Metal-organic framework and anisotropic conductive composition comprising same

Abstract

A metal-organic framework according to the present invention provides a metal-organic framework satisfying chemical formula 1. (Chemical formula 1) M+COO--(CH2)n- COO-M+ (M is a metal having a standard reduction potential of -0.8 V to 1.8 V, and n is an integer between 2 and 15.)

Description

Organometallic complex compound and anisotropic conductive composition containing the same

[0001] The present invention relates to an organometallic complex compound and an anisotropic conductive composition, an anisotropic conductive material, and a connection structure comprising the same.

[0002] Metal-organic frameworks (MOFs) have attracted attention in various industrial and research fields in recent years, and new MOF structures are continuously being developed by combining various metal ions and organic ligands.

[0003] Research is primarily focused on functionalizing the surface of MOFs to enhance interactions with specific molecules or ions. For example, methods for chemically modifying the pore walls are being studied to improve gas separation performance.

[0004] MOFs are typically used in gas storage and separation, catalysts, sensors, and drug delivery, but their properties, such as high surface area, variable pore structure, and surface functionalization, have been utilized.

[0005] Anisotropic conductive films are used in a variety of applications in the manufacturing and assembly of semiconductor packages, microelectronic devices, and the like. For example, they are used as electrical interconnect films for bonding integrated circuit chips to substrates, or as interconnect films for bonding circuit assemblies to printed circuit boards.

[0006] More specifically, the anisotropic conductive film (ACF) can be used in bonding formation of various electronic hardware, including chip-on-glass assembly (COF assembly), flip chip on flex assembly, contactless smart card module assembly, and flip chip die attach on a flexible substrate or rigid substrate.

[0007] Recently, micro LED (Light-emitting diode), also called micro light-emitting diode, refers to an ultra-small LED with a side size of less than 100㎛, and is one of the important technologies for implementing flat panel display technology.

[0008] Micro LEDs offer superior energy efficiency and optical efficiency compared to conventional LEDs, along with low heat generation per unit area. They also enable the creation of extremely small pixels, making them highly promising for applications beyond lighting, including ultra-small displays and precision medical devices. Anisotropic conductive films (ACFs) are used to attach these micro LEDs to electrodes on a substrate.

[0009] Because the size of the micro LED used in 4K (3840 * 2160) flat panel displays was at least 50 * 20㎛, a bonding process using ACF to attach electrodes was possible. However, to implement high-definition resolutions of 8K or higher, the size of the micro LED must be further reduced to 30 * 20㎛.

[0010] Therefore, when used for electrical bonding of micro devices such as micro LEDs, the conductive particles used in conventional ACFs are very large, with a diameter ranging from about 3 to 10 μm, making bonding small micro LED chips technically problematic. In other words, in the case of micro LED chips for high-definition implementation, the spacing between electrodes is less than 30 μm (or pitch), making bonding using an ACF film very difficult.

[0011] In addition, the HBM (High Bandwidth Memory) structure is one of the high-performance memory solutions used in semiconductor memory technology, and is widely used in graphics and high-performance computing systems in particular, and has the advantages of providing high bandwidth and low power consumption.

[0012] The HBM architecture features a 3D stacked structure, with multiple DRAM layers stacked vertically. These layers are vertically connected using silicon interposers (through-silicon vias) and TSV technology, which directly connect each layer by transmitting electrical signals through tiny holes that penetrate the memory layers.

[0013] To satisfy the needs of space efficiency, improved memory capacity, higher bandwidth, and increased energy efficiency, a method is required to increase the number of stacks in a given size of HBM structure. However, increasing the number of stacks by reducing the thickness of the bonding layer between DRAM layers poses difficulties in terms of reliability and manufacturing complexity.

[0014] The first aspect of the present invention aims to provide an organometallic complex compound in which a metal ion and an organic ligand individually perform functions in a decomposed state.

[0015] The second aspect of the present invention aims to provide a conductive composition having electrical conductivity, including the above-described organometallic complex compound.

[0016] The third aspect of the present invention aims to provide an anisotropic film usable for an electrode having an oxide film.

[0017] The fourth aspect of the present invention aims to provide a connection structure using the above-described anisotropic film.

[0018] An organometallic complex compound according to one aspect of the present invention is a substance having a form in which a metal ion is bonded to an organic ligand, wherein the reduced metal (M) of the metal ion is a metal having a standard reduction potential of -0.8 V to 1.8 V, and the organic ligand is an organic acid anion having at least one unshared electron pair, activated at pH 2 to 6, and having an activation temperature of 100 to 350°C.

[0019] At this time, it is preferable that the metal M has an electrical conductivity of 0.8 X 106 S / m to 7.0 X 107 S / m.

[0020] In addition, the above organometallic complex compound can satisfy the following chemical formula 1.

[0021] (Chemical Formula 1) M+COO － -(CH2)n- COO － M+ (M is a metal with a standard reduction potential of -0.8 V to 1.8 V, n is an integer from 2 to 15)

[0022] According to another aspect of the present invention, a heteroconductive composition is a composition that electrically connects opposing first and second electrodes, and is characterized by including the organometallic complex compound, a curable resin, and a phase separation inducing agent that induces phase separation of the metal and the curable resin.

[0023] At this time, the above-mentioned conductive composition may further include at least one selected from the group consisting of solder powder, conductive particles, and conductive nanoparticles.

[0024] It is preferable that the above solder powder has an electrical conductivity of 9 to 65 (MS / m).

[0025] The particle size of the above solder powder may be 1 to 10 μm.

[0026] The conductive particles and conductive nanoparticles may be a metal or alloy selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), indium tin oxide (ITO), palladium, platinum, nickel, and iridium.

[0027] The size of the above-mentioned conductive particles is preferably 2 to 50 μm.

[0028] The particle size of the above-mentioned conductive nanoparticles may be 0.01 to 5.0 μm.

[0029] It is preferable that the phase separation inducer is included in an amount of 5 to 15 parts by weight and the curable resin is included in an amount of 2.5 to 15 parts by weight relative to 30 parts by weight of the above organometallic complex compound.

[0030] The melting point of the above solder powder may be 130 to 280°C.

[0031] It is preferable that the above solder powder is included in an amount of 0.5 to 120 parts by weight.

[0032] The above-mentioned conductive particles may be included in an amount of 0.5 to 70 parts by weight.

[0033] It is preferable that the above-mentioned conductive nanoparticles are included in an amount of 0.1 to 7 parts by weight.

[0034] In the organometallic complex compound according to the present invention and the anisotropic conductive composition containing the same, the metal ion is reduced to a metallic conductive component and the organic ligand is converted to a flux component by an external stimulus, so there is no need to use a separate flux for the conductive component.

[0035] For example, the flux component derived from an organic ligand can remove oxides on the surface where the conductive component is to be bonded or lower the sintering temperature during sintering of the conductive component.

[0036] The anisotropic conductive material according to the present invention implements anisotropic conductivity without using conductive particles that implement primary conductivity, and in particular, even in the case of an electrode having an oxide film, there is no need to use a separate flux, and since there are no conductive particles that implement primary conductivity, it can be applied to fine pitches.

[0037] The anisotropic connection structure according to the present invention has high electrical conductivity by simultaneously forming an electrical connection between two electrodes using a reduced metal derived from an organometallic complex compound, and further reduces the phenomenon of conductive particles remaining outside the electrodes clumping due to the flux component derived from the organometallic complex compound. Therefore, it can be used in various connection structures.

[0038] Figure 1 is a schematic diagram showing the connection between electrodes according to the first embodiment of the third aspect.

[0039] Figure 2 is a schematic diagram showing the connection between electrodes according to the second embodiment of the third aspect.

[0040] Figure 3 is a schematic diagram showing the connection between electrodes according to the third embodiment of the third aspect.

[0041] Figure 4 is a schematic diagram showing the connection between electrodes according to the fourth embodiment of the third aspect.

[0042] Figure 5 is a conceptual diagram explaining the connection structure of the first implementation example according to the fourth aspect.

[0043] Figure 6 is a conceptual diagram explaining a connection structure according to a second implementation example of the fourth aspect.

[0044] Figure 7 is a conceptual diagram explaining a connection structure according to the third implementation example of the fourth aspect.

[0045] Figure 8 illustrates a typical HBM structure using copper pillars.

[0046] Fig. 9 is a via connection structure of an HBM to which an anisotropic conductive film including an organic metal complex compound and solder powder is applied, which is a second embodiment of the third aspect.

[0047] Fig. 10 is a via connection structure of an HBM to which an anisotropic conductive film including an organic metal complex compound and conductive particles is applied, which is a third embodiment of the third aspect.

[0048] Figure 11 shows a state in which the organometallic complex compound composition of Example 2-1 is printed on an Au / Cr / glass substrate and solder balls are attached.

[0049] Figure 12 shows the soldering process that has been completed through the reflow process.

[0050] Figure 13 shows the EDS evaluation results of the soldered solder bump, showing that reduced silver ions are contained inside.

[0051] Figure 14 shows the EDS evaluation results after heating the organometallic complex compound and solder powder composition, confirming the reduction of silver ions and solderability.

[0052] Figure 15 shows that after printing a composition containing an organometallic complex compound to form a film and heating it, reduction and soldering of silver ions occurred within the pattern.

[0053] Figure 16 shows the results of resistance measurement and EDS analysis after printing, filming, and heating the composition of Example 5-1 (PAC-174) on a 260 μm pitch FPCB.

[0054] Figure 17 shows the results of resistance measurement and EDS analysis after the composition of Example 5-2 (PAC-175) was treated in the same manner.

[0055] Figure 18 shows the results of resistance measurement and EDS analysis after processing the composition of Example 5-3 (PAC-58).

[0056] Figure 19 shows the results of resistance measurement and EDS analysis after processing the composition of Example 5-4 (PAC-E5).

[0057] Figure 20 shows the results of resistance measurement and EDS analysis after printing the composition of Example 3-1 on an FPCB and heating it.

[0058] Figure 21 shows the results of resistance measurement and EDS analysis after processing the composition of Example 3-2.

[0059] Figure 22 shows the results of resistance measurement and EDS analysis after processing the composition of Example 3-3.

[0060] Figure 23 shows the results obtained by printing the compositions of Example 5-1 and Comparative Example 5-4 on a glass substrate and soldering them at 260°C for 5 minutes.

[0061] Before describing the present invention in detail below, it is important to understand that the terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the scope of the present invention, which is limited solely by the scope of the appended claims. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

[0062] Throughout this specification and claims, unless otherwise stated, the terms "comprise," "comprises," and "comprising" are used to mean including a stated item, step, or group of items, and steps, but not to the exclusion of any other item, step, or group of items, or group of steps.

[0063] Additionally, in the drawings, the width, length, thickness, angle, etc. of components may be exaggerated for convenience. The drawings are described from the perspective of an observer as a whole, and when a component is said to be “above / below” or “on / below” another component, this includes not only cases where it is “directly above / directly below” another component, but also cases where there is another component in between.

[0064] Meanwhile, the various embodiments of the present invention may be combined with any other embodiments unless explicitly indicated otherwise. Any feature indicated as particularly preferred or advantageous may be combined with any other feature or features indicated as preferred or advantageous.

[0065] Hereinafter, the present invention will be described in more detail with reference to the drawings.

[0066] <Aspect 1>

[0067] It relates to an organometallic complex compound according to the first aspect of the present invention.

[0068] A metal-organic framework (MOF) is a substance in which a metal ion is bonded to an organic ligand. In the metal-organic framework of the first aspect, the metal (M) that can be a metal ion is a substance with high reducibility, and the reduced metal M is a metal having a standard reduction potential of -0.8 V to 1.8 V.

[0069] Also, the metal ion M, which becomes a conductive component when reduced, is 0.8 X 10 6 S / m to 7.0 X 10 7 It is desirable to have an electrical conductivity of S / m.

[0070] For example, the metal M may be any one of silver (Ag), gold (Au), platinum (Pt), palladium (Pd), copper (Cu), nickel (Ni), indium (In), tin (Sn), bismuth (Bi), zinc (Zn), chromium (Cr), and tungsten (W).

[0071] Organic ligands are substances that coordinate with metal ions. They form bonds with at least one metal ion, connecting the metal ions and maintaining a fixed spatial arrangement. The linked metal ions and organic ligands form a regular lattice structure, providing stability to organometallic complexes.

[0072] The organic ligand has at least one unshared electron pair to function as a coordination bond and flux component, and an organic acid having a pH of 2 to 6 and an activation temperature of 100 to 350°C is used. Preferably, the organic ligand may be an organic acid anion having a carboxyl group.

[0073] At this time, the activation temperature is defined as the starting point at which mass decreases as temperature increases, measured by thermogravimetric analysis (or thermal gravimetric analysis, TGA).

[0074] Meanwhile, it is preferable that the organometallic complex compound according to the present embodiment satisfies the following chemical formula 1.

[0075] (Chemical formula 1)

[0076] M + COO - -(CH2) n - COO - M +

[0077] In the chemical formula 1, n may be an integer from 2 to 15, preferably from 2 to 11, more preferably from 2 to 8. For example, as shown in the chemical formula 2 below, the organic ligand may be any one of the anions of glutaric acid, succinic acid, adipic acid, sebacic acid, salicylic acid, benzoic acid, malic acid, azelaic acid, and propionic acid.

[0078] (Chemical formula 2)

[0079]

[0080] According to this embodiment, the organometallic complex has both a conductive component and a flux component, and can be called a new term, metallic flux. For example, when the organometallic complex is used to connect an anisotropic electrode, the metal provides conductivity through reduction, and the flux can remove the oxide film formed on the electrode and lower the surface tension.

[0081] <Second Aspect>

[0082] A composition comprising an organometallic complex compound according to a second aspect of the present invention. In a first embodiment of this aspect, the organometallic complex composition can be used as a bonding composition for electrically connecting one electrode and the other electrode of an electronic component.

[0083] The organometallic complex composition includes an organometallic complex compound, a phase separation inducer, a curable resin, and curing agents for curing the curable resin.

[0084] The organometallic complex compound is a material in a state before being reduced to a metal particle having conductivity within the composition, and the organometallic complex compound presented in the first aspect can be used.

[0085] A metal-organic framework (MOF) is a material in which a metal ion is bonded to an organic ligand. The metal (M) is a highly reducible material. The reduced metal M may be a metal having a standard reduction potential of -0.8 V to 1.8 V. The organic ligand is a material that coordinates with the metal ion. The organic ligand has at least one unshared electron pair so as to form a coordination bond with at least one metal ion. An organic acid having a pH of 2 to 6 and an activation temperature of 100 to 350°C is used. Preferably, the organic ligand may be an organic acid having a carboxyl group. For a detailed description, refer to the first aspect.

[0086] A phase-separation inducer is a substance that induces phase separation between the reducing metal and the curing polymer. It is a substance that causes the reduced metal and the curing polymer to phase separate when the organometallic complex compound is reduced by heat or light (laser), which will be described later. In other words, the metal ions within the organometallic complex compound sinter upon reduction, and at this time, they phase separate from the polymers.

[0087] The phase separation inducer contains both hydrophilic and lipophilic groups within its molecule, so it is presumed that the hydrophilic groups induce phase separation by surrounding the reduced conductive metal particle mass (hereinafter referred to as a sintered body) on the surface, and the lipophilic groups come into contact with the polymer.

[0088] At this time, it is preferable that the number of carbon atoms in the lipophilic group is 5 to 25, and the hydrophilic group includes a carboxyl group (-COOH) or an amine group (- NH).

[0089] Specifically, the phase separation inducer is a compound containing a carboxyl group, and at least one fatty acid selected from the group consisting of caprylic acid, pelargonic acid, caproic acid, undecanic acid, lauric acid, myristic acid, behenic acid, palmitic acid, lignoceric acid, stearic acid, eicosanoic acid, and oleic acid, or a combination thereof, may be used.

[0090] Among the phase separation inducers, compounds containing amines may be selected from the group consisting of, for example, hexylamine, heptylamine, octylamine, oleylamine, decylamine, dodecylamine, 2-ethylhexylamine, and 1,3-dimethyl-n-butylamine, at least one or a combination thereof may be used.

[0091] At this time, the phase separation inducer induces phase separation by surrounding the conductive metal particle mass (hereinafter referred to as a sintered body) on the surface with the hydrophilic group, carboxyl group or amine group, and by contacting the polymer with the lipophilic group, alkyl group.

[0092] When an anisotropic conductive composition is heated by heat or laser while the metal and polymer are phase-separated to form a cured product, the cured product forms multiple sintered bodies through reduction of metal ions. The metal sintered bodies are rich in metal and thus electrically conductive. In addition, the area outside the sintered body does not have electrical conductivity as the curable resin is formed into a hardened polymer.

[0093] At this time, the cured product is formed by reducing metal ions, and a plurality of sintered bodies grow in the Z-axis direction to electrically connect the first electrode and the second electrode, and the plurality of sintered bodies are not connected to each other in the X and Y-axis directions.

[0094] By this phase separation induction method, conductive paths are not formed in the X and Y axes, and only the Z-axis direction becomes a conductive path through which electricity can flow. At this time, the Z-axis is, for example, the direction in which the first electrode and the second electrode face each other, and the X and Y-axis directions are directions perpendicular to the Z-axis direction.

[0095] The curable resin is a polymer resin that can be polymerized by radicals, and a resin such as an epoxy resin can be used. Examples of epoxy resins that can be used include bisphenol A type epoxy resin, substituted epoxy resin, linear aliphatic epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, heterocyclic epoxy resin, and halogenated epoxy resin, all of which contain two or more epoxy groups per molecule. In addition, two or more types of the above-mentioned epoxy resins can be used in combination.

[0096] In addition, an acrylic resin may be used as the curable resin, and at this time, as a monomer for curing, (meth)acrylate is a monomer or oligomer having one or more functional groups, and one or two or more selected from urethane acrylate, epoxy acrylate, cresol novolac acrylate, phenol novolac acrylate, phosphoric acid acrylate, etc. having one or more reactive functional groups and less than 20 may be used.

[0097] Preferred examples of acrylate monomers include neopentylglycol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, pentaerythritol penta(meth)acrylate, dipentaerythritolpenta(meth)acrylate, glycerin di(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, isodecyl(meth)acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate, stearyl(meth)acrylate, lauryl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, isobornyl(meth)acrylate, It is selected from the group consisting of tridecyl (meth)acrylate, ethoxylated nonylphenolacrylate, ethylene glycol di(meth)acrylate, ethoxylated bisphenol-AD(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, phenoxy tetraethylene glycol (meth)acrylate, 2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl phosphate, dimethylol tricyclodecane di(meth)acrylate, dipentaerythritol hexaacrylate, trimethylopropanebenzoate acrylate, and mixtures thereof. The content of the (meth)acrylate monomer is preferably about 5 to 50 wt%.

[0098] At this time, it is preferable to use a combination of a polyfunctional (meth)acrylate and a monofunctional (meth)acrylate monomer as the acrylate monomer, and in particular, the monofunctional (meth)acrylate monomer may be included in an amount of 1 to 3 wt%.

[0099] A curing agent is a substance that cures a curable resin with heat or light, and one or more amine or phosphine compounds can be used. For example, amine curing agents include 2-methyl imidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; and tertiary amine compounds include triethylamine, benzyldimethylamine, methylbenzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0100] Additionally, phosphine compounds may be used, such as triethylphosphine, tributylphosphine, 1,8-diazabicyclo(5,4,0)undecene-7; or organic phosphine compounds may be used, such as triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine (Tris(4-methoxyphenyl)phosphine), and tri(nonylphenyl)phosphine.

[0101] The curing agent for curing the acrylic resin is a substance that cures the curable resin with heat or light, and is preferably an oil-soluble curing agent or a redox curing agent such as an organic peroxide such as lauryl peroxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, or t-butyl hydroperoxide.

[0102] The solvent is for dissolving the above-mentioned components, and the solvent may be used without limitation, but may include tetrahydrofuran (THF), alcohol solvents, ether solvents, sulfide solvents, toluene solvents, xylene solvents, benzene solvents, alkane solvents, oxane solvents, amine solvents, polyol solvents, or diketone, amino alcohol, polyamine, ethanol amine, diethylnol amine, ethane thiol, propane thiol, butane thiol, pentane thiol, hexane thiol, heptane thiol, It is preferable to use a solvent comprising at least one selected from the group consisting of octane thiol, nonane thiol, decane thiol, and undecane thiol, or a combination thereof.

[0103] In the aforementioned composition, it is preferable to include 5 to 15 parts by weight of a phase separation inducer, 2.5 to 15 parts by weight of a curable resin, 2.5 to 20 parts by weight of a curing agent, and 1 to 20 parts by weight of a solvent based on 30 parts by weight of an organometallic complex compound.

[0104] If the phase separation inducer exceeds the above range compared to the organometallic complex compound, there is a problem of increased electrical resistance, and if it is below the above range, there is a problem of no phase separation induction.

[0105] Additionally, if the amount of curable resin used is less than the range, there is a possibility of poor adhesion, and if the amount of curable resin used exceeds the range, there is a problem of increased electrical resistance between the micro LED and the substrate electrode.

[0106] In addition, if the amount of the hardener is less than the range, poor adhesion may occur due to insufficient curing of the curable resin, and if the amount is more than the range, the curing speed of the curable resin may become too fast, making it difficult to obtain sufficient electrical conductivity, or the composition may become cured before transfer is performed.

[0107] Meanwhile, when curing the composition with a laser, a wavelength of 760 nm to 4900 nm can be used, and IR with a wavelength of 1000 nm to 4900 nm is particularly preferred. This is because if the wavelength is outside the above range, damage to electronic components may occur during laser curing.

[0108] Even when reducing and sintering organometallic compounds with a laser, both materials that cure with heat or light can be cured. Even when curing with a laser, heat-curable resins are possible because the laser generates heat in the electrode, which in turn provides the heat necessary for curing the curable resin.

[0109] In the second embodiment of this aspect, the organic metal complex composition may further include solder powder, and may be used as a bonding composition for electrically connecting one electrode and the other electrode of an electronic component, thereby providing better adhesive strength and connection stability.

[0110] Solder powder is used as a bonding material that electrically connects one electrode and the other electrode of an electronic component when the composition provided by the metal is used to facilitate the electrical connection between the one electrode and the other electrode, and is made of a material that can efficiently transmit electrical signals and heat during bonding.

[0111] The electrical conductivity of a material that can be used as solder powder is 8.5 X 10 5 S / m to 7 X 10 7 It is S / m (based on pure metal), and the melting point is preferably 130 to 280°C.

[0112] For example, the solder powder may include an alloy of at least one of tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), lead (Pb), indium (In), zinc (Zn), and cadmium (Cd), or a combination thereof. The particle size of the solder powder is 1 to 10 um, preferably 2 to 7 um.

[0113] In the second embodiment composition, it is preferable that solder powder is included in an amount of 0.5 to 120 parts by weight for 30 parts by weight of the organometallic complex compound.

[0114] If the solder powder is smaller than the above range, the conductivity may decrease and non-uniform phase separation may occur, and if it is larger than the above range, the possibility of metal particles agglomerating or depositing increases.

[0115] A third embodiment of an anisotropic conductive composition according to the second aspect of the present invention includes an organometallic complex compound, a phase separation inducer, a curable resin, curing agents for curing the curable resin, a solvent, and conductive particles.

[0116] That is, compared to the first embodiment, the third embodiment is an embodiment that hybridizes the conductivity by the conductive particles and the conductivity by the reduced metal sintered body by further including conductive particles. The conductive particles may be selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), ITO (indium tin oxide), palladium, platinum, nickel, and iridium, and particles having a size in the range of 2 to 50 μm may be used.

[0117] In the composition of the third embodiment, it is preferable that the conductive particles are included in an amount of 0.5 to 70 parts by weight for 30 parts by weight of the organometallic complex compound.

[0118] A fourth embodiment of an anisotropic conductive composition according to the present invention includes an organometallic complex compound, a phase separation inducer, a curable resin, curing agents for curing the curable resin, a solvent, and conductive nanoparticles.

[0119] That is, compared to the first embodiment, the fourth embodiment is an embodiment in which conductivity by the conductive nanoparticles and conductivity by the reduced metal sintered body are networked by further including conductive nanoparticles. The conductive nanoparticles may be selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), indium tin oxide (ITO), palladium, platinum, nickel, and iridium, and nanoparticles having a size in the range of 0.01 to 5.0 μm may be used.

[0120] Conductive nanoparticles are preferably included in an amount of 0.1 to 7 parts by weight per 30 parts by weight of the organometallic complex compound. Thus, by adding a small amount of conductive particles, the electrical conductivity of the sintered body can be further improved in addition to the electrical conductivity.

[0121] According to the composition of the fourth embodiment, the conductive nanoparticles contained in the connecting material and the flux derived from the organometallic complex compound upon heating or light irradiation remove the oxide film of the electrode, and at the same time, the reduced metal forms a network between the conductive nanoparticles and the upper and lower electrodes.

[0122] In this way, the reduced metal forms a bridge between the conductive nanoparticles and the nanoparticles between the upper and lower electrodes, thereby forming a network conductive path, thereby electrically connecting the upper and lower electrodes.

[0123] For a more intuitive understanding of the first to fourth embodiments in the second aspect, reference may be made to the drawings of the first to fourth embodiments in the third aspect, which will be described later.

[0124] <Third Aspect>

[0125] A first embodiment of a composition for producing an anisotropic conductive material according to a third aspect of the present invention further includes a flow control agent for film formation in the organometallic complex composition of the second aspect. Accordingly, the composition for producing an anisotropic conductive material includes an organometallic complex compound, a phase separation inducer, a curable resin, curing agents for curing the curable resin, a flow control agent, and a solvent. In order to more clearly explain the characteristics of this aspect, overlapping parts with the descriptions of the first and second aspects are omitted, and only the additional components are described.

[0126] The flow control agent is a component included to control the flow of the conductive material and to cure the composition very quickly. The acrylic polymer resin having a molecular weight of 10,000 to 1,100,000 and a glass transition temperature (Tg) of -20 to 110°C is preferable, and the acrylic polymer resin containing methacrylic is preferable.

[0127] When manufacturing a conductive material as a freestanding conductive material (e.g., film), if the molecular weight is less than 10,000, it is difficult to manufacture it by forming a film during the first heating, and when pressing during the second heating, it flows too easily due to the high temperature and high pressure, so the resin comes out too easily, resulting in high resistance and greatly reduced adhesive strength. If the molecular weight is more than 1,100,000, the film becomes too brittle and breaks easily, and the tackiness (stickiness) is too low, so the film and COF, TCP, etc. do not stick together during pressing, increasing the probability of defects.

[0128] At this time, the first heating refers to heating that enables free-standing curing from the composition and does not reduce the internal metal ions, and the second heating refers to heating that reduces the internal metal ions to form a sintered body.

[0129] In addition, when the aforementioned flow control agent is connected to the electrode of a COF (chip on flexible printed circuit) and the ITO or Ti / Al / Ti electrode section, it has an initial electrical connection resistance value that cannot be obtained with a conventional ACF and a high Tg of the acrylic rubber itself, so it is possible to obtain sufficient connection reliability by having heat and moisture resistance.

[0130] In the aforementioned composition, it is preferable to include 0.5 to 30 parts by weight of a flow control agent, 0.5 to 15 parts by weight of a phase separation inducer, 1 to 30 parts by weight of a curable resin, 1 to 20 parts by weight of a curing agent, and 1.5 to 30 parts by weight of a solvent, based on 30 parts by weight of an organometallic complex compound.

[0131] Figure 1 is a schematic diagram showing the connection between electrodes according to the first embodiment. According to this, the metal ions of the organometallic complex compound contained within the connecting material according to the composition of the first embodiment are reduced to metal depending on external conditions and then sintered to form an independent conductive path, thereby electrically connecting the upper electrode and the lower electrode.

[0132] At this time, the flux component derived from the organometallic complex removes the oxide film formed on the electrode, thereby reducing the connection resistance.

[0133] A second embodiment of a composition for manufacturing an anisotropic conductive material according to a third aspect of the present invention further comprises solder powder. The solder powder is employed to facilitate electrical connection between one electrode and the other electrode when the composition provided by the metal is used as a bonding material for electrically connecting one electrode and the other electrode of an electronic component, and is made of a material capable of efficiently transmitting electrical signals and heat during bonding.

[0134] The electrical conductivity of a material that can be employed as solder powder is 8.5 X 10 5 S / m to 7 X 10 7S / m (based on pure metal) may be used. For example, the solder powder may include an alloy of at least one of tin (Sn), silver (Ag), copper (Cu), bismuth (Bi), lead (Pb), indium (In), zinc (Zn), and cadmium (Cd), or a combination thereof.

[0135] It is preferable that the solder powder be included in an amount of 0.5 to 510 parts by weight based on 30 parts by weight of the organometallic complex compound.

[0136] If the solder powder is smaller than the above range, the conductivity may decrease and non-uniform phase separation may occur, and if it is larger than the above range, the possibility of metal particles agglomerating or depositing increases.

[0137] In this aspect, the composition for manufacturing an anisotropic conductive material becomes conductive even without conductive particles through reduction and sintering by the following mechanism.

[0138] (Formula 1)

[0139]

[0140]

[0141] Figure 2 is a schematic diagram showing the connection between electrodes according to the second embodiment. According to this, the solder powder contained within the connecting material according to the composition of the second embodiment is self-aligned by the flux component derived from the organometallic complex compound and is positioned between the upper electrode and the lower electrode, and the metal ions are reduced to the outside of the solder powder and attached according to external conditions, i.e., heating or light irradiation.

[0142] Meanwhile, residual metal or unreduced metal ions located in a space without electrodes can be prevented from ion migration by being concentrated on solder particles by the flux derived from the organometallic complex.

[0143] In this way, a conductive path can be formed between the upper electrode and the lower electrode through a metal bond by solder and reduction on the outside, thereby electrically connecting the upper electrode and the lower electrode.

[0144] A third embodiment of an anisotropic conductive composition according to a third aspect of the present invention includes an organometallic complex compound, a phase separation inducer, a curable resin, curing agents for curing the curable resin, a flow control agent, a solvent, and conductive particles.

[0145] That is, compared to the first embodiment, the third embodiment is an embodiment that hybridizes the conductivity by the conductive particles and the conductivity by the reduced metal sintered body by further including conductive particles. The conductive particles may be selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), ITO (indium tin oxide), palladium, platinum, nickel, and iridium, and particles having a size in the range of 2 to 50 μm may be used.

[0146] It is preferable that the conductive particles be included in an amount of 0.5 to 60 parts by weight based on 30 parts by weight of the organometallic complex compound.

[0147] / *124 It is preferable that the conductive particles used at this time have a size of 0.5 to 300 um. If it exceeds 300 um, there is a problem in applying it to fine pitch, and if it is less than 0.5 um, there is a problem in that soldering does not occur due to rapid oxidation.

[0148] The conductive particles may be metals having an electrical conductivity of 9 to 65 (MS / m). For example, they may be selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), indium tin oxide (ITO), palladium, platinum, nickel, and iridium, and preferably, a metal having an electrical conductivity of 40 to 65 may be used.

[0149] Additionally, depending on the situation, ITO of about 0.1-1 MS / m can be used.

[0150] Fig. 3 is a schematic diagram showing the connection between electrodes according to the third embodiment. According to this, conductive particles included in the connecting material according to the composition of the third embodiment are positioned between the upper electrode and the lower electrode, and when heated or irradiated with light, the flux derived from the organometallic complex removes the oxide film of the electrode, and at the same time, the reduced metal is attached to the surface of the metal particle. The metal ions are reduced and attached to the outside of the conductive particles according to external conditions, i.e., when heated or irradiated with light. Meanwhile, metal particles reduced by the flux derived from the organometallic complex are attached to conductive particles located in a space without electrodes, thereby preventing ion migration of metal or unreduced ions remaining between the electrodes.

[0151] In this way, a conductive path can be formed between the upper electrode and the lower electrode through contact bonding by conductive particles and reduction of the outer side thereof, thereby electrically connecting the upper electrode and the lower electrode.

[0152] A fourth embodiment of an anisotropic conductive composition according to the present invention includes an organometallic complex compound, a phase separation inducer, a curable resin, curing agents for curing the curable resin, a flow control agent, a solvent, and conductive nanoparticles.

[0153] That is, compared to the first embodiment, the fourth embodiment is an embodiment in which conductivity by the conductive nanoparticles and conductivity by the reduced metal sintered body are networked by including more conductive nanoparticles.

[0154] The conductive nanoparticles may be metals having an electrical conductivity of 9 to 65 (MS / m). For example, the conductive nanoparticles may be selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), indium tin oxide (ITO), palladium, platinum, nickel, and iridium, and preferably, a metal having an electrical conductivity of 40 to 65 may be used.

[0155] Additionally, depending on the situation, ITO of about 0.1-1 MS / m can be used.

[0156] Meanwhile, conductive nanoparticles can be used with particle sizes ranging from 0.01 to 5.0 μm. If the particle size exceeds 5.0 μm, there is a problem of reduced electrical conductivity after soldering, and if the particle size is less than 0.01 μm, there is a problem of soldering failure.

[0157] It is preferable that the conductive nanoparticles be included in an amount of 0.1 to 15 parts by weight per 30 parts by weight of the organometallic complex compound. Thus, by adding a small amount of conductive particles, the electrical conductivity can be further improved in addition to the electrically conductive sintered body.

[0158] Figure 4 is a schematic diagram showing the connection between electrodes according to the fourth embodiment. According to this, conductive nanoparticles included in the connecting material according to the composition of the fourth embodiment and flux derived from an organometallic complex compound upon heating or light irradiation remove the oxide film of the electrode, and at the same time, the reduced metal forms a network between the conductive nanoparticles and the upper and lower electrodes.

[0159] In this way, the reduced metal forms a bridge between the conductive nanoparticles and the nanoparticles between the upper and lower electrodes, thereby forming a network conductive path, thereby electrically connecting the upper and lower electrodes.

[0160] Conductive materials that can be manufactured using a composition for manufacturing anisotropic conductive materials may include anisotropic conductive films (ACF), anisotropic conductive tapes (ACT), anisotropic conductive adhesives (ACA), anisotropic conductive pastes (ACP), etc.

[0161] <Aspect 4>

[0162] The fourth aspect of the present invention is a connection structure using the composition or film of the second to third aspects.

[0163] A first embodiment of this aspect is described. A connection structure according to this embodiment includes a first electrode (20), a second electrode (30), and a connection material (70) electrically connecting the first electrode (20) and the second electrode (30).

[0164] Fig. 5 is a conceptual diagram illustrating a connection structure of a first embodiment according to the fourth aspect. The first electrode (20) and the second electrode are electrodes for electrical connection formed on a device or a flexible substrate, and the second electrode (30) is an electrode for electrical connection with the first electrode (20). At this time, the material of at least one of the electrodes is not limited, but can be preferably used as a metal electrode having an oxide layer formed on the outer surface, such as Al, Cu, Fe, Ni, Zn, Sn, or Ti.

[0165] The connecting material (70) is a material for electrically connecting the first electrode (20) and the second electrode (30), and is an anisotropic conductive connecting material that allows electricity to flow only in the connection direction of the first electrode (20) and the second electrode (30) and does not allow electricity to flow in a direction other than the connection direction of the first electrode (20) and the second electrode (30).

[0166] At this time, the connecting material is positioned between the first electrode (20) and the second electrode (30) to physically and electrically connect them, and when cured, the first electrode (20) and the second electrode (30) are formed by curing the anisotropic conductive composition film placed between them while heating and pressing.

[0167] The anisotropic conductive film is a film manufactured from a composition including an organometallic complex compound, a phase separation inducer, a curable resin, a curing agent, a curing resin, a flow control agent, and a solvent for dissolving the curing agent.

[0168] The first to fourth embodiments of the third aspect can be applied to the anisotropic challenge film.

[0169] Referring back to FIG. 1, when applying the anisotropic conductive film according to the first embodiment of the third aspect, the anisotropic conductive film between the first electrode and the second electrode has a structure in which a sintered body in which a metal ion derived from an organometallic complex is reduced when cured with a laser or heat to form a conductive path that electrically connects the first electrode and the second electrode is separated from a polymer region in which a polymer formed by curing a curable resin is located. At this time, a plurality of regions in which the sintered body is located and regions in which the polymer is located are hybridized with each other.

[0170] That is, the organometallic complex exists as a metal ion in the composition state, and in the process of reducing the metal ion of the precursor by heat or laser, the metal is reduced to a metal on the surface of the electrode portion of the chip and substrate, forming a seed layer, and metal particles gradually grow around the seed layer, and simultaneously with the growth of the metal particles, they are separated into a metal region and a binder region by a phase separation inducer, and thereafter, the metal is sintered and the binder is hardened in each different region.

[0171] Meanwhile, the organic ligand of the organometallic complex is activated by heat or laser and functions as a flux to remove the oxide layer on the electrode surface, thereby reducing the contact resistance when the sintered body comes into contact with the electrode.

[0172] Referring again to FIG. 2, the solder powder included in the connecting material according to the composition of the second embodiment of the third aspect is activated by the flux component derived from the organometallic complex compound and self-aligns by melting to move and position between the first electrode and the second electrode, thereby forming a solder joint.

[0173] At this time, the metal ions of the organometallic complex are reduced and attached to the outside of the solder powder by irradiation with a laser or heat.

[0174] The solder joint electrically connects the electrodes, and in addition, metal is attached to the outer surface of the solder joint, forming a stable conductive path.

[0175] Meanwhile, residual metal or unreduced metal ions located in a space without electrodes can be prevented from ion migration by being concentrated on solder particles by the flux derived from the organometallic complex.

[0176] Referring again to FIG. 3, the conductive particles included in the connecting material according to the composition of the third embodiment of the third aspect are positioned between the first electrode and the second electrode, and when heated or irradiated with light, the flux derived from the organometallic complex removes the oxide film of the electrode, and at the same time, the reduced metal is attached to the surface of the metal particle. The metal ions are reduced and attached to the outside of the conductive particles according to external conditions, that is, when heated or irradiated with light. Meanwhile, the metal particles reduced by the flux derived from the organometallic complex are attached to the conductive particles located in the space where there is no electrode, thereby preventing the metal or unreduced ions remaining between the electrodes from ion migration.

[0177] In this way, a conductive path can be formed between the upper electrode and the lower electrode through contact bonding by conductive particles and reduction of the outer side thereof, thereby electrically connecting the upper electrode and the lower electrode.

[0178] The size and type of the conductive particles used are the same as in the third aspect.

[0179] Referring again to FIG. 4, the conductive nanoparticles included in the connecting material according to the composition of the fourth embodiment and the flux derived from the organometallic complex compound upon heating or light irradiation remove the oxide film of the electrode, and at the same time, the reduced metal forms a network between the conductive nanoparticles and the upper and lower electrodes.

[0180] In this way, the reduced metal forms a bridge between the conductive nanoparticles and the nanoparticles between the upper and lower electrodes, thereby forming a network conductive path, thereby electrically connecting the upper and lower electrodes.

[0181] The size and type of the conductive nanoparticles used are the same as in the third aspect.

[0182] Fig. 6 is a conceptual diagram illustrating a connection structure according to a second embodiment of the fourth aspect, which is a connection structure in which two electrodes have two opposing electrodes. The connection structure according to the present embodiment includes a third electrode (120a), a fourth electrode (120b), a fifth electrode (130a), a sixth electrode (130b), and a connection material (170) electrically connecting the third electrode to the fifth electrode and the fourth electrode to the sixth electrode. Unexplained drawing reference numeral 140 denotes an oxide layer of the electrode.

[0183] The third electrode (120a) and the fourth electrode (120b) are electrodes for electrical connection formed on the substrate, and may be, for example, a backplane substrate for attaching a micro LED, and the fifth electrode is provided at a position opposite to the third electrode, such that the electrode opposite to the third electrode is referred to as the fifth electrode, and the electrode opposite to the fourth electrode is referred to as the sixth electrode, and may be an electrode having a layered structure of molybdenum-aluminum-molybdenum.

[0184] The fifth electrode (130a) and the sixth electrode (130b) are electrodes for electrical connection formed in an element formed in an electronic component, and may be, for example, a semiconductor chip or a micro LED chip. In the case of a micro LED chip, the electrodes may be gold, and one electronic component may have two electrodes, the fifth electrode (130a) and the sixth electrode (130b), which are anode and cathode.

[0185] At this time, the gap between the third electrode and the fourth electrode (the fifth electrode and the sixth electrode) is 1 to 50 ㎛, preferably 3 to 50 ㎛, and the width of each electrode is 1 to 1000 ㎛, 3 to 80 ㎛.

[0186] Meanwhile, the spacing between the third electrode and the fifth electrode (the fourth electrode and the sixth electrode) is preferably 10 nm to 10 μm, preferably 10 nm to 1000 nm, preferably 100 nm to 450 nm, and more preferably 140 nm to 440 nm. If the spacing exceeds the above range, there is a problem of increased contact resistance.

[0187] The connecting material is a material for electrically connecting the third electrode and the fifth electrode (the fourth electrode and the sixth electrode), and is an anisotropic conductive connecting material in which electricity flows only in the connection direction of the third electrode and the fifth electrode and the fourth electrode and the sixth electrode, and electricity does not flow in a direction other than the connection direction of the third electrode and the fifth electrode (the fourth electrode and the sixth electrode).

[0188] As an anisotropic challenger, the first to fourth embodiments of the third aspect can be applied.

[0189] Figure 7 is a conceptual diagram illustrating a connection structure according to a third embodiment of the fourth aspect, and describes the connection structure of a high-bandwidth memory. HBM is a structure that realizes high capacity in a small area by vertically stacking multiple layers of DRAM dies. Typically, it includes 4 to 8 DRAM dies, and the connection between them is made through through-silicon vias (TSVs).

[0190] TSV is a conductive via that runs vertically completely through a single silicon die or wafer, connecting the top surface of a single die to the bottom surface and filling the interior with a conductive material.

[0191] In order to connect TSVs in HBM, an Under Bump Metallization (UBM) layer is formed on top of the TSV, copper pillars that provide high current density, fine pitch, thermal management, and strength are created, and after aligning the two dies, heat and pressure are applied to bond the bumps together, using a thermocompression process.

[0192] Figure 8 illustrates a typical HBM structure using copper pillars. According to this, solder is provided at the ends of the pillars, and the upper and lower pillars are connected by melting the solder through thermocompression.

[0193] However, recent technological developments in HBM require finer pitches and higher performance, and in order to enable higher die stacking, connections that can reduce the gap between each die without using copper pillars as shown in Fig. 8 are required.

[0194] Accordingly, hybrid bonding that simultaneously performs copper-copper bonding, copper-copper bonding, and dielectric-dielectric bonding is being studied. To this end, a third embodiment of the present invention provides a connection structure that connects a copper electrode of a via of a die and a copper electrode using a composition and film for manufacturing an anisotropic conductive material of the third aspect.

[0195] Implementation examples of the third aspect that can be used at this time may be used.

[0196] Figure 9 is a via connection structure of an HBM, to which an anisotropic conductive film including an organometallic complex compound and solder powder is applied, which is a second embodiment of the third aspect. According to this, the anisotropic conductive film is positioned between the first die and the second die.

[0197] At this time, solder powder is positioned between the first via electrode of the first die and the second via electrode of the second die, and when light or heat is applied while pressurizing, the conductive particle and its outer surface are reduced by the organometallic complex, and the surrounding metal forms a conductive path, and the organic ligand derived from the organometallic complex acts as a flux.

[0198] Fig. 10 is a via connection structure of an HBM to which an anisotropic conductive film including an organometallic complex compound and conductive particles is applied, which is a third embodiment of the third aspect. According to this, an anisotropic conductive film is positioned between a first die and a second die. At this time, conductive particles are positioned between the first via electrode of the first die and the second via electrode of the second chip, and when light or heat is applied while pressurizing, the outer surface of the conductive particles is reduced by the organometallic complex compound, and the surrounding metal forms a conductive path, and the organic ligand derived from the organometallic complex acts as a flux.

[0199] The via connection structure of the HBM according to this embodiment can remove the oxide film of the electrode by using an organic metal complex compound (metallic flux) and reduce the connection resistance by the reduced metal.

[0200] Additionally, the use of a metallic flux reduces the likelihood of the reduced metal particles remaining in agglomeration. Furthermore, the likelihood of short circuits in the reduced metal particles is reduced.

[0201] Example 1-1: Silver (Ag)-adipic acid-based organometallic complex compound

[0202] In this example, an organometallic complex was synthesized using silver (Ag) as a metal ion and adipic acid (HOOC-(CH2)4-COOH) as an organic ligand. The synthesis process was as follows.

[0203] First, 100 mL of a 0.1 M aqueous silver nitrate (AgNO3) solution and 100 mL of a 0.1 M aqueous adipic acid solution were prepared, respectively. The two solutions were then slowly mixed to adjust the pH to 4, which falls within the pH range of 2-6 required by the patent. The mixed solutions were stirred at 60°C for 2 hours to proceed with the reaction.

[0204] After the reaction was completed, the resulting precipitate was filtered and washed with distilled water to remove impurities. Finally, the resulting solid product was dried at 80°C for 12 hours to obtain the final organometallic complex.

[0205] Example 1-2: Copper (Cu)-succinic acid-based organometallic complex

[0206] In this example, an organometallic complex was synthesized using copper (Cu) as a metal ion and succinic acid (HOOC-(CH2)2-COOH) as an organic ligand. The synthesis process was as follows.

[0207] 100 mL of a 0.1 M aqueous solution of copper sulfate (CuSO4) and 100 mL of a 0.1 M aqueous solution of succinic acid were prepared, respectively. The two solutions were slowly mixed to adjust the pH to 5. The mixed solutions were stirred at 55°C for 3 hours to proceed with the reaction.

[0208] After the reaction was completed, the resulting precipitate was filtered and washed with distilled water. The resulting solid product was dried at 75°C for 10 hours to obtain the final organometallic complex.

[0209] Example 1-3: Nickel (Ni)-maleic acid-based organometallic complex compound

[0210] In this example, an organometallic complex was synthesized using nickel (Ni) as the metal ion and maleic acid (HOOC-CH=CH-COOH) as the organic ligand. The synthesis process was as follows.

[0211] 100 mL of a 0.1 M nickel chloride (NiCl2) aqueous solution and 100 mL of a 0.1 M maleic acid aqueous solution were prepared, respectively. The two solutions were slowly mixed to adjust the pH to 3. The mixed solutions were stirred at 50°C for 4 hours to proceed with the reaction.

[0212] After the reaction was completed, the resulting precipitate was filtered and washed with ethanol. The resulting solid product was dried at 70°C for 14 hours to obtain the final organometallic complex.

[0213] Comparative Example 1-1: Silver (Ag)-hexamethylenetetramine-based complex

[0214] In Comparative Example 1-1, silver (Ag) was used as the metal ion in the same manner as in the example, but hexamethylenetetramine (C6H12N4) was used as the organic ligand to synthesize a complex. The synthesis process was as follows.

[0215] As in the examples, 100 mL of a 0.1 M aqueous silver nitrate (AgNO3) solution and 100 mL of a 0.1 M aqueous hexamethylenetetramine solution were prepared, respectively. However, unlike the examples, no separate pH adjustment process was required when mixing the two solutions. The mixed solutions were stirred at 40°C for 2 hours to proceed with the reaction.

[0216] After the reaction was completed, the resulting precipitate was filtered and washed with cold water to remove impurities. Finally, the resulting solid product was dried at 60°C for 8 hours to obtain the composite of the comparative example.

[0217] Comparative Example 1-2: Copper (Cu)-pyridine-based complex

[0218] In Comparative Example 1-2, a complex was synthesized using copper (Cu) as the metal ion and pyridine (C5H5N) as the organic ligand. The synthesis process was as follows.

[0219] A 100 mL 0.1 M aqueous solution of copper sulfate (CuSO4) and a 100 mL 0.2 M pyridine solution were prepared. The two solutions were slowly mixed, without any separate pH adjustment during the process. The mixed solutions were stirred at 45°C for 3 hours to proceed with the reaction.

[0220] After the reaction was completed, the resulting precipitate was filtered and washed with ethanol to remove impurities. Finally, the resulting solid product was dried at 70°C for 10 hours to obtain the composite of the comparative example.

[0221] Example 2: Anisotropic challenge composition

[0222] Example 2-1: Silver (Ag)-adipic acid-based anisotropic conductive composition

[0223] In Example 2-1, a composition including the organometallic complex compound of Example 1-1 was prepared. This composition mainly comprises 60 parts by weight of an organometallic complex compound (MOF), which is composed of a silver (Ag) metal ion and an adipic acid (HOOC-(CH2)4-COOH) organic ligand. 10 parts by weight of stearic acid was used as a phase separation inducer, 5 parts by weight of bisphenol A type epoxy resin was used as a curable resin, 5 parts by weight of 2-methyl imidazole was used as a curing agent, and 20 parts by weight of tetrahydrofuran was used as a solvent.

[0224] The composition was prepared as follows. First, an organometallic complex was synthesized according to the method described in Example 1-1. Next, a phase-separation inducer, a curable resin, and a curing agent were dissolved in a solvent. The synthesized organometallic complex was then added to this solution and mixed uniformly. The mixture was stirred at 60°C for 2 hours, and the resulting composition was stored at room temperature.

[0225] Example 2-2: Copper (Cu)-succinic acid-based anisotropic conductive composition

[0226] Example 2-2 used the same composition and manufacturing method as Example 2-1, but used the copper (Cu)-succinic acid-based MOF synthesized in Example 1-2 as an organometallic complex compound.

[0227] Example 2-3: Nickel (Ni)-maleic acid-based anisotropic conductive composition

[0228] Example 2-3 used the same composition and manufacturing method as Example 2-1, but used a nickel (Ni)-maleic acid-based MOF synthesized in Example 1-3 as an organometallic complex compound.

[0229] Comparative Example 2

[0230] Comparative Example 2-1: Silver (Ag)-hexamethylenetetramine-based anisotropic conductive composition

[0231] Comparative Example 2-1 used the same composition and manufacturing method as Example 2-1, but used a silver (Ag)-hexamethylenetetramine-based MOF synthesized in Comparative Example 1-1 as an organometallic complex compound.

[0232] Comparative Example 2-2: Anisotropic conductive composition without phase separation inducer

[0233] In Comparative Example 2-2, an organometallic complex compound composition excluding a phase-separation inducer was prepared. This composition contained 70 parts by weight of an organometallic complex compound (MOF) as a main component, and was composed of silver (Ag) metal ions and adipic acid organic ligands, similar to Examples 1 and 2. 5 parts by weight of bisphenol A type epoxy resin was used as a curable resin, 5 parts by weight of 2-methyl imidazole was used as a curing agent, and 20 parts by weight of tetrahydrofuran was used as a solvent.

[0234] The manufacturing method was the same as in Example 2, but no phase separation inducer was added.

[0235] Example 3

[0236] Example 3-1 Anisotropic conductive composition containing solder powder

[0237] In Example 3-1, an organometallic complex composition additionally including solder powder was prepared. This composition included 20 parts by weight of an organometallic complex (MOF) and, similarly to Example 1-1, was composed of silver (Ag) metal ions and adipic acid organic ligands. Five parts by weight of oleic acid was used as a phase-separation inducer, 10 parts by weight of urethane acrylate as a curable resin, 5 parts by weight of benzoyl peroxide as a curing agent, and 10 parts by weight of ethanol as a solvent. Additionally, 50 parts by weight of solder powder (Sn58Bi, particle size 5 μm) was included. The preparation method was similar to Example 2-1, except that the organometallic complex and solder powder were added to the solution together. In addition, the mixture was stirred at 50°C for 3 hours.

[0238] Example 3-2 Anisotropic conductive composition containing solder powder

[0239] Example 3-2 used the same composition and manufacturing method as Example 3-1, but used Sn58Bi with a particle size of 10 μm as the solder powder.

[0240] Example 3-3 Anisotropic conductive composition containing solder powder

[0241] Example 3-3 used the same composition and manufacturing method as Example 3-1, but the content of solder powder was 80 parts by weight.

[0242] Example 3-4 Anisotropic conductive composition comprising conductive particles

[0243] In Example 3-4, an organometallic complex composition additionally containing conductive particles was prepared.

[0244] The composition consisted of 30 parts by weight of a metal-organic framework (MOF), 10 parts by weight of a phase separation inducer, 5 parts by weight of a curable resin, 5 parts by weight of a curing agent, 20 parts by weight of a solvent, and 60 parts by weight of a conductive particle (silver, 10 μm in size).

[0245] Example 3-5 Anisotropic conductive composition containing solder powder

[0246] In Example 3-5, an organometallic complex composition additionally including conductive nanoparticles was prepared. The composition consisted of 60 parts by weight of an organometallic complex (MOF), 10 parts by weight of a phase separation inducer, 5 parts by weight of a curable resin, 5 parts by weight of a curing agent, 20 parts by weight of a solvent, and 10 parts by weight of conductive nanoparticles (silver, size 100 nm).

[0247] Comparative Example 3

[0248] Comparative Example 3-1 Anisotropic conductive composition containing solder powder

[0249] Comparative Example 3-1 used the same composition and manufacturing method as Example 3-1, but used a silver (Ag)-hexamethylenetetramine-based MOF synthesized in Comparative Example 1-1 as an organometallic complex compound.

[0250] Comparative Example 3-2 Anisotropic conductive composition containing solder powder

[0251] Comparative Example 3-2 used the same composition and manufacturing method as Example 3-1, but used Sn58Bi as solder powder with a particle size of 20 μm.

[0252] Comparative Example 3-3 Anisotropic conductive composition containing solder powder

[0253] Comparative Example 3-3 used the same composition and manufacturing method as Example 3-1, but used 130 parts by weight of solder powder.

[0254] Example 4: Composition for manufacturing basic anisotropic conductive material

[0255] In this Example 4, a basic composition for producing an anisotropic conductive material was prepared. The composition comprised 30 parts by weight of a metal-organic framework (MOF), 30 parts by weight of a flow control agent, 10 parts by weight of a phase separation inducer, 10 parts by weight of a curable resin, 5 parts by weight of a curing agent, and 20 parts by weight of a solvent. Bisphenol A type epoxy resin was used as the curable resin, 2-methyl imidazole as the curing agent, and tetrahydrofuran as the solvent.

[0256] The manufacturing process is as follows. First, the organometallic complex compound of Example 1-1 was synthesized. Next, a flow control agent, a phase-separation inducer, a curable resin, and a curing agent were dissolved in a solvent. The synthesized organometallic complex compound was then added to this solution and mixed uniformly. The mixture was stirred at 60°C for 2 hours, and the resulting composition was stored at room temperature.

[0257] Comparative Example 4-1: Composition for manufacturing silver (Ag)-hexamethylenetetramine anisotropic conductive material

[0258] Comparative Example 4-1 used the same composition and manufacturing method as Example 4, but used the silver (Ag)-hexamethylenetetramine-based MOF synthesized in Comparative Example 1-1 as an organometallic complex compound.

[0259] Comparative Example 4-2: Composition for manufacturing anisotropic conductive material without phase separation inducer

[0260] In Comparative Example 4-2, a composition for manufacturing an anisotropic conductive material excluding a phase separation inducer was prepared. This composition consisted of 40 parts by weight of an organometallic complex compound (MOF), 30 parts by weight of a flow control agent, 10 parts by weight of a curable resin, 5 parts by weight of a curing agent, and 20 parts by weight of a solvent.

[0261] It was composed of silver (Ag) metal ions and adipic acid organic ligands, similar to Example 4. Bisphenol A type epoxy resin was used as a curable resin, 2-methyl imidazole as a curing agent, and tetrahydrofuran as a solvent.

[0262] The manufacturing method was the same as in Example 4, but no phase separation inducer was added.

[0263] Example 5-1: Composition for manufacturing anisotropic conductive material including solder powder

[0264] In Example 5-1, a composition for producing an anisotropic conductive material including solder powder was prepared. The composition consisted of 10 parts by weight of an organometallic complex (MOF), 5 parts by weight of a flow control agent, 5 parts by weight of a phase separation inducer, 10 parts by weight of a curable resin, 5 parts by weight of a curing agent, 5 parts by weight of a solvent, and 60 parts by weight of solder powder (Sn58Bi, particle size 5 μm).

[0265] The manufacturing method was the same as in Example 4, but solder powder was additionally added.

[0266] Example 5-2: Composition for manufacturing anisotropic conductive material including solder powder

[0267] In Example 5-2, a composition for producing an anisotropic conductive material including solder powder was prepared. The composition consisted of 20 parts by weight of a metal-organic framework (MOF), 5 parts by weight of a flow control agent, 3 parts by weight of a phase separation inducer, 5 parts by weight of a curable resin, 5 parts by weight of a curing agent, 2 parts by weight of a solvent, and 60 parts by weight of solder powder (Sn58Bi, particle size 5 μm). The manufacturing method was the same as in Example 4, but solder powder was additionally added.

[0268] Example 5-3: Composition for manufacturing anisotropic conductive material including solder powder (PAC-58)

[0269] In Example 5-3, a composition for producing an anisotropic conductive material including solder powder was prepared. The composition consisted of 5 parts by weight of a metal-organic framework (MOF), 1 part by weight of a flow control agent, 1 part by weight of a phase separation inducer, 2 parts by weight of a curable resin, 1 part by weight of a curing agent, 5 parts by weight of a solvent, and 85 parts by weight of solder powder (Sn58Bi, particle size 5 μm). The manufacturing method was the same as in Example 4, but solder powder was additionally added.

[0270] Example 5-4: Composition for manufacturing anisotropic conductive material including solder powder

[0271] In Example 5-4, a composition for producing an anisotropic conductive material including solder powder was prepared. The composition consisted of 50 parts by weight of a metal-organic framework (MOF), 1 part by weight of a flow control agent, 1 part by weight of a phase separation inducer, 2 parts by weight of a curable resin, 2 parts by weight of a curing agent, 5 parts by weight of a solvent, and 38 parts by weight of solder powder (Sn58Bi, particle size 5 μm). The manufacturing method was the same as in Example 4, but solder powder was additionally added.

[0272] Examples 5-1 to 5-4 are summarized in Table 1 below.

[0273] Main Composition Example 5-1 Example 5-2 Example 5-3 Example 5-4 Metal-organic complex (MOF) 1020550 Flow control agent 5511 Phase separation inducer 5311 Curable resin 10523 Curing agent 5512 Solvent 5255 Solder powder 60608538 Sum (SUM) 100100100100 Solder powder type Sn58BiSn58BiSn58BiSn58BiParticle size (μm) 5555

[0274] Comparative Example 5

[0275] Comparative Example 5-1 Composition for manufacturing anisotropic conductive material including solder powder

[0276] Comparative Example 5-1 used the same composition and manufacturing method as Example 5-1, but used a silver (Ag)-hexamethylenetetramine-based MOF synthesized in Comparative Example 1-1 as an organometallic complex compound.

[0277] Comparative Example 5-2 Composition for manufacturing anisotropic conductive material including solder powder

[0278] Comparative Example 5-2 used the same composition and manufacturing method as Example 5-1, but used 5 μm SnO2 (tin oxide) particles as solder powder.

[0279] Comparative Example 5-3 Composition for manufacturing anisotropic conductive material including solder powder

[0280] / *257 Comparative Example 5-3 used the same composition and manufacturing method as Example 5-1, but used 600 parts by weight of solder powder for 30 parts by weight of the organometallic complex compound.

[0281] Comparative Example 5-4 Composition for manufacturing anisotropic conductive material including solder powder

[0282] Comparative Example 5-4 was performed in the same manner as Example 5-1, but Adipic acid was used instead of MOF to prepare a composition for manufacturing a conductive material.

[0283] Example 6: Composition for manufacturing anisotropic conductive material including conductive particles

[0284] In Example 6, a composition for producing an anisotropic conductive material further comprising conductive particles was prepared. The composition consisted of 30 parts by weight of an organometallic complex (MOF), 5 parts by weight of a flow control agent, 10 parts by weight of a phase separation inducer, 5 parts by weight of a curable resin, 5 parts by weight of a curing agent, 20 parts by weight of a solvent, and 60 parts by weight of conductive particles (silver, 10 μm in size).

[0285] The manufacturing method was the same as in Example 4, but conductive particles were additionally added.

[0286] Example 7: Composition for manufacturing anisotropic conductive material including conductive nanoparticles

[0287] In Example 7, a composition for producing an anisotropic conductive material including conductive nanoparticles was prepared. The composition consisted of 60 parts by weight of a metal-organic framework (MOF), 5 parts by weight of a flow control agent, 10 parts by weight of a phase separation inducer, 5 parts by weight of a curable resin, 5 parts by weight of a curing agent, 20 parts by weight of a solvent, and 10 parts by weight of conductive nanoparticles (silver, size 100 nm).

[0288] The manufacturing method was the same as in Example 4, but conductive nanoparticles were additionally added.

[0289] Example 8: Composition for manufacturing anisotropic conductive material

[0290] In Example 8, the same procedure as in Example 5-2 was followed, but a composition for manufacturing an anisotropic conductive material including conductive particles and conductive nanoparticles was manufactured.

[0291] The composition was composed of 20 parts by weight of a metal-organic framework (MOF), 5 parts by weight of a flow control agent, 3 parts by weight of a phase separation inducer, 5 parts by weight of a curable resin, 5 parts by weight of a curing agent, 2 parts by weight of a solvent, 40 parts by weight of a solder powder, 10 parts by weight of a conductive particle (copper, size 3.0 μm), and 10 parts by weight of a conductive nanoparticle (silver, size 100 nm).

[0292] The manufacturing method was the same as in Example 4, but conductive nanoparticles were additionally added.

[0293] The compositions of Examples 6 to 8 are summarized in Table 2 below.

[0294] Main composition Example 6 Example 7 Example 8 Metal-organic framework (MOF) 306020 Flow control agent 555 Phase separation inducer 1033 Curable resin 555 Curing agent 555 Solvent 20202 Solder powder--40 Conductive particles (Cu particles, size 3.0 um) 60 (Silver, 10 µm) - 10 Conductive particles (Silver, size 100 nm) - 10 (Silver, 100 nm) 10 Sum (SUM) 100 Solder powder type Sn58Bi Particle size (µm) 5

[0295] <Experimental Example>

[0296] <Experimental Example 1> Evaluation of soldering characteristics of compositions containing organometallic complex compounds

[0297] As shown in Fig. 11, the organometallic complex compound composition according to Example 2-1 of the present invention was printed on an Au / Cr / glass substrate, and a solder ball was attached thereon to perform reflow, and it was confirmed that soldering was possible due to the flux function of the organometallic complex compound, as shown in Fig. 12.

[0298] <Experimental Example 2> EDS Evaluation of a Composition Containing Solder Powder

[0299] An EDS evaluation was performed on the solder bump after soldering of Experimental Example 1 using an Au(300nm) / Cr(200nm) / Glass substrate, and the results shown in Fig. 13 were obtained. According to this, it can be confirmed that reduced silver ions are contained inside the solder bump.

[0300] <Experimental Example 3> EDS Evaluation of a Composition Containing an Organometallic Complex and Solder Powder

[0301] As a result of EDS evaluation after heating a composition containing an organometallic complex compound and solder powder, it was confirmed that the silver ions of the organometallic complex compound were reduced, as shown in Fig. 14, and soldering of the solder powder was possible due to the organic ligand component of the organometallic complex compound.

[0302] <Experimental Example 4> EDS Evaluation of Film Containing Organometallic Compound and Solder Powder

[0303] After printing a composition for manufacturing an anisotropic conductive material containing an organometallic complex compound, it was formed into a film, heated, and then EDS evaluated. As shown in Fig. 15, it was confirmed that silver ions of the organometallic complex compound were reduced within the pattern and soldering of solder powder was possible due to the organic ligand component of the organometallic complex compound.

[0304] <Experimental Example 5> EDS Evaluation of Film Containing Organometallic Compound and Solder Powder

[0305] The compositions of Examples 5-1 to 5-4 were printed on FPCB at a pitch of 260 μm, formed into a film, heated, and evaluated by EDS to confirm that the silver ions of the organometallic complex were reduced and soldering of the solder powder was possible. Figures 16 to 19 show the resistance, photograph, and elemental analysis graphs of the film on which the composition was printed.

[0306] <Experimental Example 6> EDS Evaluation of Paste Containing Organometallic Compound and Solder Powder

[0307] After printing on a 260 um pitch FPCB with the compositions of Examples 3-1 to 3-3 and heating, EDS evaluation was performed to confirm that the silver ions of the organometallic complex were reduced and soldering of the solder powder was possible. Figures 20 to 22 show the resistance, photograph, and elemental analysis graphs of the compositions on the FPCB.

[0308] <Experimental Example 7> Measuring film resistance

[0309] The resistance of the film printed with the composition of Example 5-3 and Example 5-4 at a pitch of 22 um (electrode 8 um, gap 14 um) was measured and shown in Table 3.

[0310] Example 5-3263℃(200℃), 10sec, 0.131MPa, Ω2probe123456789104.13.83.65.85.37.15.43.74.14.33.93.94.15.46.56.35.23.83.83.84probe123456789101.9221.92.12.72.51.91.81.9Example 5-3263℃(200℃), 10sec, 0.131MPa, Ω2probe111213141516171819204.654.32.14.74.84.94.55.24.54.54.94.54.24.655.14.55.14.34probe123456789102.52.32.32.62.72.832.62.92.7Example 5-4265℃(200℃), 10sec, 0.131MPa, Ω2probe123456789103.65.45.76.36.46.25.28.27.97.64.74.75.45.25.65.86.27.58.88.84probe123456789101.21.51.31.113.12.13.13.13.1Example 5-4265℃(200℃), 10sec, 0.131MPa, Ω2probe111213141516171819205.14.45.16.45.65.55.94.25.512.45.74.75. 56.17.58.65.84.29.315.44probe123456789102.31.72.12.122.32.422.53.1

[0311] <Experimental Example 8> Measuring film resistance

[0312] The pressure-dependent resistance of the film manufactured with the composition according to Example 5-4 was evaluated and summarized in Table 4.

[0313] Sample#bonding pressure (Mpa)12345678910Comparative example 5-42.12.42.52.82.82.42.32.32.22.42.6Example 5-42.12.42.52.72.22.12.22.52.32.4Comparative example 5-12.12.3XX4.2XX2.62.22.4Sample#bonding pressure12345678910Comparative example 5-42.22.22.22.51.32.22.32.42.12.8Comparative example 5-1XXXXX2237.1425XXSample#bonding pressure12345678910Third party0.073.4XXXXX5.528.7X6.7Example 5-410.62.12.42.32.22.32.52.42.42.2Comparative example 5-1XXXXXXXXXXSample#bonding pressure12345678910Third party0.05XXXXXXXXXXExample 5-46.22.12.32.11.71.92.12.42.92.2Comparative example 5-1XXXXXXXXXX

[0314] <Experimental Example 8> Determining the soldering characteristics of MOF

[0315] The compositions for manufacturing anisotropic conductive materials manufactured in Example 5-1 and Comparative Example 5-4 were printed on glass substrates using a screen printer as shown in the figure below. The printing size was 1 cm in diameter. Each printed substrate was placed on a hot plate with a surface temperature of 260°C and maintained for 5 minutes to complete soldering. Each photograph after soldering is shown in Fig. 23. It was confirmed that soldering was formed without any solder powder remaining in Example 5-1, which used the MOF manufactured in this patent. On the other hand, it was confirmed that a large number of unsoldered particles remained in Comparative Example 5-4, which did not use the MOF. These remaining particles cause short circuits and shorts. Ultimately, it can be seen that soldering is more complete when the MOF is used.

[0316] The features, structures, effects, etc. exemplified in each of the aforementioned embodiments can be combined or modified to implement other embodiments by those skilled in the art. Accordingly, the contents related to such combinations and modifications should be construed as being included within the scope of the present invention.

[0317]

Claims

A substance in which a metal ion is bonded to an organic ligand. The reduced metal (M) of the above metal ion is a metal having a standard reduction potential of -0.8 V to 1.8 V, An organometallic complex compound in which the organic ligand is an organic acid anion having at least one unshared electron pair, activated at pH 2 to 6, and having an activation temperature of 100 to 350°C. In the first paragraph, The above metal M is an organometallic complex compound having an electrical conductivity of 0.8 X 106 S / m to 7.0 X 107 S / m. In the first paragraph, An organometallic complex compound satisfying the following chemical formula 1. (Chemical Formula 1) M+COO?-(CH2)n- COO?M+ (M is a metal with a standard reduction potential of -0.8 V to 1.8 V, n is an integer between 2 and 15) An organometallic complex compound comprising a composition electrically connecting opposing first and second electrodes, wherein the composition comprises a metal (M) ion bonded to an organic ligand, wherein the reduced metal (M) of the metal ion is a metal having a standard reduction potential of -0.8 V to 1.8 V, and the organic ligand is an organic acid anion having at least one unshared electron pair, activated at pH 2 to 6, and having an activation temperature of 100 to 350°C; curable resin; and An anisotropic conductive composition comprising a phase separation inducing agent that induces phase separation of the metal and the curable resin. In paragraph 4, The above metal M is an anisotropic conductive composition having an electrical conductivity of 0.8 X 106 S / m to 7.0 X 107 S / m. In paragraph 4, An anisotropic conductive composition satisfying the following chemical formula 1. (Chemical Formula 1) M+COO?-(CH2)n- COO?M+ (M is a metal with a standard reduction potential of -0.8 V to 1.8 V, n is an integer between 2 and 15) In paragraph 4, The above anisotropic conductive composition further comprises at least one selected from the group consisting of solder powder, conductive particles, and conductive nanoparticles. In paragraph 7, The above solder powder is an anisotropic conductive composition having an electrical conductivity of 9 to 65 (MS / m). In paragraph 7, An anisotropic conductive composition wherein the particle size of the solder powder is 1 to 10 μm. In paragraph 7, An anisotropic conductive composition wherein the conductive particles and the conductive nanoparticles are metals or alloys selected from the group consisting of silver (Ag), gold (Au), indium (In), copper (Cu), indium tin oxide (ITO), palladium, platinum, nickel, and iridium. In paragraph 7, An anisotropic conductive composition in which the conductive particles have a particle diameter of 2 to 50 μm. In paragraph 7, An anisotropic conductive composition wherein the particle size of the conductive nanoparticles is 0.01 to 5.0 μm. In paragraph 4, An anisotropic conductive composition comprising 5 to 15 parts by weight of the phase separation inducer and 2.5 to 15 parts by weight of the curable resin relative to 30 parts by weight of the organometallic complex compound. In paragraph 7, An anisotropic conductive composition having a melting point of the above solder powder of 130 to 280°C. In paragraph 7, An anisotropic conductive composition comprising 0.5 to 120 parts by weight of the above solder powder. In paragraph 7, An anisotropic conductive composition comprising 0.5 to 70 parts by weight of the above conductive particles. In paragraph 7, An anisotropic conductive composition comprising 0.1 to 7 parts by weight of the above conductive nanoparticles.

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