粒子のいくらかの分離およびいくらかの沈降が観察された。4-ヒドロキシ安息香酸サンプルは、試験したリガンドの中で最良の分散および安定性を提供した(1週間にわたって)。少なくとも1つのフェニル部分を含み、当該フェニル部分が少なくとも1つのヒドロキシル基を含むヒドロキシカルボン酸リガンドを用いることで、ニッケルナノ粒子の分散安定性はさらに向上することが判明した。メカニズムは定かではないが、ヒドロキシカルボン酸がフェニル部分を含むことで、リガンドがナノ粒子に与える立体障害の効果が増加したためであると推測される。
また、ヘキサン酸をリガンドして用いた場合には、リガンド交換/導入後のニッケルナノ粒子を10重量%含有するPGBE調合液は超音波処理を行うことで、未溶解粒子を伴ういくらか暗色の溶液をもたらしたが、30分未満で完全に沈殿した。極性溶媒であるPGBEには非極性のテイルを有するヘキサン酸をリガンドに用いることで分散性が下がることが確認された。さらに、以下においてより詳細に記載されるように、Ni膜は、4-ヒドロキシ安息香酸が表面の少なくとも一部に配位したニッケルナノ粒子を含むインクをインクジェット印刷することによって首尾よく堆積された。
他の例では、開示されるようなリガンド交換金属ナノ粒子を含むインクが任意の他の適切な粘度を有することができる。適切な粘度には、7cP~20cPの範囲内の粘度が含まれる。
インクに含まれる金属ナノ粒子が、上述した、ヒドロキシカルボン酸リガンドが金属ナノ粒子の表面の少なくとも一部に配位している金属ナノ粒子であることにより、積層セラミックコンデンサの電極層をインクジェット印刷により好適に形成することができる。
(1)金属ナノ粒子および溶媒を含むインクであって、
前記金属ナノ粒子の表面の少なくとも一部は、ヒドロキシカルボン酸リガンドによって配位されており、
前記ヒドロキシカルボン酸リガンドは、カルボキシル基および少なくとも1つのヒドロキシル基を含む、
インク。
(2)前記ヒドロキシカルボン酸リガンドは少なくとも1つのフェニル部分を含み、
前記フェニル部分は少なくとも1つのヒドロキシル基を含む、上記(1)に記載のインク。
(3)前記ヒドロキシカルボン酸リガンドはヒドロキシフェニルカルボン酸リガンドである、上記(1)または上記(2)に記載のインク。
(4)前記金属ナノ粒子がニッケルナノ粒子を含む、上記(1)から上記(3)のいずれか一項に記載のインク。
(5)前記金属ナノ粒子は、直径が2nm~80nmである、上記(1)から上記(4)のいずれか一項に記載のインク。
(6)前記ヒドロキシカルボン酸リガンドが、4-ヒドロキシ安息香酸および3-(4-ヒドロキシフェニル)プロピオン酸の少なくとも1つを含む、上記(1)から上記(5)のいずれか一項に記載のインク。
(7)前記溶媒がプロピレングリコールブチルエーテルを含む、上記(1)から上記(6)のいずれか一項に記載のインク。
(8)前記インクがガラス上に配置される、上記(1)から上記(7)のいずれか一項に記載のインク。
(9)前記金属ナノ粒子が5重量%以下の有機炭素含有量を含む、上記(1)から上記(8)のいずれか一項に記載のインク。
(10)前記インクが、7cP~20cPの粘度を含む、上記(1)から上記(9)のいずれか一項に記載のインク。
(11)前記インクが30重量%以上の金属ナノ粒子を含む、上記(1)から上記(10)のいずれか一項に記載のインク。
(12)金属ナノ粒子を合成する工程と、
前記金属ナノ粒子を合成した後、リガンド交換/導入反応を行って、ヒドロキシカルボン酸リガンドを前記金属ナノ粒子の表面の少なくとも一部に結合させる工程と、
前記ヒドロキシカルボン酸リガンドが表面の少なくとも一部に結合した前記金属ナノ粒子をインク溶媒系に分散させる工程と、
を有し、
前記ヒドロキシカルボン酸リガンドは、カルボキシル基および少なくとも1つのヒドロキシル基を含む、
インクの製造方法。
(13)前記ヒドロキシカルボン酸リガンドは少なくとも1つのフェニル部分を含み、前記フェニル部分は少なくとも1つのヒドロキシル基を含む、上記(12)に記載のインクの製造方法。
(14)前記ヒドロキシカルボン酸リガンドはヒドロキシフェニルカルボン酸リガンドである、上記(12)または上記(13)に記載のインクの製造方法。
(15)前記金属ナノ粒子を合成する工程は、ニッケルナノ粒子を合成することを含む、上記(12)~上記(14)のいずれか一項に記載のインクの製造方法。
(16)前記金属ナノ粒子は、直径が2nm~80nmである、上記(12)~上記(15)のいずれか一項に記載のインクの製造方法。
(17)前記リガンド交換/導入反応を行う工程は、4-ヒドロキシ安息香酸および3-(4-(ヒドロキシフェニル)プロピオン酸の少なくとも1つを金属ナノ粒子の表面の少なくとも一部に結合させることを含む、上記(12)~上記(16)のいずれか一項に記載のインクの製造方法。
(18)前記インク溶媒系中に前記金属ナノ粒子を分散させる工程は、プロピレングリコールブチルエーテルを含む溶媒系中に前記金属ナノ粒子を分散させることを含む、上記(12)~上記(17)のいずれか一項に記載のインクの製造方法。
(19)前記インク溶媒系中に前記金属ナノ粒子を分散させる工程は、7cP~20cPの粘度を提供するのに十分な金属ナノ粒子を分散させることを含む、上記(12)~上記(18)のいずれか一項に記載のインクの製造方法。
(20)前記インク溶媒系中に前記金属ナノ粒子を分散させる工程は、前記インク溶媒系中に30重量%以上の金属ナノ粒子を分散させることを含む、上記(12)~上記(19)のいずれか一項に記載のインクの製造方法。
(21)複数の層を有する積層セラミックコンデンサの製造方法であって、
金属ナノ粒子を含むインクを少なくとも一部の基板上にインクジェット印刷してインクの層を得る工程と、
前記インクの層を焼結して電極層を形成する工程と、
を有し、
前記金属ナノ粒子の表面の少なくとも一部は、ヒドロキシカルボン酸リガンドによって配位されており、
少なくとも一部の層が前記金属ナノ粒子を含むインクより形成されている、
積層セラミックコンデンサの製造方法。
Claims (21)
- 金属ナノ粒子および溶媒を含むインクであって、
前記金属ナノ粒子の表面の少なくとも一部は、ヒドロキシカルボン酸リガンドによって配位されており、
前記ヒドロキシカルボン酸リガンドは、カルボキシル基および少なくとも1つのヒドロキシル基を含む、
インク。 - 前記ヒドロキシカルボン酸リガンドは少なくとも1つのフェニル部分を含み、
前記フェニル部分は少なくとも1つのヒドロキシル基を含む、請求項1に記載のインク。 - 前記ヒドロキシカルボン酸リガンドはヒドロキシフェニルカルボン酸リガンドである、請求項1または2に記載のインク。
- 前記金属ナノ粒子がニッケルナノ粒子を含む、請求項1から3のいずれか一項に記載のインク。
- 前記金属ナノ粒子は、直径が2nm~80nmである、請求項1から4のいずれか一項に記載のインク。
- 前記ヒドロキシカルボン酸リガンドが、4-ヒドロキシ安息香酸および3-(4-ヒドロキシフェニル)プロピオン酸の少なくとも1つを含む、請求項1から5のいずれか一項に記載のインク。
- 前記溶媒がプロピレングリコールブチルエーテルを含む、請求項1から6のいずれか一項に記載のインク。
- 前記インクがガラス上に配置される、請求項1から7のいずれか一項に記載のインク。
- 前記金属ナノ粒子が5重量%以下の有機炭素含有量を含む、請求項1から8のいずれか一項に記載のインク。
- 前記インクが、7cP~20cPの粘度を含む、請求項1から9のいずれか一項に記載のインク。
- 前記インクが30重量%以上の金属ナノ粒子を含む、請求項1から10のいずれか一項に記載のインク。
- 金属ナノ粒子を合成する工程と、
前記金属ナノ粒子を合成した後、リガンド交換/導入反応を行って、ヒドロキシカルボン酸リガンドを前記金属ナノ粒子の表面の少なくとも一部に結合させる工程と、
前記ヒドロキシカルボン酸リガンドが表面の少なくとも一部に結合した前記金属ナノ粒子をインク溶媒系に分散させる工程と、
を有し、
前記ヒドロキシカルボン酸リガンドは、カルボキシル基および少なくとも1つのヒドロキシル基を含む、
インクの製造方法。 - 前記ヒドロキシカルボン酸リガンドは少なくとも1つのフェニル部分を含み、
前記フェニル部分は少なくとも1つのヒドロキシル基を含む、請求項12に記載のインクの製造方法。 - 前記ヒドロキシカルボン酸リガンドはヒドロキシフェニルカルボン酸リガンドである、請求項12または13に記載のインクの製造方法。
- 前記金属ナノ粒子を合成する工程は、ニッケルナノ粒子を合成することを含む、請求項12~14のいずれか一項に記載のインクの製造方法。
- 前記金属ナノ粒子は、直径が2nm~80nmである、請求項12~15のいずれか一項に記載のインクの製造方法。
- 前記リガンド交換/導入反応を行う工程は、4-ヒドロキシ安息香酸および3-(4-(ヒドロキシフェニル)プロピオン酸の少なくとも1つを金属ナノ粒子の表面の少なくとも一部に結合させることを含む、請求項12~16のいずれか一項に記載のインクの製造方法。
- 前記インク溶媒系中に前記金属ナノ粒子を分散させる工程は、プロピレングリコールブチルエーテルを含む溶媒系中に前記金属ナノ粒子を分散させることを含む、請求項12~17のいずれか一項に記載のインクの製造方法。
- 前記インク溶媒系中に前記金属ナノ粒子を分散させる工程は、7cP~20cPの粘度を提供するのに十分な金属ナノ粒子を分散させることを含む、請求項12~18のいずれか一項に記載のインクの製造方法。
- 前記インク溶媒系中に前記金属ナノ粒子を分散させる工程は、前記インク溶媒系中に30重量%以上の金属ナノ粒子を分散させることを含む、請求項12~19のいずれか一項に記載のインクの製造方法。
- 複数の層を有する積層セラミックコンデンサの製造方法であって、
金属ナノ粒子を含むインクを少なくとも一部の基板上にインクジェット印刷してインクの層を得る工程と、
前記インクの層を焼結して電極層を形成する工程と、
を有し、
前記金属ナノ粒子の表面の少なくとも一部は、ヒドロキシカルボン酸リガンドによって配位されており、
少なくとも一部の層が前記金属ナノ粒子を含むインクより形成されている、
積層セラミックコンデンサの製造方法。
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JP2011014916A (ja) * | 2007-03-07 | 2011-01-20 | Samsung Electro-Mechanics Co Ltd | 金属ナノ粒子のエアロゾルを用いたフォトレジスト積層基板の形成方法、絶縁基板のメッキ方法、回路基板の金属層の表面処理方法、及び積層セラミックコンデンサの製造方法 |
JP2019131758A (ja) * | 2018-02-02 | 2019-08-08 | Dic株式会社 | インク組成物、光変換層及びカラーフィルタ |
JP2021501230A (ja) * | 2017-10-27 | 2021-01-14 | ナノシス・インク. | 量子ドットインクの性能及び安定性を改善するための多官能性リガンドの適用 |
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JP2011014916A (ja) * | 2007-03-07 | 2011-01-20 | Samsung Electro-Mechanics Co Ltd | 金属ナノ粒子のエアロゾルを用いたフォトレジスト積層基板の形成方法、絶縁基板のメッキ方法、回路基板の金属層の表面処理方法、及び積層セラミックコンデンサの製造方法 |
JP2021501230A (ja) * | 2017-10-27 | 2021-01-14 | ナノシス・インク. | 量子ドットインクの性能及び安定性を改善するための多官能性リガンドの適用 |
JP2019131758A (ja) * | 2018-02-02 | 2019-08-08 | Dic株式会社 | インク組成物、光変換層及びカラーフィルタ |
Non-Patent Citations (1)
Title |
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SOPHIE CARENCO ET AL.: "Controlled Design of Size-Tunable Monodisperse Nickel Nanoparticles", CHEMISTRY OF MATERIALS, vol. 22, no. 4, 2010, pages 1340 - 1349 |
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