阅读说明：本技术 用于高电导率精细印刷的铜油墨 (Copper inks for high conductivity fine printing ) 是由 巴瓦纳·代奥雷 尚塔尔·帕凯 帕特里克·罗兰·卢西恩·马朗方 于 2018-12-20 设计创作，主要内容包括：铜基油墨包含乙酸铜、3-二甲基氨基-1,2-丙二醇和银盐。可以将该油墨涂覆在基体上并在基体上分解以在基体上形成导电铜涂层。该油墨提供微米厚的迹线并且可以进行丝网印刷,并在最高至约500ppm氧气的存在下进行热烧结,或者在空气中进行光烧结以产生高电导率的铜特征。由该油墨产生的烧结铜迹线具有改进的空气稳定性,并且对于具有优异分辨率的5-20mil宽的丝网印刷线具有改进的薄层电阻率。(The copper-based ink contains copper acetate, 3-dimethylamino-1, 2-propanediol, and a silver salt. The ink may be coated on a substrate and decomposed on the substrate to form a conductive copper coating on the substrate. The ink provides micron thick traces and can be screen printed and thermally sintered in the presence of up to about 500ppm oxygen or photosintered in air to produce high conductivity copper features. The sintered copper traces produced from the ink have improved air stability and improved sheet resistivity for 5-20mil wide screen printed lines with excellent resolution.)

1. A method of producing a conductive copper coating on a substrate, the method comprising: coating a substrate with a copper-based ink comprising copper acetate, 3-dimethylamino-1, 2-propanediol, and a silver salt; and decomposing the ink on the substrate to form a conductive copper coating on the substrate.

2. The method of claim 1, wherein the copper acetate and 3-dimethylamino-1, 2-propanediol form a complex in the ink and the molar ratio is about 1:1 to about 1: 2.

3. The method of claim 2, wherein the molar ratio is about 1: 1.3.

4. The method of any one of claims 1 to 3, wherein the copper acetate comprises copper acetate monohydrate in an amount to provide about 5 wt% to about 25 wt% of copper in the ink, based on the total weight of the ink.

5. The method of any one of claims 1 to 4, wherein the silver salt is in the ink in an amount of about 5 wt% to about 40 wt% based on the weight of total copper from the copper acetate.

6. The method of any one of claims 1 to 5, wherein the silver salt comprises silver oxide, silver chloride, silver bromide, silver sulfate, silver carbonate, silver phosphate, silver acetate, or silver nitrate.

7. The method of any one of claims 1 to 5, wherein the silver salt comprises silver nitrate.

8. The method of any one of claims 1 to 7, wherein the ink further comprises a solvent and a binder.

9. The method of claim 8, wherein the binder comprises a hydroxyl-and/or carboxyl-terminated polyester.

10. The method as claimed in any one of claims 1 to 9, wherein the ink on the substrate is dried at a temperature of about 100 ℃ and 150 ℃ for a period of about 10-45 minutes.

11. The method of any one of claims 1 to 10, wherein the decomposing comprises photosintering.

12. The method of any one of claims 1 to 11, wherein the application of the ink on the substrate comprises screen printing.

13. A copper-based ink comprising copper acetate, 3-dimethylamino-1, 2-propanediol, and a silver salt.

14. The ink of claim 13, wherein the copper acetate and 3-dimethylamino-1, 2-propanediol form a complex in the ink and a molar ratio is about 1:1 to about 1: 2.

15. The ink of claim 14, wherein the molar ratio is about 1: 1.3.

16. The ink of any one of claims 13 to 15, wherein the silver salt is in the ink in an amount of about 5 wt% to about 20 wt% based on the weight of copper from the copper acetate.

17. An ink according to any one of claims 13 to 16, in which the silver salt comprises silver oxide, silver chloride, silver bromide, silver sulphate, silver carbonate, silver phosphate, silver acetate or silver nitrate.

18. An ink according to any one of claims 13 to 16, in which the silver salt comprises silver nitrate.

19. The ink of any one of claims 13 to 18, further comprising a solvent and a binder.

20. The ink of claim 19, wherein the binder comprises a hydroxyl-and/or carboxyl-terminated polyester.

21. An electronic device comprising a substrate having a conductive copper coating thereon produced by the method defined in any one of claims 1 to 12.

Technical Field

The present invention relates to printing inks, in particular to printing inks for printing electronic components.

Background

Inexpensive, high conductivity and high oxidation resistance are important goals for inks used in printed electronic components. Gold (Au) and silver (Ag) are expensive but stable, i.e. resistant to oxidation. Copper (Cu) is cheaper and has similar conductivity compared to these metals, however copper is easily oxidized, so it is difficult to achieve high conductivity in printed traces.

Two main types of copper inks are used: a metallic nanoparticle-based ink; and, metal-organic decomposition (MOD) inks. Nanoparticle-based copper inks are expensive and require high Cu loadings to achieve high conductivity. Nanoparticle-based inks that must be sintered at very high temperatures and/or that must require laser/flash lamp sintering are also susceptible to oxidation. Cheap version (Novacentrix)^TM) Screen printing is only good on cardboard and photosintering has to be carried out. MOD inks can be thermally sintered at lower temperatures, but typically use expensive copper precursors such as copper formate. Additionally, MOD inks are generally not viscous and therefore cannot be screen printed. Other limitations often encountered with Cu MOD inks are corrosion by strong acid vapors (e.g. formic acid) and poor conductivity due to low metal content.

Very few reports have been made of low cost, high conductivity, and oxidation resistant screen printable inks that can be thermally and photo-sintered to produce conductive traces. To obtain high conductivity Cu traces, high loading of Cu nano-inks (about 35-70% Cu in total ink) is required. Strategies to prevent oxidation require the incorporation of silver into the NP to produce bimetallic Ag-Cu nanoparticle inks, which can increase cost. Thus, reducing copper oxidation and creating cost-effective copper-based inks for printing electronic components remains a challenge. Low cost copper salts have not proven to produce good inks meeting all the requirements listed above.

There is a need for low cost, high resolution, high conductivity, oxidation resistant screen printable inks that can be thermally and/or photo-sintered to enable fine printing. Low cost copper inks that can be screen printed on a polymer matrix and can be photosintered or thermally sintered would be of immediate commercial value.

Disclosure of Invention

In one aspect, a copper-based ink is provided that includes copper acetate, 3-dimethylamino-1, 2-propanediol, and a silver salt.

In another aspect, there is provided a method of producing a conductive copper coating on a substrate, the method comprising: coating a substrate with a copper-based ink comprising copper acetate, 3-dimethylamino-1, 2-propanediol, and a silver salt; and decomposing the ink on the substrate to form a conductive copper coating on the substrate.

Advantageously, the inks are low cost and can be formulated for screen printing applications. Micron thick ink traces can be screen printed and thermally sintered in the presence of up to about 500ppm oxygen or photosintered in air to produce high conductivity copper features. The sintered copper traces produced from this ink have improved air stability compared to traces produced from other copper inks. The sintered copper traces have good bond strength. Copper nanoparticles may be included to further improve the electrical conductivity and/or oxidation resistance of the sintered copper traces and/or to further enhance the screen printability of the ink. For a 5-20mil wide screen printed line with excellent resolution, sintered copper traces with sheet resistivity of about 20m Ω/□/mil or less can be obtained.

Other features will be described or will become apparent in the course of the following detailed description. It will be understood that each feature described herein may be used in any combination with any one or more other described features, and each feature does not necessarily rely on the presence of another feature, unless it is apparent to one of ordinary skill in the art.

Drawings

For a more clear understanding, preferred embodiments will now be described in detail, by way of example, with reference to the accompanying drawings, in which:

FIG. 1 depicts a composition comprising copper acetate monohydrate (Cu (CH)₃COO)₂·H₂O) and 3-dimethylamino-1, 2-propanediol (DMAPD).

Detailed Description

Copper-based inks contain copper acetate, 3-dimethylamino-1, 2-propanediol (DMAPD), and a silver salt. DMAPD ((CH)₃)₂NCH₂CH(OH)CH₂OH) is a readily available organic compound. Copper acetate (Cu (CH)₃COO)₂) Is an inorganic compound that is readily available and may or may not be hydrated. The hydrated copper acetate may include monohydrate (Cu (CH)₃COO)₂·H₂O), which is convenient to use and inexpensive compared to anhydrous copper acetate. In the ink, copper acetate and DMAPD form a complex. The copper acetate is preferably present in the ink in an amount to provide about 40 wt% or less of copper, based on the total weight of the ink. The copper acetate is preferably present in the ink in an amount to provide about 1 wt% or more of copper, based on the total weight of the ink. The copper acetate is preferably present in the ink in an amount to provide from about 1 wt% to about 40 wt% copper, based on the total weight of the ink. More preferably, the copper acetate provides an amount of copper in the range of about 3 wt% to about 30 wt%, or about 3 wt% to about 25 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, based on the total weight of the ink. Preferably, the molar ratio of copper acetate and DMAPD in the ink is from about 1:1 to about 1: 2. More preferably, the molar ratio of copper acetate to DMAPD is about 1: 1.3. Such a molar ratio is particularly advantageous for improving the electrical conductivity of conductive copper traces formed from the ink.

The ink is preferably substantially free of any other complex-forming amine component. The complex-forming amine component is an amine-containing compound that forms a coordination complex with copper ions. The ink is preferably substantially free of any copper precursor compounds other than copper acetate. The copper precursor compound is any compound of copper ions and ligands that can be sintered to form copper metal.

The silver salt can be any organic or inorganic salt of silver that can decompose to produce metallic silver and readily removable residue, preferably a gaseous residue at the decomposition temperature of the silver salt. The silver salt comprises one or more anions. The anion is preferably derived from a mineral acid. The anion in the metal salt is preferably an oxide, chloride, bromide, sulfate, carbonate, phosphate, acetate or nitrate. Nitrate is particularly preferred. A particularly preferred metal salt filler is silver nitrate. The silver salt is preferably present in the ink in an amount of up to about 40 wt%, preferably up to about 20 wt%, based on the total weight of copper from the ketone acetate in the ink. Preferably, the amount of silver salt is 5 wt% or more based on the total weight of copper from the ketone acetate in the ink. Preferably, the amount of silver salt ranges from about 2 wt% to about 40 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, based on the total weight of copper from the ketone acetate in the ink.

The inks may also include one or more other components that may be used to formulate the inks for a particular purpose or to improve the electrical, physical, and/or mechanical properties of the conductive traces formed from the inks. In various embodiments, the ink may comprise one or more of fillers, binders, surface tension modifiers, defoamers, thixotropic modifiers, solvents, or any mixture thereof.

The filler may include a metal, another metal-containing compound, or a mixture thereof to improve the conductivity of the conductive traces formed from the ink. The filler preferably comprises copper nanoparticles (CuNP). Nanoparticles are particles having an average size along the longest dimension in the range of about 1 to 1000nm, preferably about 1 to 500nm, more preferably about 1 to 100 nm. The nanoparticles may be flakes, nanowires, needles, substantially spherical, or any other shape. The filler is preferably present in the ink in an amount up to about 40% by weight, based on the weight of copper in the copper acetate in the ink. Preferably, the amount of filler ranges from about 1 wt% to about 40 wt%, or from about 5 wt% to about 30 wt%, or from about 10 wt% to about 30 wt%, based on the weight of copper in the copper acetate in the ink.

Binders, such as organic polymer binders, may be present in the ink as processing aids for the particular deposition process. The organic polymeric binder may be any suitable polymer, preferably a thermoplastic or elastomeric polymer. Some non-limiting examples of binders are cellulosic polymers, polyacrylates, polystyrenes, polyolefins, polyvinylpyrrolidones, polypyrrolidones, polyvinyl acetals, polyesters, polyimides, polyetherimides, polyols, silicones, polyurethanes, epoxies, phenolics, phenol-formaldehyde resins, styrene allylic alcohols, polyalkylene carbonates, fluoroplastics, fluoroelastomers, thermoplastic elastomers, and mixtures thereof. The organic polymeric binder may be a homopolymer or a copolymer. Particularly preferred binders include polyesters, polyimides, polyetherimides, or any mixtures thereof. The polymeric binder preferably comprises a polyester. Suitable polyesters are commercially available or may be made by condensation of a polyol with a polycarboxylic acid and its respective anhydride. Preferred polyesters are hydroxyl and/or carboxyl functionalized. The polyesters may be linear or branched. Solid or liquid polyesters and various solution forms may be used. In a particularly preferred embodiment, the polymeric binder comprises a hydroxyl and/or carboxyl terminated polyester, such as Rokrapol^TM7075. The polymeric binder can be present in the ink in any suitable amount. The organic polymeric binder can be present in the ink in any suitable amount, preferably in a range of about 0.05 wt% to about 10 wt%, based on the total weight of the ink. More preferably, the amount ranges from about 0.05 wt% to about 5 wt%, or from about 0.2 wt% to about 2 wt%, or from about 0.2 wt% to about 1 wt%. In one embodiment, the polymeric binder is present in the ink in an amount of about 0.02 to 0.8 weight percent, more preferably about 0.05 to 0.6 weight percent.

The surface tension modifier may be any suitable additive that improves the flow and leveling of the ink. Some non-limiting examples are surfactants (e.g., cationic or anionic surfactants), alcohols (e.g., propanol), propane diol, capric acid, dodecanethiol, glycolic acid, lactic acid, and mixtures thereof. The surface tension modifier can be present in the ink in any suitable amount, preferably in a range of about 0.1 wt% to about 5 wt%, based on the total weight of the ink. More preferably, the amount ranges from about 0.5 wt% to about 4 wt%, or from about 0.8 wt% to about 3 wt%. In a particularly preferred embodiment, the amount ranges from about 1 wt% to about 2.7 wt%.

The defoamer can be any suitable defoaming additive. Some non-limiting examples are fluorosilicones, mineral oils, vegetable oils, polysiloxanes, ester waxes, fatty alcohols, glycerin, stearates, silicones, polypropylene based polyethers, and mixtures thereof. Glycerol and polypropylene based polyethers are particularly preferred. Without the anti-foaming agent, some printed traces may tend to retain bubbles after printing, resulting in non-uniform traces. The defoamer can be present in the ink in any suitable amount, preferably in a range of about 0.0001 wt% to about 3 wt%, based on the total weight of the ink. More preferably, the amount ranges from about 0.005 wt% to about 2 wt%.

The thixotropic modifying agent may be any suitable thixotropic modifying additive. Some non-limiting examples are polyhydroxycarboxylic acid amides, polyurethanes, acrylic polymers, latexes, polyvinyl alcohols, styrene/butadiene, clays, clay derivatives, sulfonates, guar gum, xanthan gum, cellulose, locust bean gum, gum arabic, sugars, sugar derivatives, casein, collagen, modified castor oil, silicones, and mixtures thereof. The thixotropic modifying agent may be present in the ink in any suitable amount, preferably in the range of about 0.05 wt% to about 1 wt%, based on the total weight of the ink. More preferably, the amount ranges from about 0.1 wt% to about 0.8 wt%. In a particularly preferred embodiment, the amount ranges from about 0.2 wt% to about 0.5 wt%.

The solvent may be an aqueous solvent or an organic solvent. In some cases, mixtures of one or more organic solvents with aqueous solvents may be used. Aqueous solvents include, for example, water and solutions, dispersions or suspensions of the compounds in water. The organic solvent may be an aromatic solvent, a non-aromatic solvent or a mixture of aromatic and non-aromatic solvents. Aromatic solvents include, for example, benzene, toluene, ethylbenzene, xylene, chlorobenzene, benzyl ether, anisole, benzonitrile, pyridine, diethylbenzene, propylbenzene, isopropylbenzene, isobutylbenzene, p-cymene, tetrahydronaphthalene, trimethylbenzene (e.g., mesitylene), durene, p-isopropylbenzene, or any mixture thereof. Non-aromatic solvents include, for example, terpenes, glycol ethers (e.g., dipropylene glycol methyl ether, diethylene glycol, methyl carbitol, ethyl carbitol, butyl carbitol, triethylene glycol and derivatives thereof), alcohols (e.g., methylcyclohexanol, octanol, heptanol), or any mixture thereof. Dipropylene glycol methyl ether is preferred. The solvent can be present in the ink in any suitable amount, preferably in a range of about 1 wt% to about 50 wt%, based on the total weight of the ink. More preferably, the amount ranges from about 2 wt% to about 35 wt%, or from about 5 wt% to about 25 wt%. The solvent typically makes up the balance of the ink.

The ink may be formulated by mixing the components together in a mixer. Generally, any mixing process is suitable. However, planetary centrifugal mixing (e.g., in Thinky)^TMIn a mixer) is particularly useful. The mixing time may have some effect on the electrical properties of the conductive traces formed from the ink. Proper mixing of the ink ensures good electrical performance of the conductive traces. The mixing time is preferably about 25 minutes or less, or about 20 minutes or less, or about 15 minutes or less. The mixing time is preferably about 1 minute or more, or about 5 minutes or more.

Prior to decomposition, an ink is deposited on the substrate to coat the substrate. Suitable substrates may include, for example, polyethylene terephthalate (PET) (e.g., Melinex)^TM) Polyolefins (e.g., silica-filled polyolefins (Teslin)^TM) Polydimethylsiloxane (PDMS), polystyrene, acrylonitrile/butadiene/styrene, polycarbonate, polyimide (e.g., Kapton @)^TM) Polyetherimides (e.g., Ultem)^TM) Thermoplastic Polyurethane (TPU), silicone film, printed wiring board substrates (e.g., FR4), wool, silk, cotton, flax, jute, modal, bamboo, nylon, polyester, acrylic, aramid, spandex, polylactide, paper, glass, metal, dielectric coatings, and the like.

The ink may be applied to the substrate by any suitable method, such as printing. The printing method may include, for example, screen printing, stencil printing, ink jet printing, flexographic printing, gravure printing, offset printing, pad printing, air brushing, aerosol printing, typesetting, slot-die coating, or any other method. An advantage of this process is that additive methods such as screen printing or stencil printing are particularly useful. For printed electronics, the ink may be applied as traces on a substrate.

After coating the substrate with the ink, the ink on the substrate can be dried and decomposed to form a copper metal coating on the substrate. Drying and decomposition may be accomplished by any suitable technique, where the technique and conditions are determined by the type of substrate and the specific composition of the ink. Drying and decomposition of the ink may be accomplished, for example, by heating and/or photonic sintering.

In one technique, the substrate is heated to dry and sinter the ink coating to form metallic copper. The heating can be conducted at a temperature of about 100 ℃ or more, about 140 ℃ or more, or about 165 ℃ or more, or about 180 ℃ or more, while producing a conductive copper coating with good oxidative stability. The temperature may range from about 140 ℃ to about 300 ℃, or from about 150 ℃ to about 280 ℃, or from about 160 ℃ to about 270 ℃, or from about 180 ℃ to about 250 ℃. Heating is preferably carried out for a time period in the range of about 1 to 180 minutes, such as 5 to 120 minutes, or 5 to 90 minutes. The heating may be staged to first dry the ink coating and then sinter the dried coating. Drying may be carried out at any suitable temperature, for example at a temperature in the range of about 100 ℃ to about 150 ℃. Drying may be carried out for any suitable length of time, for example, about 1 to 180 minutes, or 5 to 90 minutes, or 10 to 45 minutes. The sintering is performed at a sufficient balance between temperature and time to sinter the ink to form the conductive copper coating. The substrate may be dried and/or sintered under an inert atmosphere (e.g., nitrogen and/or argon). However, the improved air stability of the ink allows sintering in the presence of oxygen, for example in an atmosphere containing up to about 500ppm oxygen. The type of heating equipment also affects the temperature and time required for drying and sintering.

In another technique, the ink coating may be dried by heating and then photonically sintered. Drying may be carried out at any suitable temperature, for example, a temperature in the range of about 100 ℃ to about 150 ℃. Drying may be carried out for any suitable length of time, for example, about 1 to 180 minutes, or 5 to 90 minutes, or 10 to 45 minutes. The photonic sintering system may be characterized as a high intensity lamp (e.g., a pulsed xenon lamp) that provides a broad band of light. The lamp may deliver about 1-30J/cm to the trace²Preferably 2 to 5J/cm²The energy of (a). The preferred range of pulse width is about 0.58-1.5 ms. The photonic sintering may be performed in air or an inert atmosphere. Laser sintering may be used if desired. Photonic sintering is particularly suitable when using polyethylene terephthalate or polyimide substrates.

For screen-printed lines of 5-20mil width, the sintered copper coating formed from the ink may have a sheet resistivity of about 20m Ω/□/mil or less, or even about 15m Ω/□/mil or less. Sheet resistivity may even be in the range of about 5-10m Ω/□/mil. For 5-20mil wide screen printed lines, the sintered copper coating formed from the ink may have a volume resistivity of about 50 μ Ω. cm or less, or even about μ Ω. cm or less. In addition, with excellent line resolution, the line width after sintering varies by less than about 17%, or less than about 10%, or less than about 5%, or less than about 2.5% for screen printed lines of 5-20mil width. Even when the line width is as low as about 5 mils, the line width after sintering can vary by less than about 17%, even less than about 5%, or even less than about 2.5%. For screen printed traces, the line width may be about 600 microns or less, for example in the range of about 10 microns to about 600 microns, or about 55 microns to 550 microns. Further, the sintered copper coating formed from the ink may be flexible and capable of passing the ASTM F1683-02 bend and fold test without any open circuit interruption (i.e., without open circuit failure). A change in resistivity (R) of 20% or less is considered to pass ASTM F1683-02 bend and fold tests. Open circuit interruption is defined as complete loss of conductivity (i.e., infinite resistivity).

The substrate with the sintered copper coating thereon can be incorporated into electronic devices such as circuits (e.g., Printed Circuit Boards (PCBs), conductive bus bars (e.g., for photovoltaic cells), sensors (e.g., touch sensors, wearable sensors), antennas (e.g., RFID antennas), thin film transistors, diodes, smart packaging (e.g., smart drug packaging), adaptable inserts in devices and/or vehicles, and multilayer circuits and MIM elements including low pass filters, frequency selective surfaces, transistors and antennas on adaptable surfaces that can withstand high temperatures.