JP4925405B2 - Method for manufacturing connection structure - Google Patents

Description

  The present invention relates to a connection structure excellent in fine circuit connectivity and connection reliability and a method for manufacturing the connection structure.

  Up to now, regarding connection structures in which LSI chips are connected to fine circuits, various connection materials and connection structure configurations have been studied in order to improve connectivity, prevent short circuits, and improve connection reliability. For example, a resin film is formed on a part other than the connection electrode of the connection board, a metal ball is arranged on the connection electrode part, the corresponding electrode position is aligned, and the LSI chip is pressed and heated, thereby causing the A method of forming an electrical connection and simultaneously curing a resin film (Patent Document 1), corresponding to a connection electrode of a connection board through a resin film in which holes are formed in a non-flowable film and conductive particles are fixed. A method of connecting LSI electrodes (see Patent Documents 2, 3, 4, and 5) is known.

  Moreover, the method of connecting using an anisotropic conductive film is often used because a large number of fine circuits can be connected together while ensuring good connectivity and insulation. Regarding this method, for example, a method using an anisotropic conductive film in which the surface of conductive particles is coated with an electrically insulating resin (see Patent Document 6), a layer containing conductive particles and a layer not containing the conductive particles are laminated. A method for preventing a short circuit between adjacent circuits using an anisotropic conductive film (see Patent Documents 7 and 8) is known.

  However, the method of arranging the connection material in accordance with the connection portion has a limitation in manufacturing technology with respect to a large number of fine connections, and there is a limit to satisfy all of the connectivity, insulation, and reliability. Further, in the prior art in which conductive particles are fixed to a non-flowing film such as a resin film, the number of connected particles is ensured, and a short circuit due to aggregation of the conductive particles between the electrodes is prevented, the conductivity of the film is reduced. Since the functional particle separation of the adhesive particle fixing and the LSI chip fixing with an adhesive or the like may occur, problems such as interfacial peeling of the resin film, moisture absorption, etc. may occur, so it is not possible to satisfy both connectivity and reliability at the same time There wasn't. In addition, in the prior art using an anisotropic conductive film using insulating coated conductive particles, or an anisotropic conductive film formed by laminating a layer containing conductive particles and a layer not containing conductive particles, the conductivity at the time of connection is It was not possible to completely suppress the clogging of clogged particles in the connection terminals caused by particle flow, and it was not possible to achieve both connectivity and insulation.

JP 2004-63770 A Japanese Patent No. 3360772 JP 2000-1333050 A JP 2003-3281 A JP 2003-60333 A Japanese Patent Publication No. 7-99644 JP-A-6-45024 JP 2003-49152 A

  The present invention relates to a connection structure in which an LSI chip in which connection bumps are arranged on the outer periphery of the chip is connected to a connection substrate with an anisotropic conductive film, good electrical connectivity without impairing insulation between circuits, and It is an object of the present invention to provide a connection structure that realizes reliability and a manufacturing method thereof.

As a result of intensive studies to solve the above problems, the present inventor has conductive particles present in a standard deviation of a specific range in the connection portion, and within a specific range, a certain ratio or more. It has been found that the above-described problems can be solved by using a connection structure characterized by existing without contact with conductive particles.
That is, the present invention is as described below.

(1) An LSI chip in which connection bumps are arranged on the outer periphery of the chip is connected to the connection substrate with at least a curing agent, a curable insulating resin, and an anisotropic conductive film made of conductive particles. The standard deviation of the number of conductive particles present in the connection portion is 1.45 or more, 10% or less of the average number of conductive particles present in the connection portion, or smaller than the larger of the two, and the inner portion of the connection bump 93% or more of the number of conductive particles present in the substrate is present alone and present on the connection substrate surface side, and the conductive particles present on the connection portion of the connection bump and the inner portion of the connection bump are precious metals. At least one conductive particle selected from the group consisting of coated resin particles, noble metal-coated metal particles, metal particles, noble metal-coated alloy particles, and alloy particles, the average particle diameter thereof Is 1 to 10 [mu] m, the connection structure area of the connection bump is in the range of 500 [mu] m ² of 10000 ² A process for producing, between the LSI chip and the connection board having an array of connection bumps to the tip outer peripheral portion The LSI chip and the connection substrate by pressing the LSI chip and the connection substrate by interposing an anisotropic conductive film composed of at least a curing agent, a curable insulating resin, and conductive particles, and curing the resin. A method of manufacturing a connection structure for connecting a conductive film in an area within 1.5 times the average particle diameter of conductive particles from one surface of the film toward the thickness direction as the anisotropic conductive film. 90% or more of the number of particles is present alone, and the average particle interval between adjacent conductive particles is 0.5 to 5 times the average particle size of the conductive particles. Phi A method for manufacturing a connection structure, characterized by using a rum.
(2) The curable insulating resin is a thermosetting resin, and is 0.5 to 2.5 times the glass transition temperature of the component having the highest glass transition temperature among the components contained in the anisotropic conductive film. The connection structure according to ( 1 ), which is heat-bonded at a maximum temperature of 220 ° C. or less and reaches a maximum temperature in a time range of 50% or more of the heat-bonding time. Method.

  The connection structure of the present invention has good insulation characteristics between adjacent connection terminals, and has good electrical connectivity and good reliability between connected connection terminals. That is, the conductive particles are arranged with a certain standard deviation in the direction of the connection surface, and 93% or more of the conductive particles in the inner part of the bump under the chip are present alone and on the connection substrate surface. Good reliability can be ensured.

Hereinafter, the present invention will be specifically described.
First, the conductive particles in the connection structure of the present invention will be described.
As the conductive particles, it is preferable to use at least one selected from resin particles coated with noble metal, metal particles coated with noble metal, metal particles, alloy particles coated with noble metal, and alloy particles. As the resin particles coated with the noble metal, it is preferable to use those obtained by coating spherical particles such as polystyrene, benzoguanamine, and polymethyl methacrylate with nickel and gold in this order.

Resin particles coated with a noble metal can be formed using softer resin particles according to the hardness of the fine connection terminal (bump) to be connected.
When the bump hardness to be connected is less than 50 Hv in terms of Vickers hardness, it is preferable to use flexible resin particles such as polymethacrylate resin. Moreover, when bump hardness is 50 Hv or more, it is preferable to use hard resin particles, such as a benzoguanamine resin.

  As the metal particles coated with the noble metal, it is preferable to use a metal particle such as nickel or copper coated with a noble metal such as gold, palladium or rhodium on the outermost layer. As a coating method, a thin film forming method such as a vapor deposition method or a sputtering method, a coating method using a dry blend method, a wet method such as an electroless plating method or an electrolytic plating method can be used. From the viewpoint of mass productivity, the electroless plating method is preferable.

  As the metal particles, those selected from metals such as silver, copper and nickel are preferably used. The alloy particles preferably have a melting point of 150 ° C. or more and 500 ° C. or less, and more preferably low melting point alloy particles having a melting point of 150 ° C. or more and 350 ° C. or less. When the melting point is 500 ° C. or less, a metal bond can be formed between the connection terminals, which is preferable from the viewpoint of connection reliability. Moreover, it is preferable that melting | fusing point is 150 degreeC or more from a viewpoint of heat-resistant connection reliability.

  As the alloy particles coated with the noble metal, for example, alloy particles composed of two or more kinds selected from gold, silver, copper, nickel, tin, zinc, bismuth, indium, etc. are coated with the noble metal using the above method or the like. Can be used.

  As the alloy particles, for example, alloy particles composed of two or more selected from gold, silver, copper, nickel, tin, zinc, bismuth, indium and the like are preferable. When alloy particles having a melting point of 150 ° C. or higher and 500 ° C. or lower are used, it is preferable to coat the particle surface with a flux or the like in advance. It is preferable to use a so-called flux because the surface oxides can be removed. As the flux, fatty acids such as abietic acid can be used.

  The ratio of the average particle size to the maximum particle size of the conductive particles is preferably 2 or less, and more preferably 1.5 or less. The particle size distribution of the conductive particles is preferably narrower, and the geometric standard deviation of the particle size distribution of the conductive particles is preferably 1.2 to 2.5, and preferably 1.2 to 1.4. Is particularly preferred. When the geometric standard deviation is the above value, the variation in particle size is reduced. Usually, when a certain gap exists between two terminals to be connected, it is considered that the conductive particles function more effectively as the particle diameters become uniform.

  The geometric standard deviation of the particle size distribution is a value obtained by dividing the σ value of the particle size distribution (particle size value of 84.13% cumulative) by the particle size value of 50% cumulative. When the particle size distribution (logarithm) is set on the horizontal axis of the particle size distribution graph and the cumulative value (%, cumulative number ratio, logarithm) is set on the vertical axis, the particle size distribution is almost linear, and the particle size distribution is lognormal distribution. Follow. The cumulative value indicates the number ratio of particles having a certain particle size or less with respect to the total number of particles, and is expressed in%. The sharpness of the particle size distribution is expressed by the ratio of σ (the cumulative particle size value of 84.13%) and the average particle size (the cumulative particle size value of 50%). The σ value is an actual measurement value or a read value from the plot value of the graph.

The average particle size and particle size distribution can be measured using a known method and apparatus, and a wet particle size distribution meter, a laser particle size distribution meter, or the like can be used. Alternatively, the average particle size and particle size distribution may be calculated by observing the particles with an electron microscope or the like. The average particle size and particle size distribution of the present invention can be determined by a laser particle size distribution meter.
The average particle size of the conductive particles is preferably 1 to 10 μm, and more preferably 2 to 6 μm. The thickness is preferably 10 μm or less from the viewpoint of insulation, and is preferably less than 1 μm from the viewpoint of electrical connectivity, and is not easily affected by variations in height of connection terminals and the like.

Next, the connection structure of the present invention will be described.
The connection structure of the present invention is a structure in which an LSI chip having connection bumps arranged on the outer periphery of the chip is connected to a connection substrate with an anisotropic conductive film made of at least a curing agent, an insulating resin, and conductive particles. As the material of the connection bump, gold-based bumps such as gold, gold alloy, tin-plated gold, or bumps plated with gold on copper, nickel or the like can be used.

As the arrangement of the connection bumps, a straight type in which square bumps are arranged in a row, or a staggered type in which a plurality of rows are arranged by shifting the bumps and gaps every other bump can be used.
Area of each connection bump is preferably in the range of 500 [mu] m ² of 10000 ^2, and more preferably from 1000 .mu.m ² to 5000 .mu.m ^2. From the viewpoint of securing the number of conductive particles in the connecting portion and improving the reliability, 500 μm ² or more is preferable.

The connection substrate used in the connection structure of the present invention is preferably a transparent substrate from which the lower part of the chip can be confirmed from the back surface. For example, it is a resin film substrate such as a glass substrate, polyimide, polyethylene terephthalate, or polyethersulfone.
The connection electrode of the connection substrate is preferably a transparent electrode. For example, indium tin oxide and indium zinc oxide. In addition, a metal connection electrode can also be used.

  The average number of conductive particles present in the connection bump portion of the connection structure of the present invention is preferably 5 or more and 200 or less per bump. The number is preferably 5 or more from the viewpoint of connection reliability, and 200 or less is preferable from the viewpoint of the load during crimping connection. More preferably, it is in the range of 10 to 100.

The number of conductive particles in the connection bump portion can be measured from the back surface of the connection structure by optical microscope observation, laser microscope observation, or the like. In the case of a metal-based connection electrode that is not transparent, a plurality of dummy electrodes having openings formed in the metal electrode are arranged, and the average number of conductive particles and the number of conductive particles are determined from the number of conductive particles in the connection bump portion of the portion. Standard deviation can be determined. Moreover, even if it is a metal type connection electrode, in the case of a film substrate, if the back surface observation of the hollow of an electroconductive particle part is possible, it can use as it is.
The standard deviation of the number of conductive particles in the connection bump portion of the connection structure of the present invention is preferably 10% or less of the average number of conductive particles or less than the larger of 2, more preferably less than 2. It is preferable.

In the connection structure of the present invention, 93% or more of the number of conductive particles existing in the inner part of the connection bump formed on the outer periphery of the chip is present alone. Further, it is more preferable that 95% or more of the number of conductive particles exist alone. Furthermore, it is preferable that 93% or more, more preferably 95% or more of the number of conductive particles exists on the connection substrate surface side.
In the present invention, the inner portion of the connection bump formed on the outer periphery of the chip refers to a portion having the smallest area surrounded by one end of all terminals.
In the present invention, “the conductive particles are present alone” means that the conductive particles are present independently without agglomeration. Hereinafter, the expressions “exist alone” and “single particle” may be used in this sense.

90% or more of the conductive particles in the inner part are independent from the viewpoint of maintaining uniformity of the inner part of the chip and suppressing the occurrence of local defects at the time of expansion and shrinkage due to thermal history or the like. And it is preferable that it exists in the connection board | substrate surface side.
In the present invention, the connection substrate surface side means a region within 1.5 times the average particle size of the conductive particles from the connection substrate surface.

  In the connection structure of the present invention, the position where the conductive particles are present with respect to the thickness direction of the connection structure can be measured by a laser microscope capable of measuring the displacement in the focal direction. At the same time, it is also possible to measure the number of conductive particles that exist without contacting other conductive particles. When the displacement in the focal direction is measured using the laser microscope, the displacement measurement resolution is preferably 0.1 μm or less, and particularly preferably 0.01 μm or less.

The manufacturing method of the connection structure of the present invention may be combined with known methods. Preferably, it is preferable to connect with an anisotropic conductive film made of at least a curing agent, a curable insulating resin, and conductive particles. More preferably, an anisotropic conductive film in which 90% or more of the conductive particles in the anisotropic conductive film are previously present on the surface of one side is used, and this is used as an LSI chip in which connection bumps are arranged on the outer periphery of the chip. The LSI chip and the connection substrate are pressed between the connection substrate and the LSI chip and the connection substrate are pressed to cure the resin, thereby connecting (electrically and mechanically connecting) the LSI chip and the connection substrate. At this time, it is preferable that the anisotropic conductive film is connected with the conductive particle existing surface side of the anisotropic conductive film being the connection substrate surface side.
When connecting an LSI chip with connection bumps on the outer periphery of the chip with an anisotropic conductive film, the number of conductive particles per unit area of the inner part of the connection bump formed on the outer periphery after connection is The number of conductive particles per unit area of the previous anisotropic conductive film is 0.8 times or more, more preferably 0.9 times or more. From the viewpoint of suppressing the occurrence of local non-uniformity due to the short circuit due to the flow of conductive particles at the time of connection (short circuit due to aggregation between bumps) or the uneven distribution of the conductive particles that have flowed out, The number of conductive particles is preferably 0.8 times or more.

  Moreover, when manufacturing the connection structure of the present invention, in the case of thermocompression bonding using an anisotropic conductive film, the glass transition temperature of the component having the highest glass transition temperature among the components contained in the anisotropic conductive film. It is preferable to perform thermocompression bonding in the range of 0.5 to 2.5 times the maximum and 220 ° C. or lower. More preferably, it is in the range of 1 to 2 times. In the present invention, the glass transition temperature is expressed in degrees Celsius. From the viewpoint of preventing non-uniformity of the conductive particles due to resin flow at the time of connection, it is preferably 2.5 times or less of the glass transition temperature of the component having the highest glass transition temperature and 220 ° C. or less. From the viewpoint of suppressing voids and preventing peeling at the time of thermocompression bonding, it is preferably 0.5 times or more.

In the range of 50% or more of the thermocompression bonding time, it is preferable that the maximum temperature is reached, more preferably 80% or more. The thermocompression bonding time is preferably in the range of 3 to 60 seconds, more preferably in the range of 5 to 20 seconds.
As a method for measuring the glass transition temperature, a known method can be used. Specifically, it can be measured using a TMA-50 thermomechanical analyzer (manufactured by Shimadzu Corporation) at a temperature rising rate of 10 ° C./min.

The anisotropic conductive adhesive film used for this invention is illustrated.
As the curable insulating resin used for the anisotropic conductive film, a thermosetting resin, a photocurable resin, light and thermosetting resin, an electron beam curable resin, or the like can be used. In view of ease of handling, it is preferable to use a thermosetting insulating resin. As the thermosetting resin, an epoxy resin, an acrylic resin, or the like can be used, and an epoxy resin is particularly preferable.

  The epoxy resin is a compound having two or more epoxy groups in one molecule, and is preferably a compound having a glycidyl ether group, a glycidyl ester group or an alicyclic epoxy group, or a compound obtained by epoxidizing a double bond in the molecule. . Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, novolac phenol type epoxy resin, or modified epoxy resins thereof can be used.

  The curing agent used in the present invention may be any one that can cure the curable insulating resin. When a thermosetting resin is used as the curable insulating resin, a resin that can be cured by reacting with the thermosetting resin at 100 ° C. or higher is preferable. In the case of an epoxy resin, a latent curing agent is preferable from the viewpoint of storage stability. For example, an imidazole curing agent, a capsule type imidazole curing agent, a cationic curing agent, a radical curing agent, a Lewis acid curing agent. An agent, an amine imide curing agent, a polyamine salt curing agent, a hydrazide curing agent, and the like can be used. From the viewpoint of storage stability and low-temperature reactivity, capsule-type imidazole curing agents are preferred.

  In addition to the curing agent and the curable insulating resin, the anisotropic conductive film may contain a thermoplastic resin or the like. By blending a thermoplastic resin, it can be easily formed into a sheet. In this case, the blending amount is preferably 200 parts by mass or less, particularly preferably 100 parts by mass or less, based on 100 parts by mass of the components including the curing agent and the curable insulating resin.

  Thermoplastic resins that can be blended with the curable insulating resin of the present invention include phenoxy resin, polyvinyl acetal resin, polyvinyl butyral resin, alkylated cellulose resin, polyester resin, acrylic resin, styrene resin, urethane resin, polyethylene terephthalate resin, etc. There may be a combination of one or more resins selected from them. Among these resins, a resin having a polar group such as a hydroxyl group or a carboxyl group is preferable from the viewpoint of adhesive strength. Moreover, it is preferable that a thermoplastic resin contains 1 or more types of thermoplastic resins whose glass transition temperature is 80 degreeC or more and 300 degrees C or less.

  In the anisotropic conductive film of the present invention, an additive may be blended with the above constituent components. In order to improve the adhesion between the anisotropic conductive film and the adherend, a coupling agent can be blended as an additive. As the coupling agent, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, or the like can be used, and a silane coupling agent is preferable. Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptotrimethoxysilane, γ-aminopropyltrimethoxysilane, β-aminoethyl-γ- Aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and the like can be used.

  The blending amount of the coupling agent is preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the components including the curing agent and the curable insulating resin. 0.01 mass part or more is preferable from a viewpoint of adhesive improvement, and 1 mass part or less is preferable from a reliability viewpoint.

  For the production of the connection structure of the present invention, it is preferable to use an anisotropic conductive film in which 90% or more of the conductive particles in the anisotropic conductive film are present in the vicinity of one surface in advance. An example of the anisotropic conductive film will be described. The anisotropic conductive film is, for example, 90% or more of the number of conductive particles in a region within 1.5 times the average particle diameter of the conductive particles along the thickness direction from one surface of the anisotropic conductive film. Is preferably present alone, more preferably 95% or more is present alone.

  Furthermore, in the anisotropic conductive film, it is preferable that the average particle interval between adjacent conductive particles is 0.5 to 5 times the average particle size of the conductive particles. More preferably, the average particle size is 20 μm or less and 0.5 to 3 times the average particle size. From the viewpoint of preventing particle aggregation due to particle flow at the time of connection and ensuring insulation, the average particle diameter is preferably 0.5 times or more, and from the viewpoint of fine connection, it is preferably 5 times or less of the average particle diameter.

In the present invention, the adjacent conductive particles are selected from arbitrary conductive particles and refer to six conductive particles closest to the conductive particles. The method for obtaining the average particle spacing between adjacent conductive particles is as follows.
First, a photograph of the anisotropic conductive film is taken with an optical microscope from the surface side where the conductive particles are present. Next, arbitrary 20 conductive particles are selected, the distance from the 6 conductive particles closest to the respective conductive particles is measured, the average value of the whole is obtained, and the average particle interval is obtained. .

  The thickness of the anisotropic conductive film is preferably 10 μm or more and 30 μm or less, and more preferably 15 μm or more and 25 μm or less. From the viewpoint of mechanical connection strength, it is preferably 10 μm or more, and from the viewpoint of preventing a decrease in the number of connected particles due to particle flow during connection, it is preferably 30 μm or less.

Next, a method for producing an anisotropic conductive film in which the conductive particles in the present invention are present without contacting with other conductive particles will be exemplified.
As the method for producing the anisotropic conductive film, an adhesive layer is formed on a biaxially stretchable film or sheet, conductive particles are arranged in a single layer on the film, and the conductive particles are stretched. It is preferable to disperse and arrange the conductive particles and transfer the conductive particles to an adhesive sheet made of at least a curing agent and a curable insulating resin while maintaining the stretched state.

  As the biaxially stretchable film, a known resin film or the like can be used, but a polyethylene resin, a polypropylene resin, a polyester resin, a polyvinyl butyral resin, a polyvinyl alcohol resin, a polyvinylidene chloride resin alone or a copolymer, etc. Alternatively, it is preferable to use a flexible and stretchable resin film such as a rubber sheet such as nitrile rubber, butadiene rubber, or silicone rubber. Polypropylene resin and polyester resin are particularly preferable. The shrinkage after stretching is preferably 10% or less.

  As a method for arranging and fixing conductive particles on a biaxially stretchable film, a known method can be used. For example, a method in which an adhesive layer containing at least a thermoplastic resin is formed on the biaxially stretchable film, conductive particles are brought into contact therewith and adhered, and a single layer is arranged by applying a load with a rubber roll or the like. Can be taken. In this case, a method of repeating the adhesion-roll operation several times is preferable for filling without gaps. In the case of spherical conductive particles, since the closest packing is the most stable structure, it can be filled relatively easily. Alternatively, an adhesive is formed on the biaxially stretchable film to form an adhesive layer, and conductive particles are adhered on the adhesive layer. If necessary, the adhesion is repeated several times, and a method of arranging in a single layer is used. be able to.

  As a method for stretching a biaxially stretchable film in which conductive particles are arranged in a single layer, a known method can be used, but a biaxial stretching device is preferably used from the viewpoint of uniform dispersion alignment. From the viewpoint of particle spacing, the degree of stretching is preferably 50% or more and 400% or less, and more preferably 100% or more and 300% or less. In addition, 100% stretching means that the length of the portion stretched along the stretching direction is 100% of the length before stretching. The stretching direction is arbitrary, but biaxial stretching with a stretching angle of 90 ° is preferable, and simultaneous stretching is preferable. In the case of biaxial stretching, the degree of stretching in each direction may be the same or different.

As the biaxial stretching apparatus, a simultaneous biaxial continuous stretching apparatus is preferable.
As the simultaneous biaxial continuous stretching apparatus, a known one can be used, but a tenter type stretching machine that continuously stretches by fixing the long side with a chuck fitting and simultaneously stretching the distance in the vertical and horizontal directions is preferable. As a method for adjusting the degree of stretching, a screw method or a pantograph method can be used, but a pantograph method is more preferable from the viewpoint of accuracy of adjustment. When stretching while heating, it is preferable to provide a preheating zone before the stretched portion and a heat setting zone behind the stretched portion.

  The anisotropic conductive film of the present invention may be a single-layer film composed of at least a curing agent, a curable insulating resin, and conductive particles, and the film does not contain conductive particles and is at least insulated. A multilayer film in which resin sheets containing a conductive resin are laminated may be used.

  As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, a known one can be used, but when biaxial stretching is performed while heating, it is preferable to use a non-thermal crosslinkable pressure-sensitive adhesive. Specifically, natural rubber-based adhesives, synthetic rubber-based adhesives, synthetic resin emulsion-based adhesives, silicone-based adhesives, ethylene-vinyl acetate copolymer adhesives, and the like can be used alone or in combination. . From the viewpoint of conductive particle retention before stretching, uniformity of conductive particle dispersion during stretching, and transferability of conductive particles after stretching, a pressure-sensitive adhesive obtained by graft polymerization of a natural rubber-based pressure-sensitive adhesive with acrylate is particularly preferable. Furthermore, it is preferable to heat-process for 1 minute to 5 minutes below extending | stretching temperature before extending | stretching from the point of the uniformity at the time of heating extending | stretching.

  The thickness of the adhesive layer is preferably in the range of 1/50 to 3 times the average particle diameter of the conductive particles used, and more preferably in the range of 1/10 to 2 times. From the viewpoint of holding the conductive particles at the time of adhesion and stretching of the conductive particles, the thickness of the adhesive layer is preferably 1/50 or more of the average particle diameter of the conductive particles, from the viewpoint of particle transfer to the adhesive sheet after stretching. 3 times or less is preferable. As the method for forming the adhesive layer, a method in which a dispersion or solution in a solvent or water is applied and dried by a known method such as a gravure coater, a die coater, a knife coater, a bar coater, or a spray coat can be used. When a hot-melt type pressure-sensitive adhesive is used, it can be roll-coated without a solvent.

  In applying the conductive particles to the adhesive layer, it is preferable that the conductive particles are arranged in a single layer with almost no gap (dense packing). As a method for dense packing, the above-described method of dispersing and arranging conductive particles on a biaxially stretchable film can be used. In addition, close packing means filling so that the average particle | grain space | interval between the filled particles may be 1/2 or less of an average particle diameter. More preferably, the average particle interval between the filled particles is 1/5 or less of the average particle size.

  The film thickness of the biaxially stretched film is preferably 1/10 to 1 times the total thickness of the adhesive sheet to be transferred and the base film of the adhesive sheet, and 1/5 to 1/2. It is particularly preferred that From the viewpoint of handling properties of the stretched film, it is preferably 1/10 or more, and from the viewpoint of particle transfer to the adhesive film after stretching, it is preferably 1 time or less.

The electronic circuit components constituting the connection structure of the present invention include wiring board connection applications for display devices such as liquid crystal display devices, plasma display devices, electroluminescence display devices, and electronic device mounting applications such as LSIs for these devices, and others. Can be used for mounting electronic circuit parts such as wiring board connection parts of LSIs and LSIs. Among the display devices, it is preferably used for plasma display devices and electroluminescence display devices that require reliability.
Next, the present invention will be described with reference to examples and comparative examples.

(Connection structure manufacturing method)
After an oxide film is formed on the entire surface of a silicon piece (thickness 0.5 mm) of 1.6 mm × 15.1 mm in length and width, an aluminum thin film (1000 mm) having a width of 74.5 μm and a length of 120 μm is 40 μm inside from the outer side. 175 pieces are formed on the long side and 16 pieces are formed on the short side, respectively, so as to have an interval of 1 μm. In order to form two gold bumps (thickness 15 μm) each having a width of 28 μm and a length of 70 μm on the aluminum thin film so as to have an interval of 12 μm, a width of 10 μm inside 6.0 μm from the outer peripheral portion of each gold bump placement location. Then, a protective film of silicon oxide is formed on the entire surface other than the opening by a conventional method except for leaving the opening having a length of 60 μm. Thereafter, the gold bump is formed to obtain a test chip.

A connection pad of an indium tin oxide film (1500 mm) so that gold bumps on the aluminum thin film are connected to a gold bump on the adjacent aluminum thin film on a non-alkali glass having a thickness of 0.7 mm so as to be paired with each other. Width 68 μm, length 100 μm). Each time 20 gold bumps are connected, an indium tin oxide thin film lead wire is formed on the connection pad (this lead wire serves as a connection resistance measurement portion).
In addition, a connection pad (68 μm wide, 100 μm long) of an indium tin oxide film (1500 mm) is formed in such a positional relationship that two gold bumps on the aluminum thin film are connected to different sides. The connection wiring of the indium tin oxide thin film is formed so that every five of the connection pads can be connected, and further, every five of the connection pads can be connected so as to form a comb pattern. The connection wiring of the indium tin oxide thin film is formed. A lead wire of an indium tin oxide thin film is formed on each connection wire (this lead wire becomes an insulation resistance measurement part).

An aluminum-titanium thin film (titanium 1%, 3000 mm) is formed on each lead-out wiring to form a connection substrate. A 2.5 mm wide pressure-bonding head is provided by temporarily stretching the side of the anisotropic conductive adhesive sheet having a width of 2 mm and a length of 17 mm where the conductive particles are present so that the connection pads are all covered on the connection substrate. After pressing at 80 ° C., 0.3 MPa for 3 seconds, the polyethylene terephthalate base film is peeled off. A test chip is placed there so that the positions of the connection pads and the gold bumps are matched, and pressure bonding with 2.0 MPa is performed at a predetermined temperature for 5 seconds.
Regarding the temperature conditions at the time of thermocompression bonding, a thermocouple is arranged between the anisotropic conductive film and the connection substrate, pressure bonding is performed in the same manner as described above, temperature measurement at the time of crimping is performed, and the maximum temperature reached and the maximum Measure the time to reach the final temperature.
After the crimping, the resistance value between the lead wires (daisy chain of 20 gold bumps) is measured with a four-terminal resistance meter to obtain a connection resistance value.
In addition, the resistance between the paired lead wires is measured to obtain an insulation resistance value.

  While maintaining this insulation resistance test substrate at 85 ° C. and 85% relative humidity, a DC voltage of 25 V is applied between the pair of lead wires using a constant voltage constant current power source. The insulation resistance between the wires is measured every 5 minutes, the time until the insulation resistance value becomes 10 MΩ or less is measured, and the value is defined as the insulation decrease time. The case where the insulation decrease time is less than 240 hours is indicated as x, and the case where the insulation decrease time is 240 hours or more is indicated as ◯.

[Example 1]
38 g of phenoxy resin (glass transition temperature 98 ° C., number average molecular weight 14000), 34 g of naphthalene type epoxy resin (epoxy equivalent 136, semi-solid), 0.06 g of γ-glycidoxypropyltrimethoxysilane, mixed solvent of ethyl acetate-toluene Dissolve in (mixing ratio 1: 1) to obtain a 50% solid content solution. A liquid epoxy resin containing a microcapsule type latent imidazole curing agent (average particle diameter of microcapsule 7 μm, active temperature 125 ° C.) 28 g is mixed and dispersed in the 50% solid content solution. Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film, and air-dried at 60 degreeC for 15 minute (s), and obtained the film-like adhesive sheet of film thickness of 24 micrometers.
Gold-plated plastic particles having an average particle size of 3.0 μm (conductivity) obtained by applying a natural rubber-methyl methacrylate graft copolymer adhesive as an adhesive layer to a thickness of 2 μm on an unstretched polypropylene film having a thickness of 100 μm. The particles were applied in a single layer with almost no gap. That is, the conductive particles are prepared in a container having a thickness of several layers or more in a container larger than the film width, and the adhesive particles are pressed and adhered to the conductive particles with the application surface of the adhesive facing downward. Then, excess particles were scraped off with a scrubber made of soft rubber.
By repeating this operation twice, a conductive particle adhesion film coated with a single layer without a gap was obtained. This conductive particle adhesion film was heat-treated at 100 ° C. for 3 minutes in a dryer.
This film was fixed with 10 chucks in the vertical and horizontal directions using a biaxial stretching device (X6H-S, manufactured by Toyo Seiki, pantograph type corner stretching type biaxial stretching device), preheated at 150 ° C. for 120 seconds, Thereafter, the film was stretched and fixed by 100% at a speed of 5% / second. Then, after laminating the adhesive sheet on the stretched film, it was peeled off to obtain an anisotropic conductive film.

As a result of observation with an optical microscope, 99% of 100 conductive particles were single particles. The average particle spacing was 4.23 μm. The number of conductive particles per 10,000 μm ² was 283.
Using the anisotropic conductive film thus obtained, a connection structure was obtained by pressure bonding in the same manner as in the connection structure manufacturing method so that the connection temperature was 200 ° C. The thermocompression bonding time was 5 seconds. The maximum temperature reached at this time was 200 ° C., and the time required to reach the maximum temperature was 0.4 seconds.
The average number of conductive particles on the connection bumps (20 locations) was 18.4, and the standard deviation was 1.57 and 8.5%.
In addition, 95% of the conductive particles existing inside the connection bumps formed on the outer peripheral portion were single particles. 99% was present on the connection substrate surface side. The number of conductive particles per 10,000 μm ² was 256, which was 0.9 times that of the anisotropic conductive film.

[Example 2]
41 g of phenoxy resin (glass transition temperature 85 ° C., number average molecular weight 12000), 28 g of bisphenol A type epoxy resin (epoxy equivalent 240, semi-solid), 0.1 g of γ-glycidoxypropyltriethoxysilane mixed with ethyl acetate-toluene Dissolve in a solvent (mixing ratio 1: 1) to obtain a 50% solid content solution. A liquid epoxy resin containing a microcapsule-type latent imidazole curing agent (average particle diameter of microcapsule 7 μm, active temperature 125 ° C.) 31 g is mixed and dispersed in the 50% solid content solution. Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film, air-dried at 60 degreeC for 15 minute (s), and the film-form adhesive sheet of 23-micrometer-thickness was obtained.
A gold-plated copper particle having an average particle diameter of 3.2 μm was applied to a non-stretched polypropylene film having a thickness of 75 μm coated with 3 μm of a natural rubber-methyl methacrylate graft copolymer adhesive by the same method as in Example 1. A conductive particle adhesion film coated with a single layer without a gap was obtained. This conductive particle adhesion film was heat-treated in a dryer at 100 ° C. for 3 minutes.

This film was fixed by stretching 150% in the longitudinal and lateral directions using a biaxial stretching apparatus in the same manner as in Example 1. Then, after laminating the adhesive sheet on the stretched film, it was peeled off to obtain an anisotropic conductive adhesive sheet.
As a result of observation with an optical microscope, 98% of 100 conductive particles were single particles. Further, the average particle interval was 6.72 μm. The number of conductive particles per 10,000 μm ² was 176.

Using the anisotropic conductive film thus obtained, a connection structure was obtained by pressure bonding for 5 seconds at a connection temperature of 200 ° C. in the same manner as in the connection structure manufacturing method. The maximum temperature reached at this time was 200 ° C., and the time required to reach the maximum temperature was 0.5 seconds. The average number of conductive particles on the connection bumps (20 locations) was 10.4, and the standard deviations were 1.45 and 13.9%.
In addition, 96% of the conductive particles existing inside the connection bump formed on the outer peripheral portion were single particles. 98% was present on the connection substrate surface side. The number of conductive particles per 10,000 μm ² was 161, which was 0.92 times that of the anisotropic conductive film.

[Comparative Example 1]
In the same manner as in Example 1, an anisotropic conductive film was obtained. As a result of observation with an optical microscope, 99% of 100 conductive particles were single particles. Further, the average particle interval was 4.22 μm. The number of conductive particles per 10,000 μm ² was 285.
Using the anisotropic conductive film thus obtained, a connection structure was obtained by pressure bonding for 5 seconds at a connection temperature of 280 ° C. in the same manner as in the connection resistance measurement method. The maximum temperature reached at this time was 280 ° C., and the time required to reach the maximum temperature was 3 seconds. The average number of conductive particles on the connection bumps (20 locations) was 14.4, and the standard deviation was 3.43.
This was 23.8%. 65% was present on the connection substrate surface side.
In addition, 75% of the conductive particles existing inside the connection bumps formed on the outer periphery were single particles. The number of conductive particles per 10,000 μm ² was 215, which was 0.75 times that of the anisotropic conductive film.

[Comparative Example 2]
Acetic acid containing 37 g of phenoxy resin (glass transition temperature 98 ° C., number average molecular weight 14000), bisphenol A type epoxy resin (epoxy equivalent 190, 25 ° C. viscosity, 14000 mPa · S) 26 g, and γ-glycidoxypropyltrimethoxysilane 0.3 g Dissolve in a mixed solvent of ethyl-toluene (mixing ratio 1: 1) to obtain a 50% solid content solution.
37 g of liquid epoxy resin containing microcapsule type latent imidazole curing agent (average particle size of microcapsule 5 μm, active temperature 125 ° C.) and 2.0 g of gold-plated plastic particles having an average particle size of 3.0 μm are mixed with 50% solid content. Mix and disperse in the solution.
Then, it apply | coated on the 50-micrometer-thick polyethylene terephthalate film, air-dried at 60 degreeC for 15 minute (s), and the film-form anisotropic conductive adhesive sheet of 25-micrometer-thickness was obtained.

Of the conductive particles of the obtained anisotropic conductive adhesive sheet, 100 particles were randomly selected, and the distance from the anisotropic conductive adhesive sheet surface was measured using a laser displacement meter. As a result, it was found that the conductive particles exist randomly in the film thickness direction of the anisotropic conductive adhesive sheet. Moreover, 79% of 100 measured conductive particles were single particles. The number of conductive particles per 10,000 μm ² was 160.
Using the anisotropic conductive film thus obtained, a connection structure was obtained by thermocompression bonding at a connection temperature of 270 ° C. for 5 seconds in the same manner as in the connection resistance measurement method. The maximum temperature reached at this time was 270 ° C., and the time required to reach the maximum temperature was 0.5 seconds. The average number of conductive particles on the connection bumps (20 locations) was 8.1, and the standard deviation was 3.23. This was 39.9%. In addition, 71% of the conductive particles existing inside the connection bumps formed on the outer peripheral portion were single particles. 77% was present on the connection substrate surface side. The number of conductive particles per 10,000 μm ² was 101, which was 0.63 times that of the anisotropic conductive film.

  Table 1 shows connection resistance values and insulation test results of the connection structures of Examples and Comparative Examples. As is clear from Table 1, the anisotropic conductive adhesive sheet of the present invention exhibits very excellent insulation reliability.

  The connection structure of the present invention exhibits low connection resistance and high insulation reliability, and is suitable as a connection structure for a high-definition display device or the like that requires fine circuit connection.

It is the schematic which shows the structure of the connection structure of this invention.

Explanation of symbols

1 Connection bump 2 Conductive particles

Claims (2)

An LSI chip in which connection bumps are arranged on the outer periphery of the chip is connected to the connection substrate with at least a curing agent, a curable insulating resin, and an anisotropic conductive film made of conductive particles, and is present at the connection portion of the connection bump. The standard deviation of the number of conductive particles is 1.45 or more, 10% or less of the average number of conductive particles present in the connection portion, or smaller than the larger one of the two, and exists in the inner portion of the connection bump. 93% or more of the number of conductive particles is present alone and present on the connection substrate surface side, and the conductive particles present on the connection portion of the connection bump and the inner portion of the connection bump are coated with a noble metal. Resin particles, noble metal-coated metal particles, metal particles, noble metal-coated alloy particles, and at least one conductive particle selected from the group consisting of alloy particles, the average particle diameter of which is 1 to Is 0 .mu.m, the area of the connection bump A method of manufacturing a connection structure in the range of 500 [mu] m ² of 10000 ^2, between the LSI chip and the connection board having an array of connection bumps to the chip outer periphery, at least The LSI chip and the connection board are connected by pressing the LSI chip and the connection board, and curing the resin, with an anisotropic conductive film made of a curing agent, a curable insulating resin, and conductive particles interposed. A method of manufacturing a connection structure, wherein the anisotropic conductive film has conductive particles in a region within 1.5 times the average particle size of the conductive particles from one surface of the film toward the thickness direction. An anisotropic conductive film in which 90% or more of the number is present alone and the average particle interval between adjacent conductive particles is 0.5 to 5 times the average particle size of the conductive particles. A method for producing a connection structure, characterized by being used.   The curable insulating resin is a thermosetting resin, and ranges from 0.5 to 2.5 times the glass transition temperature of the component having the highest glass transition temperature among the components contained in the anisotropic conductive film; The method for producing a connection structure according to claim 1, wherein the thermocompression bonding is performed at a maximum temperature of 220 ° C or less, and the maximum temperature is reached in a time range of 50% or more of the thermocompression bonding time.

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