metallic paint compositions, conductor patterns, methods and devices.

专利摘要:
METAL PAINT COMPOSITIONS, DRIVER STANDARDS, METHODS AND DEVICES.The present invention relates to metal coplexes adapted to form conductive metal films through deposition and treatment. The metal complex can be a covalent complex and can comprise a first and a second linker. Low temperature treatment can be used to convert the complex to metal. Metallic films and lines can have a low resistivity and a working function similar to pure metal. Wedge metals can be used (for example, Ag, Au, Cu). The linkers can be dative linkers including amines, asymmetric amines and carboxylated linkers. Sulfur complexes can be used. Carboxylated binders can be used. The complexes can have a high concentration of metal and can be soluble in aromatic hydrocarbon solvent. The binders can be adapted to volatilize well. Injet printing can be performed. High metal yields can be achieved with high conductivity.
公开号:BR112012010962A2
申请号:R112012010962-6
申请日:2010-11-08
公开日:2020-09-08
发明作者:Richard D. Mcculough；John A. Belot；Anna Javier；Rebecca Potash
申请人:Carnegie Mellon University；
IPC主号:

专利说明:

METAL PAINT COMPOSITIONS, DRIVER STANDARDS, #.
METHODS AND DEVICES Related Orders This invention claims priority for provisional North American patent application 5 Serial No. 61 / 259,614 filed on November 9, 2009, which is hereby incorporated by reference in its entirety.
INTRODUCTION Printed electronics are projected to be a multi-billion dollar business in the next 7-10 years, with inks constituting 10-15% of the dollar amount, according to some sources. The growing interest in printable electronics such as the rapid growth of alternatives to silicon-based technologies is fueled by, among other things, the promise of large, flexible, lightweight and low-cost devices.
More particularly, there is a need for better methods for printing networks, such as, for example, copper, silver and gold. These metals are important components of the chip, ranging from interconnectors to the organic source of field effect transistors and drain electrodes. In general, improved compositions and methods for the production of metal structures are needed, particularly for commercial and inkjet printing applications. See, for example, U.S. Patent No. 7,270,694; 7,443,027; 7,491,646; 7,494,608 (assignee: Xerox); North American Patent Publication 2010/0163810 ("Metallic paints"); North American Patent Publication 2008/0305268 ("Low Temperature Conductive Thermal Inks") and North American Patent Publication, in
2006/0130700 ("Containing Silver Inkjet Inks"). r
SUMMARY Here are provided compositions, devices and methods of making compositions and devices and methods for using compositions and devices, among other modalities.
One modality (Modality A) provides, for example, a composition comprising at least one metal complex, comprising at least one metal and at least two binders, wherein at least one first binder is a sigma donor to the metal and volatilizes over heating the metal complex, and at least one second binder different from the first, which also volatilizes by overheating the metal complex, where the metal complex is soluble in a solvent at 25 ° C. Methods of decision, formulation, and use of this composition are also provided for modality A and its submodalities.
In one embodiment, the metal is silver, gold, copper, platinum, or ruthenium.
20 In one embodiment, the metal is silver, gold, or copper.
In one embodiment, the metal is silver or gold.
In one embodiment, the metallic complex comprises only one metallic center.
In one embodiment, the metal is in an oxidation state (I) or (II).
In one embodiment, the first linker is a monodentate linker.
In one embodiment, the first linker is a bidentate linker.
30 In a modality, the first ligand is a ligand D
No tridentate. i In one embodiment, the first linker is an amine compound comprising at least two nitrogens.
In one embodiment, the first linker is an asymmetric 5-amine compound comprising at least two nitrogens.
In one embodiment, the first linker is tetrahydrothiophene or an amine.
In one embodiment, the first ligand is a thioether. The thioether can be cyclic or linear.
In one embodiment, the first linker is not a phosphine.
In one embodiment, the second linker is a carboxylate.
In one embodiment, the second linker is a carboxylate 15 comprising an alkyl group.
In one embodiment, the second linker is a carboxylate represented by -OOC-R, where R is an alkyl group, where R has 10 or less carbon atoms.
In one embodiment, the second linker is a carboxylate 20 represented by OOC-R, where R is an alkyl group, where R has 5 or less carbon atoms.
In one embodiment, the composition is substantially free of nanoparticles.
In one embodiment, the composition is totally free of 25 nanoparticles.
In one embodiment, the composition has a sharp decomposition transition starting at a temperature below 200 ° C.
In one embodiment, the composition has a sharp decomposition transition starting at a temperature below
- 150 ° C. AND.
- In one embodiment, the composition can be stored at about 25 ° C for at least 100 hours without substantial metal deposition (0).
In one embodiment, the composition still comprises at least one solvent for the complex.
In one embodiment, the composition further comprises at least one aromatic hydrocarbon solvent.
In one embodiment, the composition further comprises a solvent, and the concentration of the complex is about 200 mg / ml or less.
In most cases, the solvent is an aromatic hydrocarbon solvent.
In one embodiment, the metal complex comprises at least 25% by weight of metal.
In one embodiment, the metal complex comprises at least 50% by weight of metal.
In one embodiment, the metal complex comprises at least 70% by weight of metal.
20 Ern a modality, the second binder is a carboxylate, the first binder is a polyidentated amine, and the metal is silver, gold, or copper.
In one embodiment, the second binder is a carboxylate, the first binder is an asymmetric polyidentated amine, q metal is silver or gold, where the solvent is toluene.
Another embodiment (Mode B) provides a composition comprising at least one metal complex comprising at least one metal and at least two linkers, where at least the first linker is a sulfur-containing linker, and at least the second linker is different from the first what is,
optionally, it is a carboxylate, in which the L- metal complex is soluble in a solvent at 25 ° C. Manufacturing methods, - formulation and use of this composition are also provided for Modality B and submodalities thereof. The composition can be substantially free of nanoparticles.
In one embodiment, the second linker is a carboxylate; for example, carboxylate is not optional.
In one embodiment, the content of the metal in the complex is 10 of at least 50 °: by weight.
In one case, the sulfur-containing ligand is a thioether ligand. The thioether can be cyclic or linear '.
In one embodiment, the sulfur-containing binder is tetrahydrothiophene.
In one embodiment, the sulfur-containing binder is dialkylthioether.
In one embodiment, the sulfur-containing binder is dithioalkane.
In one embodiment, the sulfur-containing binder is 20 dithiooctane.
In one embodiment, the sulfur-containing binder comprises one or two sulfur atoms.
In one embodiment, the sulfur-containing binder is a bidentate binder.
In one embodiment, the sulfur-containing binder has six carbons or less, or four carbons or less, or two carbons or less.
Another embodiment (Mode C) provides a composition comprising at least one metal complex comprising at least one metal and at least two binders, wherein at least
-4 0 6/61
P minus the first binder is an amine binder and at least k, the second binder is different from the first in which, optionally, it is a carboxylate, in which the metallic complex is soluble in a solvent at 25 ° C. Manufacturing methods, 5 formulation and use of this composition are also provided for Modality C and submodalities thereof. The composition can be substantially free of nanoparticles.
Another embodiment provides that the metal content in the complex is at least 50% by weight.
Another embodiment provides that the second linker is a carboxylate.
Another modality provides that the metal is silver, gold, copper, platinum or ruthenium.
15 Another modality provides that the metallic complex comprises only one metallic center.
Another modality provides that the metal is in an oxidation state (I) or (II).
Another embodiment provides that the first linker is a monodentate linker.
Another embodiment provides that the first linker is a bidentate linker.
Another embodiment provides that the first linker is a tridentate linker.
Another embodiment provides that the first linker is an asymmetric amine linker comprising at least two nitrogens.
Another embodiment provides that the first binder is an asymmetric amine compound comprising at least two nitrogens.
Another modality (Modality D) provides a composition
G comprising at least one neutral metal complex comprising at least one metal in an oxidation state (I) or (II), and at least two binders, wherein at least one first binder is a neutral sigma donor to the metal and volatilizes under heating of the metal complex to a temperature below 150 ° C, and at least one second anionic binder different from the first that also volatilizes under heating of the metal complex to a temperature below 150 ° C, where, optionally, the metal complex it is soluble in a solvent at 25 ° C. Methods of manufacturing, formulating and using this composition are also provided for Modality D and its submodalities.
15 Another embodiment provides that the first linker is a linker containing sulfur.
Another embodiment provides that the first linker is tetrahydrothiophene.
Another modality provides that the first ligand is 20 thioether. The thioether can be cyclic or linear.
Another embodiment provides that the first ligand comprises at least two sulfur.
Another embodiment provides that the first linker has six or less carbon atoms.
25 Another embodiment provides that the first linker has four or less carbon atoms.
Another embodiment provides that the first linker has two or less carbon atoms.
Another embodiment provides that the first linker and the second linker are carboxylates.
Another modality provides that the number of atoms of
F carbon in the complex is twenty or less.
Another embodiment provides a method comprising: depositing an ink on a surface, wherein the ink 5 comprises a composition according to the modalities described herein, and producing a conductive metal film by heating or irradiating said ink.
In one embodiment, the production step is carried out by heating.
10 In one embodiment, the production step is carried out by irradiation.
In one embodiment, the ink comprises a composition in accordance with Mode A and submodalities of mesrna.
In one embodiment, the ink comprises a composition 15 according to Mode B and submodalities thereof.
In one embodiment, the ink comprises a composition according to Mode C and its submodalities.
In one embodiment, the ink comprises a composition according to Mode D and its submodalities.
20 In one embodiment, the metal is gold, silver, or copper.
In one embodiment, the ink is substantially free of nanoparticles prior to deposition.
In one embodiment, the ink is substantially free of. nanoparticles after deposition.
25 In one embodiment, deposition is performed by inkjet deposition.
In one embodiment, production is carried out by heating to a temperature of about 250 ° C or less.
In one embodiment, production is carried out by heating to a temperature of about 200 ° C or less.
W 9/61 0 k.
In one embodiment, production is carried out by heating to a temperature of about 150 ° C or less.
In one embodiment, the film is in the form of a line, and the line has a conductivity of at least 1,000 5 S / cm.
In one embodiment, the film is in the form of a line, and the line has a conductivity of at least 5,000 S / cm.
In one embodiment, the film is in a 10-line form, and the line has a conductivity of at least 10,000 S / cm.
In one embodiment, the film is in a line shape, and the line has a working function that is 25% of the working function of pure metal.
15 In one embodiment, the film is in the form of a line, and the line has a working function that is 10% of the working function of pure metal.
In one embodiment, the film is in the form of a line, and the line has a working function that is 5% 20 of the working function of pure metal.
Another method provides a method comprising: a deposit of paint on a surface to form a deposit, converting the deposit from a metal film, in which the metal film shows a working function that 25 is within 25 percent of the function of pure metal.
In one embodiment, the deposit is heated.
In one embodiment, the deposit is irradiated.
In one embodiment, the ink comprises a composition 30 according to the embodiments described herein.
W 10/61 D
K b In one embodiment, the ink comprises a composition
W according to modality A and sub-modalities thereof. - In one embodiment, the ink comprises a composition according to the modality and B sub-modalities thereof.
5 In one embodiment, the ink comprises a composition according to the modality and C sub-modalities thereof.
In one embodiment, the ink comprises a composition according to modality D and sub-modalities thereof.
In one embodiment, the metal is silver, gold, or copper.
10 In one embodiment, the ink is substantially free of nanoparticles prior to deposition.
In one embodiment, the ink is substantially free of nanoparticles after deposition.
In one embodiment, the deposit is made by 15 inkjet depositions.
In one embodiment, the conversion is carried out by heating to a temperature of about 250 ° C or less.
In a modality, the conversion is carried out by heating to a temperature of about 200 ° C or less.
20 In one embodiment, the conversion is carried out by heating to a temperature of about 150 ° C or less.
In one embodiment, the film is in the form of a line, and the line has a conductivity of at least 1,000 S / cm.
25 In one embodiment, the film is in the form of a line, and the line has a conductivity of at least 5,000 S / cm.
In one embodiment, the film is in the form of a line, and the line has a conductivity of at least 10,000 30 S / cm.
In one embodiment, the film is in the form of a + J line, and the line has a working function that is within 10 percent of the working function of pure metal.
In one embodiment, the film is in the form of a 5 line, and the line has a working function that is within 5 percent of the working function of pure metal.
Another embodiment provides a composition comprising at least one metal complex comprising at least one metal and at least two binders, wherein at least one first binder is a donor sigma for the metal and volatilizes upon heating the metal complex, and at at least one second binder which is also volatilized by heating the metal complex, where the metal complex is soluble in a solvent at 25 ° C.
15 In one embodiment, the first linker and the second linker are the same linker.
In one embodiment, the first linker and the second linker are different linkers.
In one embodiment, metal is copper. In other 20 embodiments, the metal can also be, for example, silver, gold, platinum, ruthenium.
In one embodiment, the first linker comprises at least one nitrogen atom and at least two oxygen atoms.
25 In one embodiment, the first linker and the second linker are the same linker, and the first linker comprises at least one nitrogen atom and at least two oxygen atoms.
In one embodiment, the first linker and the second linker are the same linker, and in which the first linker
W 12/61 ¥ 0 * [- comprises at least one nitrogen atom and at least two oxygen atoms, as well as at least one fluorine. - In one embodiment, the first ligand is a tridentate ligand.
5 In one embodiment, the first linker is a Schiff-based tridentate linker.
In one embodiment, the first linker comprises at least one secondary amine group, at least one carbonyl group, and at least one ether group.
10 In other embodiments, the compositions consist essentially of the ingredients and components described herein.
Another embodiment provides a composition comprising at least one metal complex comprising at least one metal and at least two binders, it follows that at least one first binder is a donor sigma for the metal and volatilizes upon heating the metal complex to a temperature of about 250 ° C or less, and at least one second binder, which is optionally different from the first, 20 which is also volatilized by heating the metal complex to a temperature of about 250 ° C or less.
In one embodiment, the metal complex is heated to a temperature of 150 ° C or less.
In one embodiment, the metal complex is soluble at 25-25 ° C.
In one embodiment, the composition after heating provides a metal with a working function that is within 25 percent of the working function of pure metal.
In one embodiment, the composition after heating 30 provides a metal composition having a conductivity
# 13/61 0
F l- at least 1,000 S / cm. . and Another modality provides a method that includes: a deposit of paint on a surface to form a deposit, converting the deposit into a metal film, in which the metal film shows a conductivity of at least 1,000 S / cm.
Another modality provides that the conductivity is at least 5,000 S / cm.
Another modality predicts that the conductivity is at least 10.000 S / cm.
Another method provides that the conversion is carried out by heating to a temperature of about 200 ° C or less.
Another method provides that the conversion is carried out by heating to a temperature of about 150 ° C or less.
15 Yet in addition, another embodiment is a composition comprising at least one metal complex consisting essentially of at least one metal and at least two binders bound to the metal, wherein at least one first binder is a neutral donor for the metal and 20 volatilizes under heating of the metal complex, and at least one second binder different from the first, which also volatiles under heating of the metal complex and is negatively charged.
Another modality predicts that the first binder is made up essentially of nitrogen and / or sulfur.
Another embodiment provides that the second linker consists essentially of a methyl carboxylate.
Another modality provides that the complex is soluble in toluene.
30 Another modality provides that the complex consisting of
14/61 essentially of metal, the first linker, and the second linker is neutrally charged.
At least one advantage, for at least one modality, is the ability to make useful conductive metal lines and high quality films. At least one additional advantage for the embodiment, at least one is the low temperature nature of the conversion to conductive metal. At least one additional advantage, for at least one embodiment, is the high metal content of the metal paints. at least one additional advantage, for at least one modality is the high conductivity of metallic Eilms. In addition, at least one additional advantage for at least one embodiment is the inkjet capability to be printed.
Other advantages for at least some modalities include aspects described below.
BRIEF DESCRIPTION OF THE FIGURES Figure 1 illustrates a modality, showing a molecular structure derived from diffraction of a gold complex.
Figure 2 illustrates a modality in a perspective view, showing an MFA image of Au nanoparticles well separated in a triphenylphosphine oxide matrix.
Figure 3 illustrates a modality, showing a thermogravimetric analysis of a gold complex.
Figure 4 illustrates a modality, showing a molecular structure derived from diffraction of a dinuclear silver complex.
Figure 5 illustrates a modality, showing a molecular structure derived from diffraction of a mononuclear silver complex.
Figure 6 illustrates one modality, showing a log vs. temperature resistivity graph of a (DEED) Ag (isobutyrate) line drawn between two pads 5 of gold electrodes in Si / SiO2 of a 65 mg / mL toluene solution .
Figure 7 illustrates one embodiment of a top view, showing a deposited metallic silver scanning electron microscopy image.
10 Figure 8 illustrates a modality, showing dispersed energy spectroscopy of metallic silver x-rays deposited.
Figure 9 illustrates one embodiment of a top view, showing a silver inkjet deposition.
Figure 10 illustrates a modality, showing graph of resistivity log (arbitrary units) versus temperature (° C) of a line of (DEED) Ag (isobutyrate) drawn between two gold electrode pads in 20 Si / SiO, of a solution 65 mg / ml toluene.
Figure 11 illustrates a modality, showing a graph of resistivity log (arbitrary units) versus temperature (° C) of a (DEED) Ag (cyclopropate) drawn between two gold electrode pads themselves / SiO2 of a 65 mg solution / ml of toluene.
Figure 12 illustrates a modality, showing a graph of resistivity log (arbitrary units) versus temperature (° C) of a copper complex.
Figure 13 illustrates one embodiment of a top 30 view, showing a scanning microscopy image
. 0.
copper lines drawn on a substrate 4 of Sio ,.
Figure 14 illustrates one embodiment, showing x-ray dispersive energy spectroscopy of copper lines 5 drawn on a sodium substrate2.
Figure 15 illustrates a modality, showing a molecular structure derived from diffraction of a silver complex.
Figure 16 illustrates a modality, showing XPS of 10 Au films formed from a precursor solution and evolution, with sputtering cleaning steps for Au4f, Ag3d, CIS, and OIs.
Figure 17 illustrates a modality, showing Au's work function from the precursor (4.9 eV).
15 Figure 18 illustrates a modality, showing a molecular structure derived from diffraction of a silver complex.
Figure 19 illustrates a modality, showing a graph of log resistivity (arbitrary units) versus 20 temperature (° C) of a silver line drawn between two gold electrode plates.
Figure 20 illustrates an embodiment of a top view, showing an image of a silver line drawn between two gold electrode pads.
25 Figure 21 illustrates a modality, showing the gold complex synthesis procedures.
Figure 22 illustrates a modality in a perspective view, showing a micro-casting configuration.
Figure 23 illustrates one modality, showing graph 30 of resistivity log (arbitrary units) versus temperature (° C) for metallization of gold solution.
Figure 24 illustrates an embodiment of a top view, showing a scanning electron microscopy (low resolution) image of a gold line drawn 5 between two blocks of gold electrodes prepared by lithography.
Figure 25 illustrates one modality, showing X-ray dispersive energy spectroscopy of copper lines drawn between two gold 10 electrode pads.
Figure 26 illustrates one embodiment of a top view, showing printed gold inkjet lines.
Figure 27 illustrates one modality, comparing the Au XPS peaks for Au films prepared from 15 (A) precursor solution and (B) using [- sputter deposition.
Figure 28 illustrates one modality, showing the conductivity of the gold liquid.
Figure 29 illustrates a modality, molecular structure derived from diffraction of a trinuclear gold complex.
Figures include, in some cases, colored figures and characteristics, and the characteristics of colored figures form part of the disclosure.
25 DETAILED DESCRIPTION
INTRODUCTION North American provisional application priority order no. 61 / 259,614 deposited on November 9, 2009 is hereby incorporated by reference in its entirety.
* 18/61
W 0 à Microfabrication, printing, inkjet printing, electrodes and electronics are described in, for example, Madou, Fundamentals of Microfabrication, The Science of Miniaturization, 2 "Ed., 2002.
5 Organic chemistry methods and structures are described in, for example, March's Advanced Organic Chemistry, 6 "Ed., 2007.
To help make the growing demands of printing processes and other applications feasible, new inks 10 containing wire are provided here for solution-based deposition in conductive metal films, including metallic wedge films, including, for example, copper, silver films , and gold. The paint metallization approach contained in this document is based on chemical coordination and self-reducing binders that can be, for example, heated or photochemically irradiated to produce metallic films.
Standardization methods including, for example, inkjet printing, can be employed to deposit metallic inks in a specific and predetermined way, which can be transformed directly into, for example, circuits using a laser or simple heating, including low heating temperature.
The versatility of this approach provides the printing of 25 a variety of models and patterns on a variety of substrates much cheaper than conventional deposition methods without the need for lithography. Here, a composition can comprise at least one metal complex, as well as other optional components, including, for example, solvent. In one modality, the
B 19/61 .. *. composition does not comprise a polymer. In one embodiment, the composition does not include a surfactant. In one embodiment, the composition comprises only a metal and solvent complex.
In formulating compositions, examples of prerequisite synthetic criteria include, for example: (1) compounds can be air- and moisture stable, (2) compounds can show longevity and can be stored for long periods or indefinitely, ( 3) synthesis of compounds is possible on a large scale, while it is cheap with high 10 yields, (4) compounds are soluble in aromatic hydrocarbons, such as toluene and xylenes, which are compatible with printing processes such as inkjet and pipette Patch, and / or (5) compounds must decouple. cleanly, either thermally or photochemically, to 15 base wire.
METAL COMPLEX The metal complex can be a precursor to a metal film. Organic metal transition metal compounds, metal compounds, metals, and binders are described in, for example, Lukehart, Fundamental Transition Metal Organometallic Chemistry, Brooks / Cole, 1985; Cotton and Wilkinson, Advanced Tnorganic Chemistry: A Comprehensive Text, 4 "Ed., John Wiley, 2000. The metal complex can be homoleptic or heteroleptic. The metal complex can be mononuclear, dinuclear, trinuclear, and higher. The complex metal can be a covalent complex.
The metal complex can be free of metal - carbon bond.
The metal complex as a whole may not be charged so that it is not a counter ion that is not
B 20/61 + directly connected to the metal center. For example, in one. modality, the metal complex is not represented by [Mt] "[A]", in which the metal complex and its ligands are a cation. In one embodiment, the metal complex can be represented by ML1L2, where L1 and L2 are the first and second metal binders, respectively. M here may have · '"q' 1 a positive charge that is balanced by a negative charge 'P c4'" 'of L, or L ,.
The metal complex can be free of anions, such as halide, hydroxide, nitrite, cyanide, nitrate, nitroxyl, azide, thiocyanate, isothiocyanate, tetraalkylborate, tetrahaloborate, hexafluorophosphate, triflate, tosylate, sulfate, and / or carbonate.
In one embodiment, the metal complex is free of 15 fluorine atoms, particularly for silver and gold complexes.
The composition comprising the metal complex can be substantially or totally free of particles, microparticles and nanoparticles. In particular, the composition comprising the metal complex can be substantially or totally free of nanoparticles including metal nanoparticles, or free of colloidal material. See, for example, U.S. Patent No.
7,348,365 for colloidal approaches to form 25 conductive inks. For example, the level of nanoparticles can be less than 0.1% by weight, or less than 0.01% by weight, or less than 0.001% by weight. The particle composition can be examined using methods known in the art, including, for example, SEM and TEM, spectroscopy including 30 W-Vis, plasmon resonance, and the like.
Nanoparticles can have diameters from, for example, 1 nm to
W 500 nm, or 1 nm at 100 nm.
The composition comprising the metal complex can also be free of flakes.
5 In some modalities, the composition may comprise at least two different metal complexes. e Metal complexes can also be adapted for use in forming materials such as oxides and sulfides, including ITO and ZnO.
10 In one embodiment, the metal complex is not an alkoxide such as a copper alkoxide (for example, no M-O-R bond).
SOLUBILITY The metal complex can be soluble, which facilitates further processing. It can be soluble in, for example, a non-polar or less polar solvent, such as a hydrocarbon, including an aromatic hydrocarbon solvent. Aromatic hydrocarbon solvent includes benzene and toluene. Another example is a xylene or mixtures of 20 xylenes. Aromatic polyalkyl can be used. The composition comprising a metal complex can further comprise at least one solvent for the complex, including at least one aromatic hydrocarbon solvent. An oxygenated solvent can be substantially or totally excluded, including, for example, water, alcohols, glycols including ethylene glycol, polyethers, aldehydes, and the like.
The composition comprising a metal complex may further comprise at least one solvent, and the concentration of the complex may be about 200 mg / ml or less, or
H 22/61 0 +,
I about 100 mg / ml or less, or about 50 mg / ml or less. 0 a In one embodiment, the metal complex is used without a solvent.
In one embodiment, the composition is free of, or substantially free of, water. For example, the amount of water can be less than 1% by weight. Or, the amount of oxygenated solvent may be less than 0.1% by weight or less than 0.01% by weight.
In one embodiment, the composition is free of, or substantially free of, oxygenated solvent. For example, the amount of oxygenated solvent can be less than 1% by weight. Or, the amount of oxygenated solvent may be less than 0.1% by weight or less than 0.01% by weight.
METAL CENTER 15 Metals and transition metals are known in the art.
See, for example, Cotton and Wilkinson, cited above.
Coin metals can be used including silver, gold and copper. Platinum can be used. Cobalt, nickel, and palladium can be used. Lead, iron, and tin can be used, for example. Ruthenium can be used. Other examples of metals used for conductive electronics are known and can be used as appropriate.
Mixtures of metal complexes with different metals can be used. Alloys can be formed.
25 The metal complex can include only one metallic center. Or metal complexes can comprise only one or two metal centers.
The metal may be in an oxidation state (I) or (II).
30 The metal center can be complexed with a first
& 23/61 * ~ and second ligands. Additional binders, third, fourth,. and the like can be used. The metal center can be complexed in multiple locations, including complexed with three, four, five, or five six complexing locations.
The metal center can comprise a metal useful for the. the formation of electrically conductive lines, b. particularly those metals used in the semiconductor and electronics industries.
10 Still other examples of metals include Indian and Chinese.
FIRST BINDER The first binder may provide donation of sigma electrons, or dative bonds, to the metal. Sigma donation is - known in the art. See, for example, North American Patent No. 6,821,921. The first binder can be adapted to volatilize when heated without the formation of a solid product. Heating can be done in the presence or absence of oxygen. The first binder can be a reducer for the metal. The first ligand can be in the neutral state, not an anion or a cation.
The first linker can be a polyidentate linker including, for example, a bidentate linker or a tridentate linker.
The first binder can be an amine compound, comprising at least two nitrogens. The binder can be symmetrical or asymmetric.
The first binder can be an asymmetric amine compound comprising at least two nitrogens.
The first linker can be, for example, a linker 30 comprising sulfur, such as tetrahydrothiophene, or an amine. Amine binders are known in the art. See, for example, book quoted above, Cotton and Wilkinson, page
118. Also, nitrogen heterocycles like pyridine can be used.
The first linker can be an amine including an alkyl amine. The alkyl groups can be linear, branched, or cyclic. Bridged alkylene can be used H to bind multiple nitrogen together. In the amine, the number of carbon atoms can be, for example, 15 or 10 less, or 10 or less.
The molecular weight of the first binder, including an amine, can be, for example, about 1,000 g / mol or less, or about 500 g / mol or less, or about 250 g / mol or less.
15 In one embodiment, the first linker is not one. · ^. µ phosphine. In one embodiment, the first linker is not µ. hydrothiophene. In one embodiment, the first linker does not include a linker comprising sulfur. In one embodiment, the first linker does not comprise an amine. In one embodiment, the first linker does not comprise a fluorine-containing linker.
Examples of the first linker can be found in the working examples below.
SECOND BINDER 25 The second binder is different from the first binder and can volatilize after heating the metal complex, for example, it can release carbon dioxide, as well as small volatile organic molecules, in some modalities. The second binder can be adapted to volatilize when heated without the formation of a solid product. Heating can be done in the presence or absence of oxygen. The second ligand can be a chelator with a minimum number of atoms that can support an anionic charge and provide a neutral complex. This can make the complex soluble in an aromatic hydrocarbon solvent. The second ligand can be anionic. This can be self-reducing.
The second linker may be a carboxylate, which is known in the art. See, for example, text 10 already mentioned, Cotton and Wilkinson, pages 170-172. Carboxylates, including silver carboxylates are known in the art.
See, for example, U.S. Patent Nos. 7,153,635;
7,445,884; 6,991,894; and 7,524,621.
The second linker can be a carboxylate 15 comprising a hydrocarbon such as, for example, a non-alkyl group.
· B The second linker can be a carboxylate represented by OOC-R, where R is an alkyl group, where R has 10 or less carbon atoms, or five or less 20 carbon atoms. R can be linear, branched, or cyclic. The second linker can be fluorinated, if desired including, for example, comprising trifluoromethyl groups. The second linker can be a carboxylate, but not a carboxylate fatty acid. The second linker can be an aliphatic carboxylate. The second linker cannot be a formate linker.
The molecular weight of the second binder, including carboxylate, can be, for example, about 1,000 g / mol or less, or about 500 g / mol or less, or about 250 30 g / mol, or about 150 g / mol or less, or less.
* 26/61. 0 P
T In one embodiment, the second linker does not comprise one. 4 binder containing fluorine. Examples of second ligands can be found in the working examples below.
5 AN ADDITIONAL MODE In another modality, the metal complex can
The comprise at least two linkers, comprising, first and second linkers, and the linkers can be the same or different.
In particular, another embodiment provides a composition comprising at least one metal complex, comprising at least one metal and at least two binders, wherein at least one first binder is a sigma donor to the metal and volatilizes under heating of the 15 metal complex, and at least a second binder that - also volatilizes by heating the metal complex. The metal complex can be soluble in a solvent at 25 ° C.
In one embodiment, the first linker and the second linker are the same linker. In one embodiment, the first linker and the second linker are different linkers.
In one embodiment, metal is copper. In other embodiments, the metal can also be, for example, silver, gold, platinum, or ruthenium.
In one embodiment, the first linker comprises at least one nitrogen atom and at least two oxygen atoms.
In one embodiment, the first linker and the second linker are the same linker, and the first linker 30 comprises at least one nitrogen atom and at least two oxygen atoms.
. In one embodiment, the first linker and the second / linker are the same linker, and the first linker comprises at least one nitrogen atom and at least 5 two oxygen atoms, as well as at least one fluorine.
For example, fluoride may be part of a group
Trifluoromethyl.
,, In one embodiment, the first linker is a tridentate linker. In one embodiment, the first linker is a Schiff-based tridentate linker.
In one embodiment, the first linker comprises at least one secondary amine group, at least one carbonyl group, at least one, and at least one ether group.
See, for example, for this additional embodiment, working example 6 below and the linker used in it as the first and second linker.
. CHARACTERISTICS OF METALLIC COMPLEXES The metal complex can have a sudden decomposition transition starting at a temperature of 250 ° C, 20 or less than 200 ° C, or less than 150 ° C, or less than 120 ° C.
The composition can be stored at about 25 ° C for at least 100 hours, or at least 250 hours, or at least 500 hours, or at least 1,000 hours, or at least 25 months, without substantial metal deposit ( 0).
This storage can be pure or in a solvent. The composition can be stored at lower temperatures, such as, for example, less than 25 ° C to provide more stability. For example, some compositions can be stored at 0 ° C for very long periods of time,
and *.
h including, for example, at least 30 days, or at least - -. 90 days, or at least 365 days. Alternatively, for example, some compositions can be stored at -35 ° C or below for very long periods of time including, for example, at least 30 days, or at least 90 days, or at least 365 days.
Q Complexes can include, for example, at least 25% by weight of metal, or at least 50% by weight of metal, or at least 60% by weight of metal, or at least 70% by weight of metal . This provides effective use of the metal and good conductivity after conversion to the metal.
Metal complexes can be adapted to provide sufficient stability to be commercially useful, but also sufficiently reactive to provide low cost, high quality products. One skilled in the art can adapt the first and second binders to achieve the balance required for a given application.
METHODS OF MANUFACTURING COMPOSITIONS 20 Metal complexes can be made by a variety of methods. In one embodiment, metal or silver carboxylate complexes are prepared by reacting the silver or metal carboxylate with an ester so that an exchange reaction occurs to form a new metal or silver carboxylate complex. See, for example, reaction (1) below, where R can be, for example, an alkyl group including linear, branched, or cyclic alkyl, including, for example, an alkyl group with 10 or less, or five or fewer carbon atoms. The yield of the reaction can be, for example, at least 50%, or at least 29/61, 70%, or at least 90%.
d In a periodicity, the metal or silver carboxylate complex is made without the use of metal oxide, including Ag, O. In one embodiment, metal 5 or silver carboxylate is made without using a solid state reaction. See, for example, a comparative example of reaction (2) below.
·% In one embodiment, gold complexes are prepared by reacting a gold chloride complex, which is also complexed with a sigma donor, such as tetrahydrothiophene or a phosphine, with a silver carboxylate complex. The result is precipitation of silver chloride.
See, for example, reactions (3), (4), and (5) below.
In one embodiment, the metal complexes are prepared by exchanging dative bonded binders, such as the first binders. For example, tetrahydrothiophene can be exchanged for an amine.
INK TANK Methods known in the art can be used to deposit inks, including, for example, spin coating, pipetting, inkjet printing, foil coating, rod coating, dip coating, lithography or offset printing, engraving, flexography, screen printing, stencil printing, suspended casting, stroke opening, roll to roll, spraying, and stamping. The ink formulation and the substrate can be adapted with the deposition method. see also Direct Write Technologies book already mentioned. For example, chapter 7 describes inkjet printing. Contact and non-contact deposition can be used. Vacuum deposition cannot be used. Liquid deposition can be used.
V You can adapt the paint viscosity to the deposition method. For example, viscosity can be adapted for inkjet printing. Viscosity can be, for example, about 500 Cps or less. Or viscosity can be, for example, 1,000 Cps or more. You can also adapt
Q the concentration of solids in the paint. The concentration of '% solids in the ink can be, for example, about 500 mg / ml or less, or about 250 mg / ml or less, or about 100 10 mg / ml or less, or about 150 mg / ml. ml or less, or about 100 mg / ml or less. A lower amount can be, for example, about 1 mg / ml or more, or about 10 mg / ml or more. Bands can be formulated with these top and bottom embodiments, including, for example, from about 15 mg / ml to about 500 mg / ml. In addition, the wet properties of the paint can be adapted.
Additives, such as, for example, surfactants, dispersants, and / or binders can be used to control one or more ink properties, if desired. In one embodiment, an additive is not used. In one embodiment, a surfactant is not used.
Nozzles can be used to deposit the precursor, and the nozzle diameter can be, for example, minus 25 out of 100 microns, or less than 50 microns. The absence of particles can help prevent nozzle clogging.
Upon deposition, the solvent can be removed, and the initial steps for converting the metal precursor to metal can be started.
j 31/61.
0 m
CONVERTING PRECURSOR TO METAL - - Paints and compositions that comprise metal complexes can be deposited and converted into metallic structures including films and lines. Heat and / or light 5 can be used including laser light. The atmosphere around the metal film can be controlled. For example, oxygen can be included or excluded.
%, Volatile by-products can be eliminated.
METALLIC LINES AFTER DEPOSITION AND CURING 10 Metallic lines and films can be coherent and continuous. Continuous metallization can be observed with good connectivity between the grains and a low roughness surface.
Line width can be, for example, from 1 micron to 15,500 microns, or 5 microns to 300 microns. Line width can be less than one micron if standard methods on. nanoscale are used. Dots or circles can also be made.
In one embodiment, ink formulations can be converted into metallic lines and films without the formation of substantial amounts of metal particles, microparticles, or nanoparticles.
Metal and film lines can be prepared with metal characteristics and lines prepared by another 25 methods, such as crackling.
Metal lines and films can be, for example, at least 90% by weight of metal, or at least 95% by weight of metal, or at least 98% by weight of metal.
Metal and film lines can be relatively smooth 30 according to MFA measurements.
a 32/61 + Metal lines and films can be used to .. join structures, such as electrodes or other conductive structures.
The metal may have a working function that is substantially the same as a native metal working function. For example, the difference may be 25% or
Unless, or 10% or less.
¶ Lines and grids can be formed. Multilayer and multicomponent metal characteristics can be prepared.
10 SUBSTRATES A wide variety of solid materials can be subjected to the deposition of metallic paints. Polymers, plastics, metals, ceramics, glass, silicone, semiconductors and other solids can be used.
15 Organic and inorganic substrates can be used. Types
K of substrate polyester can be used. Substrates of. paper can be used. Printed circuit boards can be used. Substrates used in the applications described here can be used.
20 Substrates can comprise electrodes and other structures, including semiconductor or conductive structures.
APPLICATIONS Deposition and crackling by direct writing methods, 25 including inkjet printing, are described in, for example, Pique, Chrisey (Eds.), Direct-Write Technologies for Rapid Prototyping Applications, Sensors, Electronics, and Tntegrated Power Sources , Academic Press, 2002.
One application is forming 30 semiconductor devices, including transistors and transistors from
! (field effect. Transistors may comprise organic I "components), including conjugated or conductive polymers.
Applications include electronics, printed electronics, flexible electronics, solar cells, 5 monitors, screens, light devices, LEDS, OLEDs, organic electronic devices, catalysis, fuel cells, RFID, and biomedical.
A The deposited metal can be used as a coating layer for use with, for example, subsequent electroplating.
Applications of other technologies are described in, for example, "Flexible Electronics" by B.D. Gates, Science, vol 323, March 20, 2009, 1566-1567, including 2D and 3D applications.
15 Examples of patents in the literature that describe - methods and applications include, for example, “US patent publications 2008/0305268; 2010/0163810; 2006/0130700; and U.S. Patent Nos. 7,014,979; 7,629,017; 6,951,666; 6,818,783; 6,830,778; 6,036,889; 20 5,882,722.
WORKING EXAMPLES Example 1. Silver complexes Precursors to silver and gold complexes were silver carboxylates. For its synthesis, a known method 25 based on Ag2o (reaction 2) was compared with a cleaner and cheaper method based on silver acetate (reaction 1). These are shown below, and two exemplary R groups are shown. The Ag2o method is based on a solid state reaction, failed to go to completion, and 30 did not give analytically pure materials. In contrast, the
¶ O
L k metathesis reaction between a carboxylic acid and% r I "silver acetate was completed, provided analytically pure compounds, and proceeded in quantitative yields. The elementary analysis of the two silver 5 complexes from this reaction (1) were C, 24.59, H, 3.72 and C, 24.68, H, 2.56 for isobutyrate and cyclopropate, .U respectively. Theoretical values are C, 24.64, H, 3.62 and% C , 24.90, H, 2.61 for isobutyrate and cyclopropate, respectively, so the approach of (1) is greater than 10 (2).
O O O O A, ~ OÁ "A" ^ J (R "A (I) R = <">
O O 15 b. Ag, O ",,, A,» A, ~, AR "'
I From the silver complexes, libraries of amine Ag-carboxylate compounds can be prepared 20 that are viable for the production of metallic silver films, lines and structures (see below).
Example 2. Gold complexes The carboxylate compounds of Example 1 are also important intermediates in the production of R-Ài.i- 25 carboxylate complexes (gold inks), through the reaction of R-Au-Cl and Ag-carboxylate (R is a dative sigma donor, or an electron pair). The driving force in this reaction is the formation of an AgCl precipitate, whose low Kps value and organic insolubility removes it from the reaction equilibrium making the overall yields quite high> and q
V 0 d Chd 85%. -. Examples of gold carboxylate complexes from the reaction of R-Au-Cl and Ag-carboxylate include Ph, PAuCl + AgOC (O) CH (CH,), 3 Ph3PAuOC (O) CH {CH,), + 5 AgCl (reaction 3) THTAuCl + AgOC (O) CH (CH,), 3 THTAuOC (O) CH (CH,), + AgCl + (reaction 4) § THTAuCl + AgOC (O) (C3H,) 3 THTAuOC ( O) (C3H,) + AgCl (reaction 5) 10 Abbreviation legend and structures: 4r 'jií' ojj -ojY 3 Ph3P OC (O) CH (CH3), OC (O) (C3H5) THT 4 15 Initially, through of this reaction, as shown in ,, 4r reaction 3, known and unknown structures of> gold triphenylphosphine carboxylate complexes were fabricated, and the crystal structure of a previously unknown species is shown in Figure 1. Although these 20 have shown excellent solubility in toluene and other aromatic hydrocarbons, they were not preferred to provide uniform films under heat treatment while they may result in well separated gold nanoparticles with less conduction pathways. This is possibly due to the presence of non-volatile triphenylphosphine in the starting precursor, which makes non-volatile triphenylphosphine oxide after heating to obtain an isolation matrix. The APM image (atomic for microscopy) of these gold nanoparticles is shown in Figure 2.
I ',: jt !:!' "'36/61 j ;:: rf mpj ,," "Example 3. Other gold complexes, including THT *" q After nanoparticle formation and results with triphenylphosphine carboxylate complexes of gold, a different perspective for the production of Au films was developed. This approach was designed to, for example, (a) maximize the metal content in the precursor
Molecular K, (b) using binders that were volatile while still being able to reduce Au (I) to Au (0), (c) * support the premise that the precursor complex remains soluble in aromatic hydrocarbon solvents, and / or (d) proceed with high global returns.
Gold tetrahydrothiophene (THT) complexes were investigated. A gateway to this chemistry is, for example, through the reaction of commercially available HAuCl4 '' 15 and 2 THT equivalents to give hj Y .: - known THT-Au-Cl. From this molecule, the reaction of an Ag-carboxylate with THT-Au-Cl can proceed with a. 'l formation of an insoluble AgCl by-product, which can be easily removed by filtration, obtaining the desired, unknown 20 THT-Au-carboxylates (Reactions (4) and (5) from the previous page,). Thus, the THT molecule would reduce Au (I), and carboxylates would crack to release CO2 and a small organic radical that would abstract hydrogen from a solvent.
25 Shown in Figure 3 is the TGA (thermogravimetric analysis) of the gold complex (in detail). On the y-axis is the percentage loss of mass and on the x-axis is the temperature. Based on the theoretical value of about 53% gold residue for the proposed structure, it can be seen that the data are in good agreement with the theory. This
: f- {37/61
A 'j ",;"' üg'V '/ ij á ÉL- "[I" -: l adds additional credit that the postulated structure is X in fact the product composition of the THT-Au-Cl and Ag reaction -carboxylate. At this stage it is noted that although the sudden transition starts at about 90 ° C, the THT-5 Au-carboxylate complexes slowly galvanize Au (0) at room temperature and can be stored cold, as pure oils & or hydrocarbon solutions aromatic.
$ After synthesis of THT-Au-carboxylates, the gold films were deposited using 10 toluene precursor solutions (varying concentrations, but varied to 200 mg / mL) and Patch pipettes. As can be seen from the log resistivity graph against temperature, complete metallization takes place up to and before 110 ° C. In addition, as the solution ages, the start of metallization begins to decrease slightly in temperature. Alternatively, "100 mg / ml Au solutions have been spin-coated in
V UV / ozone and Si / Sio clean glasses, at 1000-130Orpm. The MFA images of the Au lines between two electrode pads show continuous metallization with excellent connectivity between the grains and low surface roughness. SEM / EDXS measured unambiguously shows that Au is present and the line is coherent and continuous.
Example 4. Gold Amine Cornplexes including DEED Because of the thermal instability and slight decrease in the longevity of the THT-Au-cyclopropate complex, and partly because the silver amine complexes were performing very well, two gold complexes were made react with N, N-diethyl-ethylene-diamine (DEED) (see below).
The (THT) Au (carboxylates) were dissolved in toluene, and a large excess of DEED was added. The reaction was left b µ ^ "" '38/61 | i f {, 9 Áü t' .J P '""' "" to stir overnight, and the solution was filtered and placed under vacuum the next day. Both the cyclopropate and isobutyrate complexes were synthesized by analogous routes and their syntheses are shown below. Both 5 exhibited an increase in the metallization temperature, which suggests greater stability.
O 1) THT-Au-cyclopropate with DEED + ,, gs - Auy <h, jn "" j) ,, -.- ú <H2 THT-Au-isobutyrate with DEED o - Aujj4 h2jj) ',), , ---: 4 15 H2 Example 5. Silver Amine Complexes including TMEDA and DEED The new silver carboxylate compounds, 20 synthesized from any Ag2o or Ago2c2H3 (silver acetate, a new method) see above, were reacted neat with different multidentated amines and tested for feasibility regarding the conduction of paint materials.
All reactions were carried out overnight at room temperature, the solutions were filtered by gravity, and the excess amine removed in vacuo.
Amine ligands may be able to act as electron donor species (reducers) to achieve the transformation from Ag (I) to Ag {0). In addition, they can provide volatile by-products that minimize the effects
.- K 39/61, r *. . (, -Á k .- l '· 4 f .- - " , Of film impurities. The choice of ethyl carboxylate as the other binder was to select chelators with a minimum number of atoms that would lead to a anionic charge, making the molecule neutral and therefore soluble in aromatic hydrocarbon solvents 5. It was predicted that the carboxylate would crack again to produce CO2 (gas) and small volatile organic molecules.
% The reaction between silver cyclopropionate and N, N, N ', N'-tetramethylethylenediamine (TMEDA) was attempted. Although successful, the product was a silver dinuclear complex with Argentophilic interactions, carboxylates in intramolecular bridges, and TMEDAS in intermolecular bridges. After recrystallization from TMEDA, and despite the high metal content, the complex was found to be insoluble in toluene and hygroscopic.
1.) Synthesis of silver (I) cyclopropate with N, N, N ', N'-tetramethylethylenediamine (TMEDA). nj m: -. A, "J: '" · J) / / _ Figure 4 shows a molecular structure derived from diffraction of the dinuclear complex of the above reaction.
20 Two drawbacks of the silver TMEDA system were solubility and moisture sensitivity. It has been postulated that the solubility problem can be remedied using an asymmetric bidentated amine with long alkyl chains over an N-terminal and a non-cyclic carboxylate, which does not
'gjj í'F' i · - 40/61 .J -} ..JR could effectively pack in the solid state. With respect to the latter, it was believed that moisture sensitivity can be rooted in the weak Argentophilic interaction (Ag-Ag bond) that would hydrolyze by exposure to moisture in 5 environmental conditions to place an H2O molecule in the Ag coordination sphere. Thus, silver isobutyrate was' used as a starting material and N, N-diethylethylenediamine (DEED) as the other reagent to, P¶ hopefully, produce mononuclear molecules plus 10 coordinately saturated, soluble, non-hygroscopic molecules without Ag-Ag bonds.
2) Synthesis of silver (I) isobutyrate with N, N-diethylethylenediamine (DEED) Í R-Ag,, J, U u; ,,,,)) Figure 5 shows a molecular structure derived from diffraction of the mononular complex of the above reaction.
As can be seen from the single x-ray crystal structure (above), a mononuclear Ag (I) complex was synthesized containing an ethyl carboxylate and a bidentated asymmetric amine supporting N, N-diethyls. The coordinating geometry on the silver ion is planar trigonal with both amine nitrogens attached and a single oxygen atom from the coordinated methyl carboxylate. This complex is not sensitive to moisture and is soluble in aromatic hydrocarbons such as toluene and 25 xylenes. Thus, it provides a number of advantages.
~ r ~ -r r 41/61 t
KYY € -.,, W ^ - '^ Following the successful synthesis of the above compound, toluene solutions of 65-75 mg / mL concentrations were made, and the lines were drawn between two gold electrode pads and annealed under 5 ambient conditions. The change in resistivity was measured as a function of temperature, and the resulting metal was' preliminarily characterized. For this purpose, the following data were obtained. Figure 6 is the change 'of + log resistivity (y axis) versus temperature (° C, 10 x axis). From these data, it is apparent that a noticeable loss (about 7 orders of magnitude) of resistivity occurs between 190 and 210 ° C. To test the composition and morphology of the resulting silver, scanning electron microscopy (SEM) and dispersive energy X-ray spectroscopy (EDXS) 15 were performed. The former visualizes the material at high magnification, while the latter provides information on the elemental composition. The SEM image shows ± clearly silver metal adhering to the gold electrode.
EDXS indicates that four elements are present, Ag, si, 20 O, and C. Si and O arise from the substrate and should not be considered, whereas Ag and C are relevant. Carbon is most likely a surface-bound contamination. The resulting Ag (0) is metallic.
Figure 6 shows the log graph of resistivity 25 against temperature. Figure 7 shows SEM, and Figure 8 shows EDXS of the metallic silver deposited from the Ag (I) complex above. EDXS data showed that only C, si, O and Ag are present in the film, with Si and O originating from the substrate.
30 Deposition of solution from a Patch pipette
, 42/61 l -. "" ~ en> f - ¶Ü ... (above) was the initial method used to deposit the ink. Ag. However, this only served as a preliminary experiment prior to inkjet deposition of silver lines using a 62.5 mg / mL toluene ink. As can be seen in Figure 9, inkjet deposition was successful using a 30 µm nozzle to provide ^ lines of approximately 200 µm width.
Given the success of (DEED) Ag (isobutyrate), 'carboxylates have been altered and the cyclopropate anion as a coordination linker has been explored.
Initially it was quite surprising that this complex metallized at a temperature slightly higher than the analog (DEED) Ag (isobutyrate). However, while the present inventions are not limited by scientific theory, the reason can be revealed by the crystalline packaging of silver (I) cyclopropate with N, N, N ', N'-tetramethylethylenediamine (TMEDA). In this structure, the ¥ cyclopropyl groups stack on top of each other, stabilizing the molecular structure and similar behavior 20 can be visualized here. After evaporation of the solvent, this molecule can align using the cyclopropyl groups as a zipper, thereby thermally stabilizing the resulting film producing higher metallization temperatures.
25 Silver (I) cyclopropate with DEED> «Q pu, o O H2 °" ^ g,,, 7 _ / ">« oA ,,): jm> 43/61,! .- t € ~ —7 " "7" "'Figure 10 is the log graph of resistivity as a function of the temperature of a line of (DEED) Ag (cyclopropate) drawn between two blocks of gold electrodes in Si / SiO2 of a 65 mg / ml solution of toluene. As shown in Figure 5, a drop in resistivity of about 7 times is seen again in a range of about 50 ° C to about. 190 ° C. It is interesting that metallization occurs at a higher ± temperature, suggesting greater stability, which is what would be desirable in a product with significant shelf life and longevity.
With regard to silver, a tridentated amine (N, N, N ', N', N "-pentamethyldiethylenetriamine (PMDETA) synthesis below) was used as a coordination linker. As traced, the tridentated amine is coordinated through all 15 of its nitrogen donor atoms to produce a fully coordinated complex In Figure 11 there is again a graph, log of resistivity against temperature of a line of * (PMDEA) Ag (isobutyrate) made between two pads of gold electrodes on Si / SiO2 from of a 65mg / ml solution of toluene. As can be seen, this complex undergoes metallization at an even higher temperature than the two previous silver complexes with an almost identical 7-fold change in resistivity. This is probably 'due to two Firstly, a fully coordinated Ag (I) 25 is less labile and mobile than a triple coordinated cation, and secondly, the tridentated amine has a much higher boiling point than bide amines. made it less volatile and less able to decompose to the base metal.
30 1) Silver (I) cyclopropate with N, N, N ', N', N "-
W, 44/61 -. -J, tqç —-F & tj pentamethyldiethylenetriamine (PMDETA), 0 pure J-âp O>) "O-Ag / _ /" > 5 "N N 7" '° - ^ à,: "J" n Example 6. Copper complex A tridentate Schiff-based binder was synthesized
W by reaction of a partially fluorinated acetoacetone derivative with ethanolamine. The tridentated Schiff base was purified by recrystallization to give the product at about 50%. This binder was then reacted with copper methoxide, Cu (OMe) 2 in benzene and refluxed overnight.
A graph of temperature resistivity graph 15 is also shown (Figure 12) indicating a drop of k approximately 4 orders of magnitude suggestive in resistivity of copper metal formation. SEM / EDXS (figures 13 and 14), between two gold electrode pads, confirms the presence of the three elements, Cu, Si, and O.
20 Both si and O arrive from the substrate, while copper comes from the thermal decomposition of the complex.
OOF, cjb, n ,, no Go "b, nzene HNC -:) - Cu": - µNH _ or " NH, '" fjuxo "F> ~ jt ~ CU (OMe) 2, e¶ux ° "'F ^ RO."' "" "OY '<CF3 25 Example 7. Additional Structure Information Given the success of (DEED) Ag (isobutyrate), the cyclopropate anion was used as a coordination linker.
As can be seen from the diffraction-derived molecular structure (Figure 15), this mononuclear complex
, 45/61 -. ^ '- ~ 4 "contains the bidentate amine and the cyclopropyl carboxylate. The geometry of the fully coordinated Ag'" ion is tetrahedral with both amine nitrogen atoms attached, as well as the carboxylate oxygen atoms. In contrast, only one oxygen carboxylate was linked to the above, shown above, (DEED) Ag * (isobutyrate). Different thermal behavior W
DÊ (higher thermalization temperatures) of this compound with the two interactions Ag-O suggests that these (among the packaging factors 10, see below) may be responsible for greater stability.
Example 8. Additional manifestations, including XPS and working function Atomic force microscopy (MFA): An MFA 15 image showed the presence of a deposited gold (0) film "(molten rotation, 1300 rpm from toluene solution) 100 mg / mL) on a glass substrate. As evidenced by this 25 µm2 image, the height varied from about 40 to 60 nm with a low surface roughness 20 of 7.90 nm. The film was uniform, without holes, defects or nanoparticles and these observations were substantially continuous across the sampled areas.After MFA measurements, the electrical properties of the sample were interrogated, and these are subsequently described (see below).
25 Electrical conductivity measurements: electrical conductivity measurements were performed on thin films derived from (THT) Au-cyclopropate by the four-point contact spring pressure method under environmental conditions. The films were formed from solutions of molten toluene rotating at 1000-1300 rpm. Metallization
>.
46/61, 6! , h · "" of the film was then obtained by heating on a heating plate for about 1 minute at a temperature of about 150 ° C. This method led to Au films with thicknesses ranging from 20-50 nm. Conductivity was measured 5 using a four point probe station. The film thickness was measured by MFA on the punches in the 0 films made by the probes. Conductivity [S.cm "'] was
V calculated according to the following equation: * l 0 "= (1)
4.53xRx l where R is the resistance (R = V / I) where l is the thickness 10 of the film in cm. It was found that the Au formed from the metal paints in centrifuged casting gave conductivities on the average of about 4 x 106 Scrn "', which is only a smaller magnitude than that observed with + atomized Au samples.
15 X-Ray Excited Photoelectron Spectroscopy (XPS) and Ultraviolet Photoelectron Spectroscopy (UPS): The interface was examined using XPS and UPS measurements.
Sample Preparation The starting substrate was a highly doped wafer (n +) (1.5 X 1.5 inch '). The wafers were marked with caustic oxide buffer (BOE) in a clean room 100 at Carnegie Mellon University to remove the native oxide layer. Subsequently, the final samples were prepared as follows: 25 Atomized Au film: 5 nm Ti (adhesion layer) and 50 nm Au were atomized on the si n + doped wafer.
Thin Au film of metal precursor solution: Si n + wafer was cleaned at 120 ° C in a UV-O3 plasma cleaner for 20 and 47/61 W '~ * "' minutes. The wafer was then placed on a hot plate initially at room temperature. Subsequently, the precursor Au solution was dropped into the wafer as a 100 mg / mL toluene solution. The temperature was then raised to -150 ° C to evaporate the solvent and form the metal film. «UPS and XPS measurements + m The measurements were performed using a multiple sample surface scanning analysis in a Phi 5000 Versaprobe system 10. This system comprises a monochromatic source focused on AI Ka X-ray (1,486.7 ev source), a He source and an analyzer hemispheric.
XPS configurations: The X-ray beam was focused normal to the sample, unless specified, and the 15 emitted photoelectrons were collected at an emission angle of 45 ° in relation to the normal sample. Wide digitization data were collected by means of pass energy of 117.4 ev. High-resolution scans were obtained using 23.5 eV power pass. The XPS spectra were 20 referenced to an energy scale with Cu 2P3 / 2 binding energies at 932.67 ± 0.05 eV and Au 4f at 84.0 ± 0.05 ev. Atomized cleaning of the samples was performed using 2 kv Ar "atomization in a 3 x 3 mm area of the specimen. The atomization rate for 2 kv Ar" in a 3 mm X 3 mm scan area is determined to be 6 , 5 nm / min, using reference material Sio2 / Si with the known thickness from X-ray reflectivity and ellipsometry.
UPS configurations: UPS measurements were performed using the He I line (hv = 21.2ev). The passage of energy used
- 0 48/61 "~ .- ~ · h € · X '~ was 0.585 ev. During UPS measurements - 5 V polarization was applied to the sample to separate samples and analyze high power cuts.
The XPS and UPS spectra were processed using the 5 CasaXPS soEtware licensed by PNNL (Pacific Northwest National Laboratory). The values of the work function # were determined from the UPS spectrum by adjusting and linearly the high and low power cuts q (secondary cutting edge and Fermi edge, respectively) 10 of the spectrum and determining their intersections with the axis connection energy.
XPS Results XPS is a surface science technique whose depth of penetration (the sampling depth at 15 from the vacuum level at the top of the sample) is about 50 to 65 Â. It is able to explore the atomic composition of thin films, as well as their neighboring atoms, oxidation states, and in relative abundance. For each element, there will be a characteristic bonding energy 20 associated with each atomic orbital of the nucleus, that is, each element will give rise to a characteristic set of "peaks in the photoelectron x-ray spectrum in kinetic energies determined by the photon energy and the respective connection energies.
25 The presence of peaks at particular energies, therefore, indicates the presence of a specific element in the sample under study - in addition, the intensity of the peaks is related to the concentration of the element within the sampled region. Thus, the technique provides a quantitative analysis of the surface composition.
, W 49/61 ~. cy '
X «. In gold films deposited from the solution,. drop of 100 mg / mL solutions of toluene dropped on a Si-doped square and heated to about 150 ° C, four elements are observed - Au, Ag, C, and O. Ag adventitia 5 is an expected result of synthesis precursor Au (see above) and can be removed by additional filtration from -
P precursor solution or centrifugation of the reaction followed by
New W - t by filtration. However, in this example his presence was constant throughout the film. C and O can result either from contamination of the surface (commonly seen in XPS in handling the sample under ambient conditions before loading in the ultra-vacuum chamber) or incomplete thermal decomposition of the precursor solution. Via atomization experiments, these light elements plus 15 probably originate from the old method of contamination. As can be seen (Figure 16) from depth spectra of XPS profiles (atomized with Ar "which slowly ablate the surface, hence the term" depth profile ") in which the peaks of Au and Ag 20 remain constant ( Au actually increases as c) C and O are removed by the collision of Ar ions), while peaks C and O decrease or disappear significantly, respectively. The elementary compositions of a film by atomized, for four minutes (in our hands the maximum time for which the experiments were carried out) are as follows: Au (70.3%), Ag (5.8%), C ( 17.9%), and O (5.9%). The position of the Au 4f peak power connection unequivocally shows that the gold is in the state of zero oxidation and, as such, can be considered metallic (even more confirmed by the UPS). Based on the peak positions of the C vC 50/61 ~ ~ 'and 0 atoms
M 4. and O, these are most likely linked to each other e. most likely they exist as carbonates or carboxylates, again resulting from either atmospheric spurious contamination or incomplete combustion of the 5 precursors in air.
An important data is c) spectrum of UPS (Figure 17). -
P UPS is an extremely sensitive surface technique that
Y and scans the outermost cells 1-2 units (10 Å) from the sample. From this spectrum, it can be determined that the metallic gold film is in fact and behaves like a metal with respect to the incoming photons. It is also possible to calculate the K'aj gold working function based on the differences between the Fermi energy level (Ep) and the cutting energy (ECO). Based on this calculation, 0Au was determined from the film derived from a precursor solution to be 4.9 ev. For a sample of atomized gold, our standard comparison, 0Au is 4.7 ev. This means that the gold system described here is compatible with the organic semiconductor polymers they use to manufacture thin film transistors.
Example 9. Additional manifestations, structural information, silver thioether It has been theorized that sulfur compounds can act as a better reducer when compared to nitrogen. As such, a sulfur compound with a sufficient number of side chains ensures that solubility has been sought. A commercially available compound, 3,6-dithiaoctane was found, with the synthesis also readily available in the literature. As such, thioether 30 (B) is not a new compound. Silver isobutyrate, described ev - * -_ 51/61 ^ ~ W n ~ g in a previous section, was reacted with 3.6 -. dithiaoctane in toluene and refluxed overnight. The solution was then filtered and the solvent was removed in vacuo. The remaining yellow solid was then examined for its chemical composition and its ability to form Ag (0) metal.
"0 , 0 · /" j_ A, _, r ^, _ /
A B Crystals were grown and sent for analysis of the derived diffraction structure was obtained as shown in Figure 18. Observe the Argentophilic interactions (for example, dimerization of the silver centers), as well as intermolecular bridges of sulfur binders. This structure can be very similar to the initial TMEDA silver complex previously reported. However, this silver thioether complex is quite soluble in organic aromatic solvents. Using 100 mg / mL toluene solution from the metal complex and a Patch pipette, lines were drawn between two gold electrode pads, annealed under environmental conditions, and a preliminary thermal stability analysis was measured. Looking at the change in resistivity as a function of temperature (Figure 19), it can be seen that the silver thioether complex decomposes into base metal at about 100 ° C, which is a much lower temperature when compared to the whole silver amine complex (> 100 ° C). This lower temperature of metallization is attributed to the strong reducing power of the thioether compared to the amine binders.
0> 52/61 .e m 'r Figure 19 shows a log graph of resistivity vs - temperature, and Figure 20 shows a silver line drawn between the gold electrodes after metallization.
The metal complex was also quite stable, both in solution and in crystalline form as a solid, it can be stored in a refrigerator for weeks, 0u perhaps, or more likely indefinitely, with change
T * 0 apparently little or none in appearance or properties. In solution, it recrystallizes after some time, but can be readily redissolved in a hot water bath and used again.
In summary, the synthesis and characterization of a new silver thioether complex are shown, its crystal structure shown, and it was used to deposit 15 silver metal. The use of sulfur-containing binders represents a departure from our previous efforts in nitrogen binders, and due to their superior reduction power, lower metallization temperatures.
Example 10. Diriietiltioeter 20 Although THT-Au-carboxylate complexes have shown promising metallization results leading to metallic gold at low temperatures (90 - 100 ° C) its thermal stability was slightly less than desirable while being stored at -35 ° C, temperature at 25 ° C where they are indefinitely stable. This may be the result of the low steric burdens offered by the THT binder, whose alpha methylene groups for the sulfur atom were fixed backwards by an ethane bridge. To address this gap, we tried to increase the steric 30 thioether
«" R "53/61 ep ~> gas ~
THE . O O,. ) Aü — Cl + Ag_oju ") Aú_) + AgCl on the gold ion, using a dimethylthioeter ligand (or dimethyl sulfide). This also removes two carbon atoms and four hydrogen atoms compared to the ligand
P 'THT thus increasing the metal content available for
G 5 metallization. The synthesis is shown above. The reaction was carried out with stirring overnight at room temperature in toluene using commercially available C2H6SAuCl. Its driving force is the formation of the insoluble AgCl precipitate which is removed by simple gravity filtration. This logic proved to be correct, as the increase in the steric volume over the Au atom gives greater stability and this complex is stable indefinitely at O ° C. Surprisingly, it metallizes at a temperature similar to THT-au-carboxylates and offers high-quality gold films with exceptional conductivities. . This complex crystallized from toluene solutions, and a crystal suitable for X-ray diffraction was identified. The diffraction-derived molecular structure features 3 independent Au atoms with both terminal and sulfur bridges, as well as carboxylates bound once. There are formal aurophilic interactions between gold atoms. The molecular derived structure is shown in Figure 29.
Example 11. Additional examples.
25 Figure 21 illustrates additional aspects for the synthesis of metal complexes. The only necessary purification step p b 54/61 Ml M-W 't ~ .W n is simple filtration. Reactions go on. high yield and analytical grade. The compounds are stable in relation to air and humidity. The final product must be stored cold to reduce gold formation.
5 Figure 22 shows a microcapillary approach controlled initially by a micromanipulator arm and then "a final approach by the piezo stack.
W £ 0 Figure 23 shows graphs of the impact of aging on temperature resistivity.
10 Figure 24 shows a drawn gold line and gold cushions.
Figure 25 shows EDX data showing high gold content. Figure 26 shows an experiment for 15 inkjet printing of the gold line, with 10 rng THTAu Cyclopropanate / 1 mL dry xylene solution, 5 mm / sec travel time, 1 drop / O, 04 mm, with 30 microns of opening the head in SiO2.
Figure 27 shows gold spike XPS comparing a precursor solution approach versus an atomized approach.
Figure 28 provides additional data on conductivity and resistivity, as well as an FMA image, for a gold filter.
66 MODALITIES DESCRIBED IN THE NORTH PROVISIONAL APPLICATION NORTH 25 AMERICAN 61 / 259,614 The following 66 modalities are described in the North American provisional application 61 / 259,614 which are incorporated by reference in their entirety.
Mode 1. A composition comprising at least 30 metal complexes comprising at least one metal and
% "D'q at least two ligands, where at least a first ligand is a sigma donor for the metal and volatilizes under heating of the metal complex, and at least a second ligand different from the first, which also volatilizes 5 by heating the metal complex, where the metal complex is soluble in a solvent at 25 ° C.
"Modality 2. The composition of modality 1, in which the
4. This metal is silver, gold, copper, or platinum. '0 Mode 3. The composition of mode 1, in which the 10 metal is silver, gold, or copper.
Modality 4. The composition of modality 1, in which the metal is silver or gold.
Mode 5. The composition of mode 1, in which the metal complex comprises only the metal center.
15 Modality 6. The composition of modality 1, in which the metal is in an oxidation state (I) or (II).
Modality 7. The composition of modality 1, in which the first ligand is a bidentate ligand.
Mode 8. The composition of mode 1, where the first linker is a tridentate linker.
Modality 9. The composition of modality 1, in which the first linker is an amine compound, comprising at least two nitrogens.
Mode 10. The composition of mode 1, wherein the first linker is an asymmetric amine compound comprising at least two nitrogens.
Mode 11. The composition of mode 1, in which the first linker is a thiophene or an amine. Thiophene can be hydrothiophene.
Modality 12. The composition of modality 1, in which the first ligand is not a phosphine.
Modality 13. The composition of modality 1, in which o. second linker is a methyl carboxylate.
Mode 14. The composition of mode 1, wherein the second linker is a carboxylate comprising an alkyl group. and Modality 15. The composition of modality 1, wherein the second b binder is a carboxylate represented by -OOC-R, 'V where R is an alkyl group, where R has 10 or less 10 carbon atoms.
Modality 16. The composition of modality 1, in which the second linker is a carboxylate represented by OOC-R, in which R is an alkyl group, in which R has 5 or less carbon atoms.
Mode 17. The composition of mode 1, in that the composition is substantially free of nanoparticles.
Modality 18. The composition of modality 1, in which the composition is totally free of nanoparticles.
Mode 19. The composition of mode 1, in which the composition has a sharp decomposition transition starting at a temperature below 200 ° C.
Mode 20. The composition of mode 1, in which the composition has a sharp decomposition transition starting at a temperature below 150 ° C.
Mode 21. The mode 1 composition, wherein the composition can be stored at about 25 ° C for at least 100 hours without substantial metal deposition (0).
Mode 22. The composition of mode 1, wherein the composition still comprises at least one solvent for the complex.
- * 57/61 - ¥ Mode 23. The mode 1 composition, where the - composition still comprises at least one aromatic hydrocarbon solvent.
Mode 24. The composition of mode 1, wherein the composition still comprises at least one solvent, and the concentration of the complex is about 200 mg / ml or less.
"Mode 25. The composition of mode 1, where the G A '¶ solvent is an aromatic hydrocarbon solvent.
V Mode 26. The composition of mode 1, wherein the metal complex comprises at least 25% by weight of metal.
Modality 27. The composition of modality 1, in which the. metal complex comprises at least 50% by weight of metal.
Modality 28. The composition of modality 1, wherein the metal complex comprises at least 70% by weight of metal.
Mode 29. The composition of mode 1, in which the second binder is an ethyl carboxylate, and the first binder is a polyidentated amine, and the metal is silver, gold, or copper.
Mode 30. The composition of mode 1, in which the second binder is an ethyl carboxylate, the first binder is an asymmetric polyidentated amine, the metal is silver or gold, and the solvent is toluene.
Mode 31. A composition comprising a complex comprising a coinage metal, an ethyl carboxylate linker, and a tetrahydrothiophene linker.
Mode 32. A composition comprising a gold hydrothiophene carboxylate complex.
t 58/61 ~ 4 '. Modality 33. A composition comprising a gold hydrophiophene isobutyrate complex. Mode 34. A composition comprising a hydrothiophene gold cyclopropate complex.
5 Modality 35. A composition comprising a gold tetrahydrothiophene complex, wherein said complex is transformed into metallic gold and volatile non-metallic material under heating above about 90 ° C.
Mode 36. A composition comprising a complex comprising a coining wire, an ethyl carboxylate linker, and a bidentated asymmetric amine, referred to as N, N-diethyl support amine.
Mode 37. A composition comprising a gold N, N-diethylethylenediamine carboxylate complex.
15 Mode 38. A composition comprising a gold N, N-diethylethylenediamine isobutyrate complex.
Mode 39. A composition comprising gold complexed with ethyl carboxylate and amine.
Mode 40. A composition comprising a gold N, N-diethylethylenediamine cyclopropate complex.
Mode 41. A composition comprising a gold N, N-diethylene diamine complex, wherein said complex is transformed into metallic gold and non-metallic volatile material under heating above about 90 ° C.
Mode 42. A composition comprising a silver N, N-diethylethylenediamine carboxylate complex.
Mode 43. A composition comprising an N, N-diethylethylenediamine silver isobutyrate complex.
30 Modality 44. A composition comprising a
, 59/61 · ~
W ~ N, N-diethylethylenediamine silver isopropate complex.
. Mode 45. A composition comprising a silver N, N-diethylene diamine complex, wherein said complex is transformed into metallic silver and non-metallic volatile material under heating above about 190 ° C.
Mode 46. A composition comprising a complex comprising a coinage metal, an ethyl carboxylate, and a tridentate amine, said support amine 10 N, N, N ', N', N-pentamethyls.
Mode 47. A composition comprising an N, N, N ', N', N "-pentamethyldiethylenetriamine silver carboxylate complex.
Mode 48. A composition comprising an N, N, N ', N', N "-pentamethyldiethylenetriamine silver isobutyrate complex.
Mode 49. A composition. comprising a complex N, N, N ', N', N "-pentamethyldiethylenetriamine of silver, wherein said complex is transformed into metallic silver and volatile non-metallic material after heating above about 90 ° C.
Mode 50. A composition comprising a minting metal and a trifused Schiff base binder.
Mode 51. A composition comprising copper and a tridentified Schiff-based binder.
Mode 52. A composition comprising Cu (NH (CH, CH, OCH,) (C (CF,) CHCOCH3).
Mode 53. A composition comprising a complex comprising copper and a tridentated Schiff base binder 30, wherein said complex is transformed into
-Y 60/61 t'b 'metallic copper and volatile non-metallic material after heating to about 90 ° C.
Mode 54. An ink comprising a composition according to modalities 31-53, optionally further comprising solvent.
Mode 55. A method comprising: a deposit of ink on a surface, in which the ink comprises a composition according to modalities 1-54, and producing a conductive metal film by means of heating or irradiation of said ink.
Mode 56. Mode method 55, in which the deposit is made by inkjet deposition.
Mode 57. Mode method 55, in which production is carried out by heating to a temperature of about 250 ° C or less.
Mode 58. An article comprising a conductive metal film produced according to method methods 55-57.
Modality 59. A method comprising: the reaction of 20 gold hydrothiophene chloride with a silver carboxylate to produce gold hydrothiophene carboxylate and silver chloride.
Mode 60. A method comprising: the reaction of a gold hydrothiophene carboxylate with a diamine to produce a gold diamine carboxylate complex.
Mode 61. A method that comprises: the reaction of silver carboxylate with an asymmetric bidentated amine to produce a silver amine carboxylate complex.
Mode 62. A method comprising: the reaction of 30 silver carboxylates with a tridentated amine to produce
'W is · 61/61} r- a silver amine carboxylate complex.
V Mode 63. A method comprising: the reaction of a copper methoxide with a tridentified Schiff base to produce a complex comprising copper and said tridented 5 Schiff base.
Incorporation 64. A composition comprising a complex produced according to method methods 59-63.
Mode 65. A composition comprising at least 10 a metal complex comprising at least one metal and at least two linkers, wherein at least one first linker is an amino linker, and at least a second linker other than the first, which it is a carboxylate, in which the metal complex is soluble in a solvent at 25 ° C, and in which the metal content in the complex is at least 50% by weight.
Mode 66. A composition comprising at least one neutral metal complex comprising at least one metal in an oxidation state (I) or (II), and at least two ligands, wherein at least one first ligand is a neutral sigma donor for the metal and volatilizes by heating the metal complex to a temperature below 150 ° C, and at least one second anionic binder other than the first, which also volatilizes by heating the metal complex to a temperature below 25 ° 150 ° C, where the metal complex is soluble in a solvent at 25 ° C.

权利要求:
Claims (10)
[1]
1. Composition, c, a, r, a, ct, e, r, íza, as it comprises at least one metal complex comprising at least one metal and at least two binders, at least one first 5 binder is a sigma donor to the metal and volatilizes by heating the metal complex, and at least one second binder other than the first one that also volatilizes by heating the metal complex, in which the metal complex is soluble in a solvent at 25 ° As the metal complex comprises at least 25% by weight of metal.
[2]
2. Composition according to claim 1, £ a, r, a, et, e, r, iz, a, due to the fact that the metal is silver, gold, copper, platinum or ruthenium, or that the complex of metal comprises only one metallic center, or that the metal is in an oxidation state of (I) or (II).
[3]
3. Composition, according to claim 1, £ a, r, a, c, t, e, r, iza, da, by the fact that the first ligand is a monodentate ligand, Oll that the first ligand is a ligand bidentate, or that the first linker is a tridentate linker, or that the first linker is an amine compound comprising at least two nitrogens, or that the first linker is an asymmetric amine compound comprising at least two nitrogens, or that the first linker it is an amine, or that the first linker is a sulfur-containing linker, or that the first linker is a thioether, or that the first linker is not a phosphine.
[4]
4. Composition according to claim 1, characterized by the fact that the second linker is a carboxylate, or that the second linker is a carboxylate comprising an alkyl group, or that the second linker is a carboxylate represented by OOC-R, where R is an alkyl group, where R has 5 or less carbon atoms.
[5]
5. Composition according to claim 1, 5, e, a, r, a, ct, e, r, iza, d, a because the composition is substantially free of nanoparticles, or that the composition is entirely free of nanoparticles, or that the composition has a sharp decornposition transition starting at a temperature below 200 ° C, or that the composition has a sharp decomposition transition starting at a temperature below 150 ° C, or that the composition can be stored at about 25 ° C for at least 100 hours without substantial metal deposition (0), or that the composition further comprises at least one solvent for the complex, or that the composition further comprises at least one aromatic hydrocarbon solvent, or that the composition further comprises at least one solvent, and the concentration of the complex is about 200 mg / ml or less.
[6]
A composition according to claim 1,, c, a, r, a, c.t, and, r, i.z.a, d, a, in that the solvent is an aromatic hydrocarbon solvent.
[7]
7. Composition according to claim 1, ça, r, a, ct, e, r, í.z, a, da, by the fact that the metal complex comprises at least 50% by weight of metal, or that the metal complex comprises at least 70% by weight of metal.
[8]
8. Composition, according to claim 1, and fixed by the fact that the second binder is a carboxylate, the first binder is a polyidentated amine, and the metal is silver, gold, or copper, or that the second binder is a carboxylate , the first binder is an asymmetric polyidentated amine, the metal is silver or gold, and the solvent is toluene or xylene.
[9]
9. Method, e, a, r, a, et, e, r, í.za, do, by the fact that it comprises: 5 depositing an ink on a surface, where the ink comprises a composition as defined in any one claims 1 to 8, and producing a conductive metal film by heating or irradiating said ink.
[10]
10. Method, according to claim 9, £ a, r, a, e, t, e, r, iza, do, by the fact that the production step is carried out by heating or irradiation, in which the heating is preferably carried out at a temperature of about 250 ° C or rhenenes, or where heating is carried out more preferably at a temperature of about 200 ° C or less, or heating is carried out even more preferably at a temperature of about 150 ° C or less.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3702259A|1970-12-02|1972-11-07|Shell Oil Co|Chemical production of metallic silver deposits|

---

GB1517608A|1975-12-29|1978-07-12|Texaco Development Corp|Silver catalyst for ethylene epoxidation|

---

US4097414A|1976-08-30|1978-06-27|Texaco Development Corp.|Modified ethylene oxide catalyst and a process for its preparation|

---

US4758588A|1983-06-20|1988-07-19|Research Corporation Technologies|Diaminocyclohexane platinum complexes|

---

US5041640A|1990-09-20|1991-08-20|Warner-Lambert Company|Process for mono-, di-, trisubstituted acetic acids|

---

US5378508A|1992-04-01|1995-01-03|Akzo Nobel N.V.|Laser direct writing|

---

US5534312A|1994-11-14|1996-07-09|Simon Fraser University|Method for directly depositing metal containing patterned films|

---

SE513959C2|1994-12-30|2000-12-04|Sandvik Ab|Method of coating cemented carbide tool cutters|

---

US5882722A|1995-07-12|1999-03-16|Partnerships Limited, Inc.|Electrical conductors formed from mixtures of metal powders and metallo-organic decompositions compounds|

---

JPH1072673A|1996-04-30|1998-03-17|Nippon Terupen Kagaku Kk|Production of metallic paste and metallic coating|

---

US6010969A|1996-10-02|2000-01-04|Micron Technology, Inc.|Method of depositing films on semiconductor devices by using carboxylate complexes|

---

US5846615A|1997-02-28|1998-12-08|The Whitaker Corporation|Direct deposition of a gold layer|

---

US6511936B1|1998-02-12|2003-01-28|University Of Delaware|Catalyst compounds with β-diminate anionic ligands and processes for polymerizing olefins|

---

AU1602099A|1998-08-21|2000-03-14|Sri International|Printing of electronic circuits and components|

---

US6638573B1|1999-07-14|2003-10-28|Osaka Municipal Government|Spectacles frame surface treatment method|

---

EP1441864B1|2000-01-21|2009-11-18|Midwest Research Institute|Method for forming thin-film conductors through the decomposition of metal-chelates in association with metal particles|

---

US20020013487A1|2000-04-03|2002-01-31|Norman John Anthony Thomas|Volatile precursors for deposition of metals and metal-containing films|

---

US20030216246A1|2001-09-21|2003-11-20|Cook Jessica A|Transition metal complexes containing sulfur ligands, and polylefin production processes using them|

---

KR100807947B1|2001-01-30|2008-02-28|삼성전자주식회사|Method for preparing Asymmetric betaketoiminate ligand compound|

---

JP4073788B2|2001-04-30|2008-04-09|ポステック・ファウンデーション|Colloidal solution of metal nanoparticles, metal-polymer nanocomposite, and production method thereof|

---

KR20030022911A|2001-09-11|2003-03-19|삼성전자주식회사|Organic metal precursors for metal patterning and metal patterning method using the same|

---

US7524528B2|2001-10-05|2009-04-28|Cabot Corporation|Precursor compositions and methods for the deposition of passive electrical components on a substrate|

---

US7629017B2|2001-10-05|2009-12-08|Cabot Corporation|Methods for the deposition of conductive electronic features|

---

US6951666B2|2001-10-05|2005-10-04|Cabot Corporation|Precursor compositions for the deposition of electrically conductive features|

---

US20030148024A1|2001-10-05|2003-08-07|Kodas Toivo T.|Low viscosity precursor compositons and methods for the depositon of conductive electronic features|

---

US7553512B2|2001-11-02|2009-06-30|Cabot Corporation|Method for fabricating an inorganic resistor|

---

KR20030057133A|2001-12-28|2003-07-04|삼성전자주식회사|Organic Metal Precursor for Forming Metal Pattern and Method for Forming Metal Pattern Using the Same|

---

KR100772790B1|2002-04-30|2007-11-01|삼성전자주식회사|Organometallic Precursors for Forming Metal Pattern and Method for Forming Metal Pattern Using The Same|

---

KR100765684B1|2002-07-03|2007-10-11|삼성전자주식회사|Organometallic Precursors for Forming Metal Alloy Pattern and Method for Forming Metal Alloy Pattern Using The Same|

---

JP4069809B2|2003-06-12|2008-04-02|富士ゼロックス株式会社|Ink set for inkjet recording and inkjet recording method|

---

US20050081907A1|2003-10-20|2005-04-21|Lewis Larry N.|Electro-active device having metal-containing layer|

---

US6991894B2|2003-11-03|2006-01-31|Eastman Kodak Company|Thermally developable imaging materials with barrier layer|

---

US20050129843A1|2003-12-11|2005-06-16|Xerox Corporation|Nanoparticle deposition process|

---

US7445884B2|2004-06-09|2008-11-04|Konica Minolta Medical & Graphic, Inc.|Photothermographic material, development method and thermal development device thereof|

---

US7550179B2|2004-08-30|2009-06-23|E.I Du Pont De Nemours And Company|Method of copper deposition from a supercritical fluid solution containing copper complexes with monoanionic bidentate and neutral monodentate ligands|

---

US7270694B2|2004-10-05|2007-09-18|Xerox Corporation|Stabilized silver nanoparticles and their use|

---

US20060130700A1|2004-12-16|2006-06-22|Reinartz Nicole M|Silver-containing inkjet ink|

---

US7153635B1|2005-09-23|2006-12-26|Eastman Kodak Company|Thermally developable materials processable at lower temperatures|

---

KR101159073B1|2005-09-23|2012-06-25|삼성전자주식회사|New metal-organic precursor material and fabrication method of metal thin film using the same|

---

JP2009535497A|2006-04-12|2009-10-01|ナノマステクノロジーズインコーポレイテッド|Nanoparticles, method for producing the same, and use thereof|

---

US20080003364A1|2006-06-28|2008-01-03|Ginley David S|Metal Inks|

---

US7491646B2|2006-07-20|2009-02-17|Xerox Corporation|Electrically conductive feature fabrication process|

---

US8143431B2|2007-06-05|2012-03-27|Air Products And Chemicals, Inc.|Low temperature thermal conductive inks|

---

US7524621B2|2007-09-21|2009-04-28|Carestream Health, Inc.|Method of preparing silver carboxylate soaps|EP2705734B1|2011-05-04|2014-12-10|Liquid X Printed Metals, Inc.|Metal alloys from molecular inks|

---

US20130156971A1|2011-10-28|2013-06-20|Liquid X Printed Metals, Inc.|Transparent conductive- and ito-replacement materials and structures|

---

KR101376913B1|2011-12-27|2014-03-20|삼성전기주식회사|Copper organic metal, manufacturing mehtod for copper organic metal and copper paste|

---

CN103183978B|2011-12-27|2016-03-30|比亚迪股份有限公司|Goods of ink composite and application and surface selective metallization and preparation method thereof|

---

US20130236656A1|2012-02-27|2013-09-12|Liquid X Printed Metals, Inc.|Self-reduced metal complex inks soluble in polar protic solvents and improved curing methods|

---

KR20150006091A|2012-02-29|2015-01-15|이슘 리서치 디벨롭먼트 컴퍼니 오브 더 히브루 유니버시티 오브 예루살렘, 엘티디.|Inks containing metal precursors nanoparticles|

---

KR102009320B1|2012-08-09|2019-08-12|엘지디스플레이 주식회사|Nano particle and manufacturing of the same|

---

JPWO2014046306A1|2012-09-21|2016-08-18|住友化学株式会社|Composition for forming conductive film|

---

KR101288106B1|2012-12-20|2013-07-26|피이솔브|Metal precursors and their inks|

---

KR101547622B1|2012-12-26|2015-08-27|주식회사 두산|Metal ink composition having low viscosity and printed circuit board using the same|

---

KR101425855B1|2013-02-21|2014-08-14|서울대학교산학협력단|Electroconductive ink composite including metal-organic precursor and method for Forming the metal line using the same|

---

JP2014196384A|2013-03-29|2014-10-16|富士フイルム株式会社|Conductive film-forming composition and method for producing conductive film using the same|

---

JP6369460B2|2013-05-31|2018-08-08|日立化成株式会社|Etching composition|

---

CA2950628A1|2014-06-19|2015-12-23|National Research Council Of Canada|Molecular inks|

---

US9803098B2|2014-07-30|2017-10-31|Pesolve Co., Ltd.|Conductive ink|

---

US9683123B2|2014-08-05|2017-06-20|Pesolve Co., Ltd.|Silver ink|

---

US9624582B2|2014-12-16|2017-04-18|Eastman Kodak Company|Non-aqueous metal catalytic composition with oxyazinium photoreducing agent|

---

US9586200B2|2014-12-16|2017-03-07|Eastman Kodak Company|Forming catalytic sites from reducible silver complexes|

---

US9592493B2|2014-12-16|2017-03-14|Eastman Kodak Company|Forming silver catalytic sites from silver phosphite carboxylates|

---

US9377688B1|2014-12-16|2016-06-28|Eastman Kodak Company|Metal catalytic composition with silver N-heterocycle complex|

---

US9586201B2|2014-12-16|2017-03-07|Eastman Kodak Company|Forming catalytic sites from reducible silver-heterocyclic complexes|

---

US9387460B2|2014-12-16|2016-07-12|Eastman Kodak Company|Metal catalytic composition with silver-oxime complex|

---

US9375704B1|2014-12-16|2016-06-28|Eastman Kodak Company|Metal catalytic composition with silver carboxylate-trialkylphosphite complex|

---

US9587315B2|2014-12-16|2017-03-07|Eastman Kodak Company|Forming silver catalytic sites from reducible silver-oximes|

---

JP6835427B2|2015-07-08|2021-02-24|株式会社シマノ|Surface decoration structure of fiber reinforced plastic parts|

---

DE102015115549A1|2015-09-15|2017-03-16|Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh|Conductive nanocomposites|

---

WO2017134769A1|2016-02-03|2017-08-10|学校法人工学院大学|Metal film-forming composition and metal film-forming method|

---

WO2018213640A1|2017-05-17|2018-11-22|Mariana Bertoni|Systems and methods for controlling the morphology and porosity of printed reactive inks for high precision printing|

---

TW201930490A|2017-08-03|2019-08-01|美商電子墨水股份有限公司|Conductive ink compositions comprising gold and methods for making the same|

---

US10633550B2|2017-08-31|2020-04-28|Xerox Corporation|Molecular organic reactive inks for conductive silver printing|

---

JP2021513474A|2018-02-13|2021-05-27|リクイッド エックス プリンティッド メタルズ インコーポレイテッド|E-textiles made with particle-free conductive ink|

---

CN110444793B|2019-08-16|2021-02-05|上海元城汽车技术有限公司|Durable proton exchange membrane, preparation method and application thereof|

---

WO2021155370A1|2020-01-30|2021-08-05|Liquid X Printed Metals, Inc.|Force sensor controlled conductive heating elements|

法律状态:
2020-09-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-01-12| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

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2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US25961409P| true| 2009-11-09|2009-11-09|

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US61/259,614|2009-11-09|

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PCT/US2010/055874|WO2011057218A2|2009-11-09|2010-11-08|Metal ink compositions, conductive patterns, methods, and devices|

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