Material for adhesion

[Detailed Description of the Invention]

(Field of the Invention) The present invention relates to a suitable adhesion material for junction of metal, metal and metal, ceramics and ceramics, and ceramics. (PRIOR ART) Before, various conjugation methods as the conjugation method of the - question or a conjugation method of the contaminant question of metal and ceramics are known like metal, metal, ceramics, and ceramics. For example, as a conjugation method of metal and metal, there are the welding-by-fusion methods, such as electric welding, gas welding, and friction welding, and methods which do not fuse a substrate include the pasting-up method by processing or a right Machine contact name agent with a low. As a conjugation method of ceramics and ceramics, there are the pasting-up method, a heat-resistant metal method (refer to JP,61-58870,A), etc. by organic adhesives. As a conjugation method of a contaminant question [ ceramics / metal and ], it is to junction between these - quality of the materials of the, the pasting-up method by organic adhesives, and active metal solder -- it burns and there are the The method, the phase reaction method, etc. After meta-Rise(ing) by Mo, W, etc. to a ceramic substrate, a nickel plate is given, there are a metal base and a heat-resistant metal method to solder, and the conjugation method by a chemical reaction, such as building a hydrate compound using the inorganic adhesive of an oxide system, has also appeared with the latest art. (Object of the Invention) However, if the welding-by-fusion method which is a metal comrade's peculiar conjugation method among the various above-mentioned conjugation methods is removed, there is a fault that all are weak with heat and adhesive strength is not enough, either. On the other hand, although the junction art which uses the insertion material of junction art or the shape of foil by vapor deposition, sputtering, thermal spraying, etc. is also proposed slightly, it cannot be said to be the conjugation method it is lacking in practicality and adhesive strength not only has the fault that it is scarce, but may be satisfied with economical efficiency of a conjugation method for the use range being limited etc. Then, these people proposed metallic adhesion material by Japanese Patent Application No. No. 150003 [ 61 to ] previously as an adhesion material which can cancel these faults. This adhesion material uses Cu or nickel, and Tj-Zr, or Nb and Ag as a composition ingredient, and each of these ingredients are the metallic adhesion materials which consist of the end of composite powder engagement combination was carried out mechanically, and especially its adhesive strength is high, and it is suitable for junction of the - question of various kinds of metal and ceramics, or the contaminant question. However, when especially this metallic adhesion material is applied to the member which repeats a thermal excursion, For example, when the heat dissipation board which stuck copper foil on alumina substrates is used for the power module for large electric power, or when changing [ to / from the freezing point / near the 100 degreeC ] operating environmental temperature by a power transmission part article or autoparts, when the thermal excursion was repeated, junction power deteriorated, and the problem of resulting in destruction arose. It is made in order to solve question = three-question Sight spot of the metallic adhesion material concerning the account proposal of present invention," -, It has heat resistance, and adhesive strength is high, and adhesive strength degradation is small to a cold heat cycle, And it can use not only for junction between metal and the - quality of the material of ceramics but for junction of the contaminant question of metal and ceramics simple, and aims at providing a new metallic adhesion material with which it is satisfied of practicality and economical efficiency. (Means for solving problem) In order to achieve the above-mentioned object, this artificer tried analysis about the mechanism which adhesive strength deteriorates and results in destruction by a cold heat cycle, when the metallic adhesion material proposed previously was applied first. As a result, it became clear that it was a portion of a diffusion zone, i.e., the reaction layer of an active metal (Ti, Nb, Zr) and ceramics, that destruction takes place. Then, as a result of repeating research variously about the policy which prevents such destruction, it turned out that thickness of a diffusion zone is made thin and a metal plate and a ceramic board should just come to join directly via a diffusion zone fundamentally. However, when it was going to reduce the quantity of rule To 4-Re and an active metal in the quantity of the active metal, the problem on which junction power also decreases produced the thickness of the diffusion zone. however -- making the particle diameter of an active metal small as much as possible, as a result of repeating research further from other viewpoints, in order that this artificer may solve this problem -- diffusion -- it found out that it was solvable by supposing that it is easy. That is, by finding out that firm associative strength can be demonstrated, even if a diffusion zone is thin, and making particle diameter fine in that case, when easily spread by making the particle diameter of an active metal small, even if it lessened quantity of the active metal ingredient simultaneously, it found out that firm associative strength could be demonstrated. Based on such knowledge, these people proposed a new metallic adhesion material by Japanese Patent Application No. No. 210704 [ 62 to ] previously. However, when it was repeatedly used for a long period of time also with the substrate joined using umbrella Metallic quality adhesion material, the stress of cyclic compression arising, therefore making a substrate result in destruction according to the difference of the coefficient of thermal expansion of both materials understood. So, when research is repeated, in order to aim at improvement in the reliability of - layer, in order to adjust the coefficient of thermal expansion of an adhesion layer, it becomes clear that a proper quantity of specific components may be added, and it makes the present invention here. That is, the charge of adhesion material concerning the present invention contains 0.5~10% of at least 1 Taneji among Ti, Nb, and Zr as Cu:20-50%, Mo: 15~50% and a NiCr alloy: Contain the end of composite powder it has the composition which the remainder becomes from Ag and unescapable impurities including either of 20~60% and in which each ingredient carried out engagement combination mechanically by the mechanical alloy method. The present invention is explained still in detail below. (OPERATION) Cu, N", and Ag are required in order to achieve the low material duty of a Cu-Ag system, a nickel-Ag system, or Cu-nickel-A4 system and to raise junction intensity. nickel is effective in preventing the metal base side from exfoliating at the time of cooling after junction, when joining in combination with a metal base especially using a steel plate, there is an operation which prevents easing a coefficient of thermal expansion, and Cu is effective in making welding temperature low. However, if nickel is used with a metal simple substance, the melting point of a jointing material will upper H Carry out, and there is the difficulty of using, like junction takes high temperature. From these reasons, the remainder of the content sum total of Cu of 20~50%, preferably each ingredient which shows Ag below by adding 35~50%, preferably 20~50% are added. It is necessary to add Ti at least 0.5% or more from the relation of the above-mentioned Cu, nickel, and Ag for the improvement in performance as charges of adhesion material, such as junction intensity. However, since the altitude of a joining layer will become high and will become weak at a heat shock if it exceeds 10%, it is not desirable. Therefore, Ti is added in 0.5~10%, preferably 1~3% of range. The same effect is acquired even if it uses Nb, Zr, or these by composite instead of Tj. In compound addition, those amount sum totals of addition are taken as 0.5~10% of range. in order to adjust the coefficient of thermal expansion of a joining layer and to maintain adhesive strength also to cold heat repetition use in the present invention -- Mo or NjCr Including Cr -- any one sort is added. In Mo, since adhesive strength will decline if such an effect is not acquired less than ["-5% ] but it adds mostly exceeding 50%, it is not desirable. In NjCr, an effect is accepted in 20~60% of range. NjCr Including Cr composition is Cr : The thing of remainder nickel is suitable 20~50%. When adding these ingredients, it is necessary to use powder (5 micrometers or less, preferably 2 micrometers or less). In the case of a Nj Cr alloy, it is also possible to add the fine powder of Nj and Cr independently, but the melting point goes up in that case, and the effect on heat cycle nature is not acquired. The reason the rise of the melting point is not accepted even if it increases the amount of addition of Mo and a NiCr alloy so that more clearly than the 1st table in the below-mentioned example shows that the role of an additive is a filler. At least one sort in a rare earth element (Y is included) can be added to the above-mentioned ingredient system if needed. Quantity to add may be made into 5 ppm-3wt%, and may use a misch metal. By adding a rare earth element, if it adds when joining Ceramic substrates, such as SjC, especially, an effect is remarkable. It is necessary to manufacture the metallic adhesion material which has the above-mentioned chemical component by what is called a mechanical alloy method. For that purpose, the composite powder end what is called of a mechanical alloy form in which each ingredient carried out engagement combination mechanically can be obtained by carrying out time required mixture churning and grinding the metallic powder of each ingredient under high speed 1 and high energy, using stirrers, such as a Crush machine, a ball mill, and attritor. If it carries out in the end of such composite powder, and welding temperature is chosen appropriately, junction intensity will be made Toward] 2 notably. Since engagement combination of the fine powder of each ingredient is carried out mechanically, each ingredient fine powder which adjoins precisely at welding temperature fuses on the surface, combination between particles becomes firm, and this is considered that the duty of a kind of laver is achieved and junction intensity increases. When it was used after each ingredient had alloyed at the high temperature exceeding such suitable welding temperature (it is 800~900degreeC at an Ag-Cu system) incidentally, reduction to which the effect falls was seen. In the simple mixed state, since it was in the mixed state which each ingredient separated, even if it heated, the above-mentioned effect was not able to be expected. However, it is necessary to make such a particle size in the end of composite powder into particle diameter (what carried out the all path of the 5-micrometer mesh) of 5 micrometers or less, and to make it into what improved activity. In the proposal of the point of this point and these people, although the particle diameter in the end of composite powder set to 44 micrometers or less, preferably 10 micrometers or less, since it is only indicated about the end of composite powder it specifically has about at least 10-micrometer particle diameter, it differs from the present invention. By the present invention, although there are many amounts of addition, such as Ti, Nb, and Zr, if the particle size of Ti powder becomes fine, it can paste up now also in a little amount of active metals, and can make junction power degradation very small also especially to a cold heat cycle. However, at less than 0.5%, it becomes poor joining an active metal. Activation is subject to the influence of calcination (combination) atmosphere, and it is easier to be activated , under a vacuum than N2 atmosphere. In order to obtain the composite powder end of the above-mentioned particle size, use fine powder of 10 micrometers or less as materials for mechanical alloying. occupying [ the end of composite powder ]-80% or more of whole metallic adhesion material power i? Completion -- better -- it is convenient even if each ingredient powder, such as To, some Cu(s), Ag, and Ti powder, is mixing. The metallic adhesion material which comprises such end of composite powder substantially can be used in various modes, and is made into powder, a sheet shaped (a powder-compacting fabrication object, a powder rolling fabrication object), the shape of a paste, etc. When Ti is contained in use, it is preferred to use it at a predetermined temperature in consideration of the point etc. which oxidize in the air at the time of heating junction. For example, as the desirable operating mode in the case of a powdered metallic adhesion material, changing into the state where it was filled up with adhesion material powder and the frame thin on substrates, such as metal and ceramics, was first inserted in the adhesion side after Serra 1-Si It was -- subsequently -- inside of non-oxidizing atmosphere, or 10-" -- under the decompression below Torr, time required heating is carried out and it joins to 600-900"C at the basis of the load of 1-100 kg/cm2. Since adhesion material will alloy and the junction effect will fall if it heat-treats on the temperature exceeding 900 degreeC, it is necessary to care about this point. =11 When using it by the shape of a paste, the powder of the charge of adhesion material is distributed in an organic solvent. As an organic solvent, all [ Telepine ], a butyl Carpito rule, butyl Carpitol acetate, etc. can be used, and it is appropriate for the powder volume under paste to consider it as 60~90wt%. They are means, even if a little surface-active agents other than an organic solvent are added and it adds ethyl cellulose etc. as a binder. As the desirable operating mode in the case of using it as insertion material, The shape of a paste is used at one side of the substrate which puts a powder-compacting fabrication object or a powder rolling fabrication object between substrates, and is joined, or is joined, after printing and drying, degreasing processing of the part for a binder is carried out near 600 degreeC under an inactive atmosphere, and the film thickness after degreasing joins at at least 10 micrometers or more. Since junction becomes impossible when degreasing processing is carried out under the high temperature more than 600 degreeC, it minds. In [ any ] the case of a junction mode, as a joining condition, it is 0.5~1. Heating junction is carried out at the temperature of 750~950degreeC, preferably 830~930 degreeC under decompression of 10 to 3 or less Torr, or in inactive Atmosphere 2 mind, applying the load of 0 kg / 0m2. A welding phenomenon arises that heating temperature is the high temperature more than 950 degreeC, and joining becomes insufficient [ below 750 degreeC ]. As a desired value of the thermal expansion coefficient of insertion material, when junction of alumina and copper is considered, alumina is 7. It is 0x10''-G/degreeC and copper is 1. 7 and I X 1 Since it is 0-'/°C, ideally, it is mean value 13x10-'/' C. However, it is not preferred by controlling the thermal expansion coefficient of insertion material that welding temperature becomes high from the remaining stress after junction becoming large. Next, the example of the present invention is shown. (EXAMPLE) While preparing the end of copper powder (average particle diameter of 1.5 micrometers) as the end of precursor powder in titanium sponge (it is part class to -10 micrometers) powder, and the end (average particle diameter of 1.6 micrometers) of silver dust, NiCr alloy (nickel:80% Cr: 20%) powder (average particle diameter of 3.4 micrometers) and Mo fine powder (average particle diameter of 3.8 micrometers) were prepared, and it blended at a rate (wt%) shown in the 1st table. First, mixed pulverization was carried out for 5 hours using the Crush machine, and these were made into the end of composite powder. After mixed pulverization, when average particle diameter was measured by the Fischer Zabu sheave Sizer, it was 1.3 micrometers. When this organization in the end of composite powder was observed, in the matrix of Cu and Ag, Ti, Mo, N]Cr, etc. distributed uniformly and were really which carried out engagement combination mechanically joining together. The following Stomach and this end of mixed pulverized powder were blended at a following rate, and preliminary kneading was carried out for 5 hours using the Crush machine. The object of preliminary kneading is for improving dispersibility by making the powder surface active and making Vehicle contact. The above-mentioned end of mixed pulverized powder 80-weight section ethyl cellulose 1.5 Texanol 16.711 surface-active agents After the 1.8 preliminary cross was completed, this Mixed building was performed using 3 Rolle Mill, and it was considered as the pace 1~-like charge of adhesion material. About a part of end of the - above-mentioned mixture pulverized powder, briquet was used and it was considered as the charge of adhesion material. Next, it is each substrate of 96%AQ203 substrate of the size of about 2 and 5 nv mouth X0.635mmt, an AflN board, and a SiC board as a substrate, All over each one side of the copper plate of 25mm mouth X 0 and the 5 mmt-4 method, 5US304 board, and the partner substrate of 5S34 Without, the screen (200 meshes, bias tension, and emulsion 45 micrometers in thickness) was used, and the above-mentioned paste was printed with the screen printer. It dried for 30 minutes by 120 degreeC after printing, and carried out degreasing processing for 20 minutes in the nitrogen air current by 600 degreeC. Subsequently, in the substrate combination shown in the 1st table, the partner substrate was piled up, and it stuck and joined so that it might become sand inch structure focusing on the above-mentioned substrate under an 850 degreeC11O-5Torr vacuum. The sample of a 10-mm mouth was started with the meek processing machine after junction, and junction intensity was measured. The measuring method of junction intensity set the sample, as shown in Drawing 1, and it measured intensity with the Bush pull tester. It was the partner substrate board which sandwiched one in the substrate among the figure and with which 2 sandwiched substrate 1 to the being [ it / under = ] 15 heart, and these substrates 2 have pasted up by joining layer 3, soldered copper plate 4 to one substrate board 2, soldered Copper beets I~(10mmphi) 5 to substrate board 2 of another side, and measured intensity with the above-mentioned tester. Except for the case where the case where a substrate is not joined at all, and a substrate break, the load at the time of a fracture when it fractures in a bonded surface showed the judgment of junction intensity. The cold heat cycle test was also done. In this examination, equip a cold heat cycle test device with the above-mentioned joined sample as it is, and make maintenance and maintenance during +150-degreeCX 30 minutes into 1 cycle for -55-degreeCX 30 minutes. It checked with the number of cycles until a substrate breaks. The above result is written together to the 1st table. Comparative example Ha 1 which adds neither Mo nor a NiCr alloy so that more clearly than the table, As for comparative example No with few amounts of addition of Mo or a N i Cr alloy, 2~Nn 3, and No 10~N011, once, although secured, there are few cold heat cycles, and junction intensity is Attach] superfluously about Mo or a NiCr alloy.

6 Adding -- comparative example Na9.Nalpha15 has insufficient junction intensity. To these, junction intensity is secured enough, and each example of the present invention has the large number of cold heat cycles, and it turns out that the coefficient of thermal expansion is effectively adjusted also in various kinds of substrate combination. The same result is obtained even if the use modes of adhesion material differ.

[Following space] these basic ingredient systems (Ti -Cu -Ag) -- the following experiments were conducted on the case where an additive (Mo or NiCr alloy) is added in order to improve a thermal expansion coefficient for the improvement in reliability. The 1st experimental method mixes enough the metallic powder of the combination composition shown in the 1st table by a ball mill, After carrying out mechanical alloy processing, compression molding of the sample of 15mmphiX15mmH was carried out by the pressure of 3 ton / cm2, and after sintering 850 degrees for Cx15 minutes under the vacuum of 1.0-" T orr, the thermal expansion coefficient was measured under Ar atmosphere with the Rigaku TTA device. Since an operating condition was limited depending on remaining stress and the environment used after junction and it was not desirable when welding temperature rose rapidly with the additive, the melting point which becomes a standard of welding temperature with a differential thermal analysis system simultaneously was measured as the 2nd license. Measurement of the melting point was measured in Ar atmosphere with the Rigaku DTA device. These experimental results are written together to the 1st table. From the table, when substrates are alumina and copper, while a thermal expansion coefficient is 13 X 10-'/' C in both abbreviation mean value, in the example of the present invention, comparative example No, 1~N [13, No, and 1.0~Na1l. show the value near a copper thermal expansion coefficient. Since the melting point does not become high but adds especially nickel with NjCrIncludingCr type, the thing of the example of the present invention can prevent high-melting-ization. (EFFECT OF THE INVENTION) With," As explained two times in full detail, since the chemical component shall be adjusted by a specific component system and, as for the charge of adhesion material concerning the present invention, a powder form shall include the end of composite powder at least, it has heat resistance, and adhesive strength is high and the adhesive strength outstanding also to especially the cold heat cycle is obtained. It can use not only for junction between metal and the same quality of the material of ceramics but for junction of the contaminant question of metal and ceramics simple.

[Brief Description of the Drawings]

Drawing 1 is a figure explaining the junction intensity measuring method of a joining layer. 1 .. substrate, 2 ... partner substrate board, 3 .. a joining layer and four copper plates 4.5 .. Copper rivet.