JPH0730253A - Method of manufacturing multilayer ceramic board - Google Patents
Method of manufacturing multilayer ceramic boardInfo
- Publication number
- JPH0730253A JPH0730253A JP15467393A JP15467393A JPH0730253A JP H0730253 A JPH0730253 A JP H0730253A JP 15467393 A JP15467393 A JP 15467393A JP 15467393 A JP15467393 A JP 15467393A JP H0730253 A JPH0730253 A JP H0730253A
- Authority
- JP
- Japan
- Prior art keywords
- green sheet
- glass
- ceramic substrate
- multilayer ceramic
- firing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 78
- 238000010304 firing Methods 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 36
- 239000011521 glass Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 26
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- 239000004020 conductor Substances 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 238000009766 low-temperature sintering Methods 0.000 abstract description 6
- 239000000470 constituent Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Ceramic Products (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体ＬＳＩ、チップ部
品などの電子部品を搭載し、かつそれらを相互配線する
ための多層セラミック配線基板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a multilayer ceramic wiring board for mounting electronic components such as semiconductor LSIs and chip components and interconnecting them.
【０００２】[0002]
【従来の技術】近年、低温焼結多層ガラス・セラミック
基板の開発によって、使用できる導体材料に、金、銀、
銅、パラジウムまたはそれらの混合物が用いられるよう
になった。これらの金属は従来使用されたタングステ
ン、モリブデンなどに比べ導体抵抗が低く、かつ使用で
きる設備も安全で低コストに製造できる。2. Description of the Related Art In recent years, with the development of low-temperature sintered multilayer glass / ceramic substrates, usable conductor materials include gold, silver,
Copper, palladium or mixtures thereof have come into use. These metals have lower conductor resistance than conventionally used tungsten, molybdenum, etc., and the equipment that can be used is safe and can be manufactured at low cost.
【０００３】一方これらの金属の内、貴金属である金、
銀、パラジウムは高価で、かつ価格変動が大きいことか
ら、安価で価格変動の少ないＣｕ電極材料の使用が望ま
れている。On the other hand, of these metals, the precious metal gold,
Since silver and palladium are expensive and have large price fluctuations, it is desired to use Cu electrode materials that are inexpensive and have little price fluctuations.
【０００４】ここではそれらの低温焼結多層基板の代表
的な製造方法の一例を述べる。低温焼結多層基板を得る
方法には大きく分けて３種類の方法がある。まず第１に
多層基板の内層電極に銀を用い、低温焼結基板のグリー
ンシートを所望の枚数積層し、空気中で焼成し、その後
最上層に銀、パラジウムペーストを印刷、焼成して低温
焼結多層基板を得る方法である。これは内部にインピー
ダンスの小さい銀を用い、最上層に半田耐熱を有する銀
・パラジウムを使用するものである。第２は、内部の電
極に前者と同様に銀を用い、最上層に銅を用いる方法で
ある。この方法では最上層配線に銅を用いることで、前
者の銀・パラジウムに比べ低いインピーダンス、半田濡
れの点で有効なものが得られる。しかし、最上層に用い
る銅は銀との共晶温度が低いため、６００℃程度の低温
焼成銅ペーストを用いなければならない。その結果、接
着強度、半田濡れの点で課題が多い。最後に第３の方法
として、内層および最上層に銅電極を用いる方法があ
る。この方法によるものは導体抵抗、半田濡れ性、コス
トの点で最も良いがすべて窒素などの中性雰囲気で焼成
しなければならず、その作製が困難である。一般に銅電
極を使用するには、基板上にＣｕペーストをスクリーン
印刷にて配線パターンを形成し、乾燥後、Ｃｕの融点以
下の温度（８５０〜９５０℃程度）で、かつＣｕが酸化
されず導体ペースト中の有機成分が十分燃焼するように
酸素分圧を制御した窒素雰囲気中で焼成を行なうもので
ある。多層する場合は、同様の条件で絶縁層を印刷焼成
して得られる。しかし、焼成工程における雰囲気を適度
な酸素分圧下にコントロールすることは困難であり、ま
た多層化する場合、各ペーストを印刷後その都度焼成を
繰り返し行なう必要があり、リードタイムが長くなり、
設備などのコストアップにつながるなどの課題を有して
いる。そこで特公平３−２０９１４号公報において、多
層セラミック基板の作製にあたり、酸化第二銅ペースト
を用い、脱バインダ工程、還元工程、焼成工程の３段階
とする方法がすでに開示されている。それは酸化第二銅
を導体の出発原料とし多層体を作製し、脱バインダ工程
は、炭素に対して充分な酸素雰囲気で、かつ内部の有機
バインダを熱分解させるに充分な温度で熱処理を行な
う。次に酸化第二銅を銅に還元する還元工程、基板の焼
結を行なう焼成工程により成立しているものである。こ
れにより、焼成時の雰囲気制御が容易になり緻密な焼結
体が得られるようになった。Here, an example of a typical manufacturing method of these low temperature sintered multilayer substrates will be described. There are roughly three types of methods for obtaining a low-temperature sintered multilayer substrate. First of all, silver is used for the inner layer electrodes of the multilayer substrate, a desired number of green sheets of low temperature sintered substrates are laminated and fired in air, and then silver and palladium paste is printed and fired on the uppermost layer to perform low temperature firing. This is a method for obtaining a bonded multilayer substrate. This uses silver with low impedance inside and silver / palladium having solder heat resistance as the uppermost layer. The second is a method in which silver is used for the internal electrodes and copper is used for the uppermost layer as in the former case. In this method, by using copper for the uppermost layer wiring, it is possible to obtain an effective one in terms of lower impedance and solder wetting than the former silver / palladium. However, since the copper used for the uppermost layer has a low eutectic temperature with silver, a low temperature firing copper paste of about 600 ° C. must be used. As a result, there are many problems in terms of adhesive strength and solder wetting. Finally, as a third method, there is a method of using copper electrodes for the inner layer and the uppermost layer. This method is the best in terms of conductor resistance, solder wettability, and cost, but it must be fired in a neutral atmosphere such as nitrogen, and its manufacture is difficult. Generally, in order to use a copper electrode, a wiring pattern is formed by screen-printing a Cu paste on a substrate, and after drying, the temperature is equal to or lower than the melting point of Cu (about 850 to 950 ° C.), and Cu is not oxidized to form a conductor Firing is performed in a nitrogen atmosphere in which the oxygen partial pressure is controlled so that the organic components in the paste are sufficiently burned. In the case of multiple layers, it is obtained by printing and firing the insulating layer under the same conditions. However, it is difficult to control the atmosphere in the firing step under an appropriate oxygen partial pressure, and in the case of multilayering, it is necessary to repeat firing each time after printing each paste, resulting in a long lead time.
There are issues such as increasing the cost of equipment. Therefore, Japanese Patent Publication No. 3-20914 discloses a method of producing a multilayer ceramic substrate by using a cupric oxide paste in three steps of a binder removal step, a reduction step, and a firing step. It uses cupric oxide as a starting material for a conductor to prepare a multilayer body, and in the binder removal step, heat treatment is performed in a sufficient oxygen atmosphere for carbon and at a temperature sufficient to thermally decompose the organic binder inside. Next, the reduction step of reducing cupric oxide to copper and the firing step of sintering the substrate are established. As a result, it became easy to control the atmosphere during firing, and a dense sintered body could be obtained.
【０００５】多層セラミック基板は、焼成時に焼結に伴
う収縮が生じる。この焼結に伴う収縮は、使用する基板
材料、グリーンシート組成、粉体ロットなどにより異な
る。これにより多層セラミック基板の作製においていく
つかの問題が生じている。まず第１に、多層セラミック
基板の作製において前述のように内層配線の焼成を行な
ってから最上層配線の形成を行なうため、基板材料の収
縮誤差が大きいと、最上層配線パターンと寸法誤差のた
め内層電極との接続が行えない。その結果、収縮誤差を
予め許容するように最上層電極部に必要以上の大きい面
積のランドを形成しなければならず、高密度の配線を必
要とする回路には使用できない。また収縮誤差にあわせ
て最上層配線のためのスクリーン版をいくつか用意して
おき、基板の収縮率に応じて使用する方法が取られてい
る。この方法ではスクリーン版が数多く用意しなければ
ならず不経済である。The multilayer ceramic substrate contracts during sintering during firing. The shrinkage due to the sintering depends on the substrate material used, the green sheet composition, the powder lot, and the like. This causes some problems in the production of multilayer ceramic substrates. First of all, in the production of a multilayer ceramic substrate, the inner layer wiring is fired as described above before the uppermost layer wiring is formed. Therefore, if the shrinkage error of the substrate material is large, the uppermost layer wiring pattern and the dimension error may occur. Cannot connect to the inner layer electrode. As a result, a land having an unnecessarily large area must be formed in the uppermost layer electrode portion so as to allow a shrinkage error in advance, and it cannot be used in a circuit that requires high-density wiring. In addition, a method is used in which several screen plates for the uppermost layer wiring are prepared according to the shrinkage error and used according to the shrinkage rate of the substrate. This method is uneconomical because many screen versions must be prepared.
【０００６】一方、最上層配線を内層焼成と同時に行な
えば大きなランドを必要としないが、この同時焼成法に
よっても基板そのものの収縮誤差はそのまま存在するの
で、最後の部品搭載時のクリーム半田印刷において、そ
の誤差のため必要な部分に印刷できない場合が起こる。
また部品実装においても所定の部品位置とズレが生じ
る。On the other hand, if the uppermost layer wiring is performed at the same time as the inner layer firing, a large land is not required, but since the shrinkage error of the substrate itself is still present even by this simultaneous firing method, in the cream solder printing at the time of the last component mounting. However, there may be a case where the necessary part cannot be printed due to the error.
Also, when mounting components, there is a deviation from the predetermined component position.
【０００７】第２にグリーンシート積層法による多層基
板は、グリーンシートの造膜方向によって幅方向と長手
方向によってもその収縮率が異なる。このことも多層セ
ラミック基板の作製の障害となっている。Secondly, the shrinkage rate of the multi-layer substrate formed by the green sheet laminating method is different depending on the film-forming direction of the green sheet depending on the width direction and the longitudinal direction. This is also an obstacle to the production of the multilayer ceramic substrate.
【０００８】これらの収縮誤差をなるべく少なくするた
めには、製造工程において、基板材料およびグリーンシ
ート組成、の管理はもちろん、粉体ロットの違いや積層
条件（プレス圧力、温度）を十分管理する必要がある。
しかし、一般に収縮率の誤差は±０．５％程度存在する
と言われている。In order to reduce these shrinkage errors as much as possible, it is necessary to control not only the substrate material and the green sheet composition but also the difference in powder lot and the laminating conditions (press pressure, temperature) in the manufacturing process. There is.
However, it is generally said that the error of the shrinkage ratio is about ± 0.5%.
【０００９】このことは多層基板にかかわらずセラミッ
ク、およびガラス・セラミックの焼結を伴うものに共通
の課題であり、基板材料の焼結が厚み方向だけ起こり、
平面方向の収縮がゼロの基板が作製できれば上記のよう
な課題が解決でき、工業上極めて有効である。This is a problem common to ceramics and glass-ceramics, regardless of the multilayer substrate, and the sintering of the substrate material occurs only in the thickness direction.
If a substrate with zero shrinkage in the plane direction can be manufactured, the above problems can be solved and it is extremely effective in industry.
【００１０】上記課題を解決するため、ガラス・セラミ
ック低温焼結基板材料に少なくとも有機バインダ、可塑
剤を含むグリーンシートを作製し、導体ペースト組成物
で電極パターンを形成し、前記グリーンシートと別の電
極パターン形成済みの第１のグリーンシートとを所望枚
数積層し、しかる後、前記低温焼結ガラス・セラミック
よりなる第１のグリーンシートの積層体の両面、もしく
は片面に、前記ガラス・セラミック低温焼結基板材料の
焼成温度では焼結しない無機組成物よりなる第２のグリ
ーンシートで挟み込むように積層して積層体を焼成す
る。しかる後、焼結しない無機組成物を取り除くことに
より焼成時の収縮が平面方向で起こらないガラス・セラ
ミック基板を得る製造方法がすでに提案されている。In order to solve the above-mentioned problems, a green sheet containing at least an organic binder and a plasticizer is prepared on a glass / ceramic low-temperature sintered substrate material, an electrode pattern is formed with a conductor paste composition, and another green sheet is prepared. A desired number of the electrode pattern-formed first green sheets are laminated, and then the glass / ceramic low temperature baking is performed on both sides or one side of the laminated body of the first low temperature sintered glass / ceramics. The laminated body is fired by being sandwiched by the second green sheets made of an inorganic composition that is not sintered at the firing temperature of the binder substrate material. Then, a manufacturing method for obtaining a glass-ceramic substrate in which shrinkage during firing does not occur in the planar direction by removing the non-sintering inorganic composition has been already proposed.
【００１１】[0011]
【発明が解決しようとする課題】しかしながら、前記の
焼成時の収縮が平面方向で起こらないガラス・セラミッ
ク基板の製造方法において以下に示すような問題が明ら
かになった。However, the following problems have been clarified in the method of manufacturing a glass-ceramic substrate in which the shrinkage during firing does not occur in the planar direction.
【００１２】ガラス・セラミックよりなる第１のグリー
ンシートの積層体の両面、もしくは片面に焼成温度では
焼結しない無機組成物よりなる第２のグリーンシートを
積層した後、焼成処理を行う際に、前記ガラス・セラミ
ック積層体中の有機バインダの除去が十分行われ難い。
無機組成物の第２のグリーンシートは、ガラス・セラミ
ック基板の平面方向の焼成収縮を抑えるために、ガラス
・セラミックの第１のグリーンシートに比べ、含有する
バインダ量が少なく、より緻密に無機粉体が詰まってい
る。そして、このように無機粉体の詰まった構造体がガ
ラス・セラミックの第１のグリーンシート積層体表面を
覆うため、焼成中、ガラス・セラミックの第１のグリー
ンシート中の有機バインダの燃焼、分解によって発生す
るガスが外に抜け難くなる。焼成中、ガラス・セラミッ
クの第１のグリーンシート中にバインダが残存するとガ
ラス・セラミック基板の焼結が十分進行せず、ガラス・
セラミック基板の強度が低下したり、また残留カーボン
の影響でガラス・セラミック基板に黒いシミが残るなど
の問題が生じる。When a second green sheet made of an inorganic composition that does not sinter at the firing temperature is laminated on both sides or one side of the laminated body of the first green sheet made of glass / ceramic, and then firing treatment is performed, It is difficult to sufficiently remove the organic binder in the glass / ceramic laminate.
The second green sheet of the inorganic composition contains a smaller amount of binder than the first green sheet of the glass / ceramic in order to suppress firing shrinkage in the plane direction of the glass / ceramic substrate, and the inorganic powder is more dense. My body is clogged. Then, since the structure in which the inorganic powder is packed covers the surface of the glass / ceramic first green sheet laminate, the organic binder in the glass / ceramic first green sheet is burned and decomposed during firing. The gas generated by this becomes difficult to escape to the outside. If the binder remains in the first green sheet of glass / ceramic during firing, sintering of the glass / ceramic substrate does not proceed sufficiently,
There are problems that the strength of the ceramic substrate decreases, and that black stains remain on the glass-ceramic substrate due to the effect of residual carbon.
【００１３】本発明は上記課題に鑑み、平面方向の収縮
が無いガラス・セラミック基板の製造において、焼成中
の基板のグリーンシートからのバインダ除去を効果的に
行うことができる多層セラミック基板の製造方法を提供
するものである。In view of the above problems, the present invention is a method for producing a multi-layered ceramic substrate capable of effectively removing the binder from the green sheet of the substrate during firing in the production of a glass-ceramic substrate that does not shrink in the plane direction. Is provided.
【００１４】[0014]
【課題を解決するための手段】本発明は上記課題を解決
するため、ガラス・セラミック低温焼結基板材料に少な
くとも有機バインダ、可塑剤を含む第１のグリーンシー
トを作製し、導体ペースト組成物で電極パターンを形成
し、このグリーンシートを所望枚数積層する。しかる
後、前記ガラス・セラミック低温焼結基板材料の焼成温
度では焼結しない無機組成物と少なくとも有機バイン
ダ、可塑剤を含む第２のグリーンシートを形成し、この
第２のグリーンシートの一部に孔開け加工を施す。さら
に、前記第２のグリーンシートに形成した孔に、前記ガ
ラス・セラミックの第１のグリーンシートに含まれる有
機バインダより分解温度の低い樹脂を充填する。樹脂の
充填は、樹脂を有機溶剤で溶かしペースト状になったも
のを孔に充填し溶剤を乾燥させることにより行われる。
この無機組成物の第２のグリーンシートで前記ガラス・
セラミックの第１のグリーンシートの積層体を挟み込む
ように積層し、前記積層体を焼成する。しかる後、焼結
しない無機組成物を取り除くことにより、十分に焼結し
平面方向での収縮が起こらないガラス・セラミック基板
を作製するものである。In order to solve the above-mentioned problems, the present invention prepares a first green sheet containing at least an organic binder and a plasticizer on a glass / ceramic low-temperature sintered substrate material, and uses a conductor paste composition. An electrode pattern is formed and a desired number of green sheets are laminated. Then, a second green sheet containing an inorganic composition that does not sinter at the firing temperature of the glass-ceramic low temperature sintering substrate material, at least an organic binder and a plasticizer is formed, and a part of the second green sheet is formed. Make a hole. Further, the holes formed in the second green sheet are filled with a resin having a lower decomposition temperature than the organic binder contained in the first glass-ceramic green sheet. The filling of the resin is performed by dissolving the resin in an organic solvent to form a paste, filling the holes, and drying the solvent.
With the second green sheet of this inorganic composition, the glass
The first green sheets of ceramic are laminated so as to sandwich the laminate, and the laminate is fired. Then, the non-sintering inorganic composition is removed to produce a glass-ceramic substrate that is sufficiently sintered and does not shrink in the plane direction.
【００１５】[0015]
【作用】本発明は前記のような工程を行なうことによっ
て、焼成時に厚み方向だけに収縮し、平面方向には収縮
しない多層ガラス・セラミック基板において、焼成中の
ガラス・セラミックの第１のグリーンシートからのバイ
ンダの除去を促進し、焼結性の高い多層セラミック基板
を提供するものである。以下に本発明の作用を説明す
る。According to the present invention, the first green sheet of glass / ceramic during firing is obtained in the multilayer glass / ceramic substrate that shrinks only in the thickness direction during firing and does not shrink in the plane direction by performing the above steps. It is intended to provide a multi-layer ceramic substrate having high sinterability by facilitating the removal of the binder from the. The operation of the present invention will be described below.
【００１６】まず本発明の製造法は、ガラス・セラミッ
ク低温焼結基板材料に少なくとも有機バインダ、可塑剤
を含む第１のグリーンシートを作製し、導体ペースト組
成物で電極パターンとビア電極を形成し、この第１のグ
リーンシートを所望枚数積層して多層化し、前記ガラス
・セラミック低温焼結基板材料の焼成温度では焼結しな
い無機組成物と少なくとも有機バインダ、可塑剤を含む
第２のグリーンシートを形成し、この第２のグリーンシ
ートの一部に孔開け加工を施し、形成した孔に、前記ガ
ラス・セラミックよりなる第１のグリーンシートに含ま
れる有機バインダより分解温度の低い樹脂を充填し、こ
の第２のグリーンシートを前記ガラス・セラミックの第
１のグリーンシートの積層体の両面、もしくは片面に積
層する。これにより、前記積層体を焼成しても、厚み方
向以外は収縮が起こらない。これは、両面もしくは片面
に積層した焼結しない材料で挟み込まれているため、平
面方向の収縮が阻止されるためと考えられる。また、ガ
ラス・セラミックの第１のグリーンシートの積層体に積
層される、焼成温度では焼結しない無機組成物よりなる
第２のグリーンシートには、分解温度の低い樹脂で充填
された孔が形成されているため、焼成中、この樹脂はガ
ラス・セラミックの第１のグリーンシート中のバインダ
の燃焼、分解温度より低温で消失し、残った孔を通して
ガラス・セラミックの第１のグリーンシート中のバイン
ダ分解ガスの抜けが促進される。焼成後、不必要な焼結
しない材料を取り除けば、所望の多層セラミック基板が
得られる訳である。First, according to the manufacturing method of the present invention, a first green sheet containing at least an organic binder and a plasticizer is prepared on a glass / ceramic low temperature sintered substrate material, and an electrode pattern and a via electrode are formed with a conductor paste composition. A desired number of the first green sheets are laminated to form a multilayer, and a second green sheet containing an inorganic composition that does not sinter at the firing temperature of the glass / ceramic low temperature sintering substrate material, an organic binder, and a plasticizer is provided. And forming a hole in a part of the second green sheet, and filling the formed hole with a resin having a decomposition temperature lower than that of the organic binder contained in the first green sheet made of the glass-ceramic, This second green sheet is laminated on both sides or one side of the laminated body of the glass-ceramic first green sheet. Thereby, even if the laminate is fired, no shrinkage occurs except in the thickness direction. It is considered that this is because the material is sandwiched between the non-sintering materials laminated on both sides or one side, so that the contraction in the plane direction is prevented. Further, the second green sheet made of an inorganic composition that does not sinter at the firing temperature, which is laminated on the laminated body of the first glass / ceramic green sheets, has holes filled with a resin having a low decomposition temperature. Therefore, during firing, the resin disappears at a temperature lower than the combustion and decomposition temperature of the binder in the glass-ceramic first green sheet, and the binder in the glass-ceramic first green sheet passes through the remaining holes. The escape of decomposition gas is promoted. After firing, the desired non-sintering material is removed to obtain the desired multilayer ceramic substrate.
【００１７】前記焼成温度では焼結しない無機組成物よ
りなる第２のグリーンシートに加工する孔径は小さすぎ
ると樹脂の充填が十分行えず、好ましくない。反対に加
工孔径が大きい場合には、孔に充填した樹脂が消失した
後、孔開け部のガラス・セラミックの第１のグリーンシ
ートの積層体の平面方向の収縮が十分阻止されず、部分
的に平面方向の収縮が起こるため多層セラミック基板の
反りや変形が生じる。以上の理由より、加工孔径は０．
１〜５ｍｍであれば良く、望ましくは０．２〜２ｍｍの
範囲である。If the pore size of the second green sheet made of an inorganic composition that does not sinter at the firing temperature is too small, the resin cannot be sufficiently filled, which is not preferable. On the contrary, when the processed hole diameter is large, after the resin filled in the holes disappears, the shrinkage in the plane direction of the laminated body of the glass-ceramic first green sheet in the hole-opening portion is not sufficiently prevented, and it is partially Since the shrinkage in the plane direction occurs, the multilayer ceramic substrate warps or deforms. For the above reasons, the processed hole diameter is 0.
It may be 1 to 5 mm, preferably 0.2 to 2 mm.
【００１８】前記ガラス・セラミックの第１のグリーン
シートの積層体の焼成は通常８００℃〜１０００℃の範
囲で行なわれる。銅電極、銀電極を使用する場合は９０
０℃で行なう。Firing of the laminated body of the first green sheet of glass / ceramic is usually performed in the range of 800 ° C to 1000 ° C. 90 when using copper or silver electrodes
Perform at 0 ° C.
【００１９】またガラス・セラミック低温焼結基板材料
の焼成温度では焼結しない無機組成物の第２のグリーン
シートの無機成分には、Ａｌ3 Ｏ3 ，ＭｇＯ，ＺｒＯ
2 ，ＴｉＯ2 ，ＢｅＯ，ＢＮ，の内少なくとも１種以上
を含。９００℃の焼成温度で行なう低温焼結基板材料に
は、Ａｌ3 Ｏ3 が最も有効である。The inorganic component of the second green sheet of the inorganic composition which does not sinter at the firing temperature of the glass / ceramic low temperature sintering substrate material includes Al 3 O 3 , MgO and ZrO.
At least one of 2 , 2 , TiO 2 , BeO, and BN is included. Al 3 O 3 is most effective for the low temperature sintering substrate material which is performed at a firing temperature of 900 ° C.
【００２０】[0020]
【実施例】以下本発明の一実施例について、図面を参照
しながら説明する。図１は本発明の一実施例のグリーン
シート積層体の上面図と断面図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a top view and a sectional view of a green sheet laminate according to an embodiment of the present invention.
【００２１】（実施例１）まず多層セラミック基板作製
方法を説明する。基板材料のガラス・セラミックにはホ
ウ珪酸鉛ガラス粉末にセラミック材料としてのアルミナ
粉末を重量比で５０対５０とした組成物（日本電気硝子
社製 ＭＬＳ−１９）を用いた。このガラス・セラミッ
ク粉を無機成分とし、有機バインダとしてポリビニルブ
チラール、可塑剤としてヂ−ｎ−ブチルフタレート、溶
剤としてトルエンとイソプロピルアルコールの混合液
（３０対７０重量比）を混合しスラリーとした。Example 1 First, a method for producing a multilayer ceramic substrate will be described. A composition (MLS-19 manufactured by Nippon Electric Glass Co., Ltd.) in which lead borosilicate glass powder and alumina powder as a ceramic material were mixed in a weight ratio of 50:50 was used for the glass ceramic of the substrate material. This glass / ceramic powder was used as an inorganic component, polyvinyl butyral as an organic binder, di-n-butyl phthalate as a plasticizer, and a mixed solution of toluene and isopropyl alcohol (30:70 weight ratio) as a solvent to form a slurry.
【００２２】このスラリーをドクターブレード法で有機
フィルム上に厚み約２００μｍの第１のグリーンシート
成形した。このとき、造膜から乾燥、打ち抜き、さらに
は必要に応じてバイアホール加工を行う各工程を連続的
に行うシステムを使用した。この第１のグリーンシート
に銀ペーストを用いて導体パターンの形成およびビアホ
ール埋め印刷をスクリーン印刷法によって行った。導体
ペーストは、Ａｇ粉末（平均粒径１μｍ）に接着強度を
得るためのガラスフリット（日本電気硝子社製ＧＡ−９
ガラス粉末、平均粒径２．５μｍ）を５ｗｔ％加えたも
のを無機成分とし、有機バインダであるエチルセルロー
スをターピネオールに溶かしたビヒクルとともに加え
て、３段ロールにより適度な粘度になるように混合した
ものを用いた。なおビアホール埋め用のＡｇペーストは
更に無機成分として前記ガラス・セラミック粉末を１５
重量％加えたものを使用して行なった。This slurry was formed into a first green sheet having a thickness of about 200 μm on an organic film by the doctor blade method. At this time, a system was used in which the steps of drying, punching, and if necessary, via hole processing were continuously performed from the film formation. A conductive pattern was formed on the first green sheet by using a silver paste and via hole filling printing was performed by a screen printing method. The conductor paste is a glass frit (GA-9 manufactured by Nippon Electric Glass Co., Ltd.) for obtaining adhesive strength to Ag powder (average particle size 1 μm).
5% by weight of glass powder, average particle size 2.5 μm) was added as an inorganic component, and ethyl cellulose, which is an organic binder, was added together with a vehicle in which terpineol was dissolved and mixed by a three-stage roll so as to have an appropriate viscosity. Was used. In addition, the Ag paste for filling the via hole further contains the above glass / ceramic powder as an inorganic component.
It was carried out using the one to which wt% was added.
【００２３】次に、焼結の起こらない第２のグリーンシ
ートは無機成分としてアルミナ（住友化学工業社製 Ａ
ＬＭ−４１ 平均粒径１．９μｍ）粉末のみを用い、前
記ガラス・セラミック基板用の第１のグリーンシートと
同様の組成で、同様の方法で作製した。この第２のグリ
ーンシートの厚みは約３００μｍである。作製した第２
のグリーンシートには孔開け加工を施した。孔開け加工
は、上下左右とも５ｍｍのピッチで第２のグリーンシー
ト全体に施した。加工孔径は、５００μｍであった。加
工孔充填用の樹脂として第１のグリーンシートに用いた
バインダより分解温度が５０℃程度低い、低重合度のポ
リビニルブチラール樹脂を用意し、これをトルエンに溶
解させペースト状にしたものを、メタルマスクを用いた
スクリーン印刷によって前記加工孔に充填、乾燥した。
前記導体形成済みの第１のグリーンシートを所定の枚数
積み重ね、さらにその両面に前記樹脂充填済みの第２の
グリーンシートを重ね合わせる。この状態で熱圧着して
積層体を形成した。熱圧着条件は、温度が８０℃、圧力
は２００Ｋｇ／ｃｍ2 であった。Next, the second green sheet, which does not sinter, is made of alumina (A manufactured by Sumitomo Chemical Co., Ltd.) as an inorganic component.
Only LM-41 powder having an average particle size of 1.9 μm) was used, and the composition was the same as that of the first green sheet for the glass / ceramic substrate, and the same method was used. The thickness of this second green sheet is about 300 μm. The second made
The green sheet of has been perforated. The perforation process was performed on the entire second green sheet at a pitch of 5 mm both vertically and horizontally. The processed hole diameter was 500 μm. As a resin for filling processing holes, a polyvinyl butyral resin having a low polymerization degree and having a decomposition temperature lower than that of the binder used for the first green sheet by about 50 ° C. is prepared, and the resin is melted in toluene to form a paste. The processed holes were filled and dried by screen printing using a mask.
A predetermined number of the conductor-formed first green sheets are stacked, and the resin-filled second green sheets are further stacked on both sides thereof. In this state, thermocompression bonding was performed to form a laminate. The thermocompression bonding conditions were a temperature of 80 ° C. and a pressure of 200 Kg / cm 2 .
【００２４】図１にその構成を示す。１は前記基板材料
による第１のグリーンシート層、２は内層電極層、３は
ビア電極、４はアルミナによる第２のグリーンシート
層、５は第２のグリーンシート層４に施した加工孔に充
填された樹脂、６は９６％アルミナ焼結基板である。FIG. 1 shows the configuration. Reference numeral 1 is a first green sheet layer made of the substrate material, 2 is an inner electrode layer, 3 is a via electrode, 4 is a second green sheet layer made of alumina, and 5 is a processed hole formed in the second green sheet layer 4. The filled resin, 6 is a 96% alumina sintered substrate.
【００２５】次に前記第１，第２のグリーンシート１，
４の積層体を９６％アルミナ焼結基板６上に乗せ焼成す
る。条件はベルト炉によって空気中の９００℃で１時間
焼成で行なった。（９００℃の保持時間は約１２分であ
る。）このとき形成される多層セラミック基板の反りと
厚み方向の焼結収縮を助けるため、アルミナ焼結基板を
乗せて加圧するようにして焼成を行なった。Next, the first and second green sheets 1,
The laminated body of No. 4 is placed on the 96% alumina sintered substrate 6 and fired. The conditions were firing in a belt furnace at 900 ° C. in air for 1 hour. (The holding time at 900 ° C. is about 12 minutes.) In order to assist the warpage of the multilayer ceramic substrate formed at this time and the sintering shrinkage in the thickness direction, the alumina sintered substrate is put on and fired under pressure. It was
【００２６】焼成後の積層体の表面には未焼結のアルミ
ナ層が存在するため、酢酸ブチル溶剤中で超音波洗浄を
行なったところアルミナ層がきれいに取り除くことがで
きた。Since an unsintered alumina layer exists on the surface of the laminated body after firing, the alumina layer could be removed cleanly by ultrasonic cleaning in a butyl acetate solvent.
【００２７】この焼成後の多層セラミック基板は反りも
無く、多層セラミック基板の収縮率は０．１％以下で、
平面方向の収縮が起こっておらず、また多層セラミック
基板上には残留カーボンによるシミも見られず十分焼結
した多層セラミック基板が得られた。 （実施例２）基板材料のガラス・セラミックよりなる第
１のグリーンシートは実施例１と同様の組成の物を用い
た。厚み２００μｍの第１のグリーンシートにビアホー
ルを形成した後、ＣｕＯペーストを用いて導体パターン
の形成およびビアホール埋め印刷をスクリーン印刷法に
よって行った。実施例１では、最上層パターンの形成を
基板焼成後に行なったが、本実施例においては、最上層
パターンも第１のグリーンシート上に印刷した。導体ペ
ーストは、ＣｕＯ粉末（平均粒径３μｍ）に接着強度を
得るためのガラスフリット（日本電気硝子社製 ＬＳ−
０８０３ガラス粉末、平均粒径２．５μｍ）を３ｗｔ％
加えたものを無機成分とし、有機バインダであるエチル
セルロースをターピネオールに溶かしたビヒクルととも
に加えて、３段ロールにより適度な粘度になるように混
合したものを用いた。なおビア埋め用のＣｕＯペースト
は更に無機成分として前記ガラス・セラミック粉末を１
５重量％加えたものを使用して行なった。The fired multilayer ceramic substrate has no warp, and the shrinkage rate of the multilayer ceramic substrate is 0.1% or less.
No shrinkage in the plane direction occurred, and no stain due to residual carbon was observed on the multilayer ceramic substrate, and a fully sintered multilayer ceramic substrate was obtained. (Example 2) The first green sheet made of glass-ceramic as a substrate material had the same composition as in Example 1. After forming a via hole in the first green sheet having a thickness of 200 μm, formation of a conductor pattern using CuO paste and via hole filling printing were performed by a screen printing method. In Example 1, the formation of the uppermost layer pattern was performed after firing the substrate, but in the present Example, the uppermost layer pattern was also printed on the first green sheet. The conductor paste is a glass frit (LS-made by Nippon Electric Glass Co., Ltd.) for obtaining adhesive strength to CuO powder (average particle size 3 μm).
0803 glass powder, average particle size 2.5 μm) 3 wt%
What was added was used as an inorganic component, and an organic binder, ethyl cellulose, was added together with a vehicle in which terpineol was dissolved, and mixed by a three-stage roll so as to have an appropriate viscosity. In addition, the CuO paste for filling vias further contains 1% of the above glass / ceramic powder as an inorganic component.
It was carried out using the one to which 5% by weight was added.
【００２８】次に焼結の起こらない第２のグリーンシー
トは無機成分として酸化ベリリウム（関東化学社製
平均粒径１μｍ）粉末のみを用い前記ガラス・セラミッ
ク基板用の第１のグリーンシートと同様のグリーンシー
ト組成で、同様の方法で作製した。前記酸化ベリリウム
グリーンシートの厚みは約６００μｍである。作製した
酸化ベリリウムグリーンシートには孔開け加工を施し
た。孔開け加工は、上下左右とも１５ｍｍのピッチでグ
リーンシート全体に施した。加工孔径は、１．５ｍｍで
あった。加工孔充填用の樹脂としてグリーンシートに用
いたバインダより分解温度が３０℃程度低い、低重合度
のアクリル系樹脂を用意し、これをメチルエチルケトン
に溶解させペースト状にしたものを、メタルマスクを用
いたスクリーン印刷によって前記加工孔に充填、乾燥し
た。Next, the second green sheet that does not sinter is an inorganic component of beryllium oxide (manufactured by Kanto Chemical Co., Inc.).
An average particle size of 1 μm) was used alone, and a green sheet composition similar to that of the first green sheet for the glass / ceramic substrate was used and prepared in the same manner. The thickness of the beryllium oxide green sheet is about 600 μm. The prepared beryllium oxide green sheet was perforated. The perforation processing was performed on the entire green sheet at a pitch of 15 mm both vertically and horizontally. The processed hole diameter was 1.5 mm. As a resin for filling processing holes, an acrylic resin with a low degree of polymerization, which has a decomposition temperature about 30 ° C lower than the binder used for the green sheet, is prepared by dissolving it in methyl ethyl ketone to form a paste. The processed holes were filled by the screen printing and dried.
【００２９】前記導体形成済みの第１のグリーンシート
を所定の枚数積み重ね、さらにその両面に前記孔開け加
工済み酸化ベリリウムよりなる第２のグリーンシートを
重ね合わせる。この状態で熱圧着して積層体を形成し
た。熱圧着条件は、温度が８０℃、圧力は２００Ｋｇ／
ｃｍ2であった。A predetermined number of the first green sheets on which the conductor has been formed are stacked, and the second green sheets made of the perforated beryllium oxide are stacked on both sides thereof. In this state, thermocompression bonding was performed to form a laminate. The thermocompression bonding conditions are a temperature of 80 ° C. and a pressure of 200 kg /
It was cm2.
【００３０】次に、焼成の工程を説明する。まず最初
は、脱バインダ工程である。発明に使用した第１のグリ
ーンシート、ＣｕＯペーストの有機バインダは、ポリビ
ニルブチラールおよびエチルセルロースである。したが
って空気中での分解温度は、５００℃以上あれば良いの
で、６００℃の温度で前記積層体の脱脂処理を行なっ
た。この工程で、酸化ベリリウムよりなる第２のグリー
ンシートの加工孔に充填した樹脂は第１のグリーンシー
トおよびＣｕＯペースト中の有機バインダの燃焼、分解
が生じるより先に消失するため、第１のグリーンシート
およびＣｕＯペースト中のバインダは、加工孔を通って
速やかに除去される。その後前記積層体を水素ガス１０
０％雰囲気中で２００℃ー５時間で還元した。このとき
のＣｕ層をＸ線回折により分析したところ１００％Ｃｕ
であることを確認した。Next, the firing process will be described. The first is a binder removal step. The organic binders of the first green sheet and CuO paste used in the invention are polyvinyl butyral and ethyl cellulose. Therefore, since the decomposition temperature in air should be 500 ° C. or higher, the degreasing treatment of the laminate was performed at a temperature of 600 ° C. In this step, the resin filled in the processing holes of the second green sheet made of beryllium oxide disappears before the combustion and decomposition of the organic binder in the first green sheet and CuO paste occur, so that the first green sheet disappears. The binder in the sheet and CuO paste is quickly removed through the processed holes. Then, the laminated body is treated with hydrogen gas 10
Reduction was carried out at 200 ° C. for 5 hours in a 0% atmosphere. When the Cu layer at this time was analyzed by X-ray diffraction, 100% Cu
Was confirmed.
【００３１】次に焼成工程は、純窒素中９００℃である
メッシュベルト炉で焼成した。以上のようにして作製し
た積層体の表面の酸化ベリリウム層を実施例１と同様に
超音波洗浄にて取り除き、形成された多層セラミック基
板の収縮率を評価したところ、多層セラミック基板の収
縮率は０．０５％以下であり、また反りも無い十分焼結
した多層セラミック基板が得られた。Next, in the firing step, firing was performed in pure nitrogen in a mesh belt furnace at 900 ° C. The beryllium oxide layer on the surface of the laminate produced as described above was removed by ultrasonic cleaning in the same manner as in Example 1, and the shrinkage rate of the formed multilayer ceramic substrate was evaluated. A fully sintered multilayer ceramic substrate having a content of 0.05% or less and no warp was obtained.
【００３２】本実施例では、最上層パターンとしてＣｕ
Ｏペーストを第１のグリーンシート上に印刷し、同時焼
成してＣｕの最上層パターンを得たが、これは実施例１
で示したように、ビア電極位置に酸化ベリリウムよりな
る第２のグリーンシートの孔開け加工を施し、焼成、酸
化ベリリウム除去後、Ｃｕペーストを印刷、焼成してＣ
ｕの最上層パターンの形成を行なってもよいことは云う
までもない。In this embodiment, Cu is used as the uppermost layer pattern.
The O paste was printed on the first green sheet and co-fired to obtain a Cu top layer pattern.
As shown in, the second green sheet made of beryllium oxide is perforated at the position of the via electrode, and after firing and removing beryllium oxide, a Cu paste is printed and fired to remove C.
It goes without saying that the uppermost layer pattern of u may be formed.
【００３３】なお本実施例において、未焼結材料として
Ａｌ2 Ｏ3 およびＢｅＯを用いたが、その他ＭｇＯ，Ｚ
ｒＯ2 ，ＴｉＯ2 ，ＢＮを用いても同様の効果が得られ
た。In this example, Al 2 O 3 and BeO were used as the unsintered materials, but other MgO, Z
The same effect was obtained using rO 2 , TiO 2 , and BN.
【００３４】[0034]
【発明の効果】本発明は前記のような工程を行なうこと
によって、焼成時において厚み方向だけ収縮し、平面方
向には収縮しない多層セラミック基板において、焼成時
のグリーンシート中のバインダ除去を促進し、十分に焼
結した多層セラミック基板が歩留まり良く得られる。According to the present invention, by performing the above steps, in a multilayer ceramic substrate that shrinks only in the thickness direction and does not shrink in the planar direction during firing, it promotes the removal of the binder in the green sheet during firing. A sufficiently sintered multilayer ceramic substrate can be obtained with a high yield.
【図１】（ａ）は本発明の一実施例のグリーンシート積
層体の構成を示す図 （ｂ）は同断面図FIG. 1A is a diagram showing a configuration of a green sheet laminate according to an embodiment of the present invention, and FIG. 1B is a sectional view of the same.
１ ・・・ ガラス・セラミックよりなる第１のグリー
ンシート層 ２ ・・・ 内部電極層 ３ ・・・ ビア電極 ４ ・・・ アルミナよりなる第２のグリーンシート層 ５ ・・・ アルミナよりなる第２のグリーンシートに
施した加工孔に充填した樹脂 ６ ・・・ ９６％アルミナ焼結基板1 ... First green sheet layer made of glass / ceramic 2 ... Internal electrode layer 3 ... Via electrode 4 ... Second green sheet layer made of alumina 5 ... Second made of alumina Filled in the processed holes made in the green sheet of No.6: 96% alumina sintered substrate
Claims (14)
成した少なくとも有機バインダ、可塑剤を含むガラス・
セラミックよりなる第１のグリーンシートを所望枚数積
層した後、前記ガラス・セラミックの焼成温度では焼結
しない無機組成物と少なくとも有機バインダ、可塑剤を
含む第２のグリーンシートに孔開け加工を行い、前記加
工孔に前記ガラスセラミックの第１のグリーンシートに
含まれる有機バインダより分解温度の低い樹脂を充填
し、その後、前記無機組成物の第２のグリーンシート
を、前記ガラス・セラミックの第１のグリーンシート積
層体の両面、もしくは片面に積層した後、焼成処理を行
い、その後前記焼結しない無機組成物を取り除くことを
特徴とする多層セラミック基板の製造方法。1. A glass containing at least an organic binder having an electrode pattern formed of a conductor paste composition and a plasticizer.
After laminating a desired number of first ceramic green sheets, a second green sheet containing an inorganic composition that does not sinter at the glass-ceramic firing temperature, at least an organic binder, and a plasticizer is perforated. The processed hole is filled with a resin having a decomposition temperature lower than that of the organic binder contained in the first glass-ceramic green sheet, and then the second green sheet of the inorganic composition is filled with the first green sheet of the glass-ceramic. A method for producing a multilayer ceramic substrate, comprising laminating on both sides or one side of a green sheet laminate, followed by firing treatment, and then removing the non-sintered inorganic composition.
なる第２のグリーンシートに加工する孔径が０．１〜５
ｍｍであることを特徴とする請求項１に記載の多層セラ
ミック基板の製造方法。2. The second green sheet made of an inorganic composition that does not sinter at the firing temperature has a pore size of 0.1 to 5
The method according to claim 1, wherein the multilayer ceramic substrate has a thickness of mm.
で行なうことを特徴とする請求項１に記載の多層セラミ
ック基板の製造方法。3. The method for producing a multilayer ceramic substrate according to claim 1, wherein the firing temperature is 800 ° C. to 1000 ° C.
る第２のグリーンシートが、Ａｌ2 Ｏ3 ，ＭｇＯ，Ｚｒ
Ｏ2 ，ＴｉＯ2 ，ＢｅＯ，ＢＮ，の内少なくとも１種以
上を含むグリーンシートからなることを特徴とする請求
項１に記載の多層セラミック基板の製造方法。4. The second green sheet made of an inorganic composition that does not sinter in the firing treatment is Al 2 O 3 , MgO, Zr.
The method for producing a multilayer ceramic substrate according to claim 1, wherein the green sheet comprises at least one of O 2 , TiO 2 , BeO, and BN.
波洗浄法で取り除くことを特徴とする請求項１に記載の
多層セラミック基板の製造方法。5. The method for producing a multilayer ceramic substrate according to claim 1, wherein the inorganic composition that does not sinter in the firing treatment is removed by an ultrasonic cleaning method.
／Ｐｔ，Ｃｕのいずれかを主成分とすることを特徴とす
る請求項１に記載の多層セラミック基板の製造方法。6. The conductive paste is Ag, Ag / Pd, Ag
2. The method for producing a multilayer ceramic substrate according to claim 1, wherein one of / Pt and Cu is a main component.
圧して焼成を行なうことを特徴とする請求項１に記載の
多層セラミック基板の製造方法。7. The method for producing a multi-layer ceramic substrate according to claim 1, wherein the green sheet laminate is pressurized and fired during the firing treatment.
組成物で電極パターンを形成した少なくとも有機バイン
ダ、可塑剤を含むガラス・セラミックよりなる第１のグ
リーンシートを所望枚数積層した後、前記ガラス・セラ
ミックの焼成温度では焼結しない無機組成物と少なくと
も有機バインダ、可塑剤を含む第２のグリーンシートに
孔開け加工を行い、前記加工孔に前記ガラス・セラミッ
クの第１のグリーンシートに含まれる有機バインダより
分解温度の低い樹脂を充填し、その後、前記無機組成物
の第２のグリーンシートを、前記ガラス・セラミックよ
りなる第１のグリーンシート積層体の両面、もしくは片
面に積層した後、これらを空気中で多層体内部の有機バ
インダが分解・飛散する温度で熱処理し、しかる後、水
素もしくは水素と窒素の混合ガス雰囲気中で還元熱処理
を行い、さらに、前記還元熱処理済み多層体を窒素雰囲
気中で焼結させ、しかる後、焼結しない無機組成物を取
り除くことを特徴とする多層セラミック基板の製造方
法。8. A desired number of first green sheets made of glass-ceramic containing at least an organic binder and a plasticizer in which an electrode pattern is formed of a conductor paste composition containing cupric oxide as a main component are laminated, and then, A second green sheet containing an inorganic composition that does not sinter at the firing temperature of the glass / ceramic, at least an organic binder, and a plasticizer is perforated, and the processed hole is included in the first green sheet of the glass / ceramic. A resin having a lower decomposition temperature than that of the organic binder, and then a second green sheet of the inorganic composition is laminated on both sides or one side of the first green sheet laminate made of the glass-ceramic, These are heat-treated in air at a temperature at which the organic binder inside the multilayer decomposes and scatters, and then hydrogen or hydrogen and nitrogen is mixed. Production of a multilayer ceramic substrate characterized by performing reduction heat treatment in a mixed gas atmosphere of oxygen, further sintering the reduction heat-treated multilayer body in a nitrogen atmosphere, and then removing an inorganic composition that does not sinter. Method.
なる第２のグリーンシートに加工する孔径が０．１〜５
ｍｍであることを特徴とする請求項８に記載の多層セラ
ミック基板の製造方法。9. The second green sheet made of an inorganic composition that does not sinter at the firing temperature has a pore size of 0.1 to 5 to be processed.
The method for manufacturing a multilayer ceramic substrate according to claim 8, wherein the thickness is mm.
り除いた後、さらに最上層部にＣｕペーストで配線パタ
ーンを形成し、窒素雰囲気中で焼成することを特徴とす
る請求項８記載の多層セラミック基板の製造方法。10. The multilayer structure according to claim 8, wherein after the inorganic composition which is not sintered in the firing process is removed, a wiring pattern is further formed on the uppermost layer portion with a Cu paste and the wiring pattern is fired in a nitrogen atmosphere. Ceramic substrate manufacturing method.
囲で行なうことを特徴とする請求項８に記載の多層セラ
ミック基板の製造方法。11. The method for manufacturing a multilayer ceramic substrate according to claim 8, wherein the firing treatment is performed in the range of 800 ° C. to 1000 ° C.
第２のグリーンシートが、Ａｌ2 Ｏ3 ，ＭｇＯ，ＺｒＯ
2 ，ＴｉＯ2 ，ＢｅＯ，ＢＮ，の内少なくとも１種以上
を含むグリーンシートからなることを特徴とする請求項
８に記載の多層セラミック基板の製造方法。12. The second green sheet of an inorganic composition which does not sinter in the firing treatment comprises Al 2 O 3 , MgO, ZrO.
9. The method for producing a multilayer ceramic substrate according to claim 8, wherein the green sheet comprises at least one of 2 , 2 , TiO 2 , BeO, and BN.
音波洗浄法で取り除くことを特徴とする請求項８に記載
の多層セラミック基板の製造方法。13. The method for producing a multilayer ceramic substrate according to claim 8, wherein the inorganic composition that does not sinter in the firing treatment is removed by an ultrasonic cleaning method.
加圧して焼成を行なうことを特徴とする請求項８に記載
の多層セラミック基板の製造方法。14. The method for producing a multilayer ceramic substrate according to claim 8, wherein the green sheet laminate is pressed during the baking process to be baked.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15467393A JPH0730253A (en) | 1993-06-25 | 1993-06-25 | Method of manufacturing multilayer ceramic board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15467393A JPH0730253A (en) | 1993-06-25 | 1993-06-25 | Method of manufacturing multilayer ceramic board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0730253A true JPH0730253A (en) | 1995-01-31 |
Family
ID=15589408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15467393A Pending JPH0730253A (en) | 1993-06-25 | 1993-06-25 | Method of manufacturing multilayer ceramic board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730253A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003008217A (en) * | 2001-06-27 | 2003-01-10 | Sumitomo Metal Electronics Devices Inc | Method of manufacturing low-temperature baking ceramic board having cavity |
| KR100673537B1 (en) * | 1999-12-10 | 2007-01-24 | 고등기술연구원연구조합 | Low-temperature co-fired ceramic substrate on metal and its manufacturing method |
| US7381283B2 (en) | 2002-03-07 | 2008-06-03 | Yageo Corporation | Method for reducing shrinkage during sintering low-temperature-cofired ceramics |
| JP2009135500A (en) * | 2007-11-29 | 2009-06-18 | Samsung Electro Mech Co Ltd | Constraining green sheet and manufacturing method of multi-layer ceramic substrate using the same |
| WO2009119198A1 (en) * | 2008-03-25 | 2009-10-01 | 株式会社村田製作所 | Process for producing ceramic substrate |
| US7951446B2 (en) | 2007-11-06 | 2011-05-31 | Samsung Electro-Mechanics Co., Ltd. | Constraining green sheet and manufacturing method of multi-layer ceramic substrate |
| US8178193B2 (en) | 2007-10-29 | 2012-05-15 | Samsung Electro-Mechanics Co., Ltd. | Constraining green sheet and method of manufacturing multi-layer ceramic substrate using the same |
-
1993
- 1993-06-25 JP JP15467393A patent/JPH0730253A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100673537B1 (en) * | 1999-12-10 | 2007-01-24 | 고등기술연구원연구조합 | Low-temperature co-fired ceramic substrate on metal and its manufacturing method |
| JP2003008217A (en) * | 2001-06-27 | 2003-01-10 | Sumitomo Metal Electronics Devices Inc | Method of manufacturing low-temperature baking ceramic board having cavity |
| US7381283B2 (en) | 2002-03-07 | 2008-06-03 | Yageo Corporation | Method for reducing shrinkage during sintering low-temperature-cofired ceramics |
| US8178193B2 (en) | 2007-10-29 | 2012-05-15 | Samsung Electro-Mechanics Co., Ltd. | Constraining green sheet and method of manufacturing multi-layer ceramic substrate using the same |
| US7951446B2 (en) | 2007-11-06 | 2011-05-31 | Samsung Electro-Mechanics Co., Ltd. | Constraining green sheet and manufacturing method of multi-layer ceramic substrate |
| JP2009135500A (en) * | 2007-11-29 | 2009-06-18 | Samsung Electro Mech Co Ltd | Constraining green sheet and manufacturing method of multi-layer ceramic substrate using the same |
| US7887905B2 (en) | 2007-11-29 | 2011-02-15 | Samsung Electro-Mechanics Co., Ltd. | Constraining green sheet and manufacturing method of multi-layer ceramic substrate using the same |
| WO2009119198A1 (en) * | 2008-03-25 | 2009-10-01 | 株式会社村田製作所 | Process for producing ceramic substrate |
| US8123882B2 (en) | 2008-03-25 | 2012-02-28 | Murata Manufacturing Co., Ltd. | Process for producing ceramic substrate |
| JP5229316B2 (en) * | 2008-03-25 | 2013-07-03 | 株式会社村田製作所 | Manufacturing method of ceramic substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0179404B1 (en) | Ceramic substrate and its manufacturing method | |
| JP2785544B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| US5370759A (en) | Method for producing multilayered ceramic substrate | |
| JP3351043B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JP3003413B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JPH05327218A (en) | Manufacture of multilayer ceramic base | |
| JPH0730253A (en) | Method of manufacturing multilayer ceramic board | |
| JPH06237081A (en) | Manufacture of multilayer ceramic substrate | |
| JPH05213679A (en) | Interface area between metal and ceramics in metal/ceramic substrate and formation method thereof | |
| JP3387189B2 (en) | Ceramic substrate and its manufacturing method | |
| JP3082475B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JP2803414B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JP2803421B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JP3100796B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JPH06223621A (en) | Conductor paste composition | |
| JPH11224984A (en) | Production of ceramic multilayered substrate | |
| JPH05327220A (en) | Manufacture of multilayer ceramic base | |
| JP2812605B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JP2855959B2 (en) | Method for manufacturing multilayer ceramic substrate | |
| JP3112258B2 (en) | Circuit board and its manufacturing method | |
| JP2003095755A (en) | Method of manufacturing ceramic circuit board by firing ceramic at low temperature | |
| JP3188086B2 (en) | Ceramic wiring board, its manufacturing method and its mounting structure | |
| JPH0786739A (en) | Manufacture of multilayer ceramic board | |
| JPH05343851A (en) | Manufacture of multilayer ceramic substrate | |
| JPS62145896A (en) | Manufacture of ceramic copper multilayer wiring board |