JP4369672B2 - Manufacturing method of glass ceramic substrate - Google Patents

Description

【０１３８】
表１に示す結果から、実施例４〜７の各拘束グリーンシートを使用して得られたガラスセラミック基板は、焼成時の収縮および反りが抑制され、高い寸法精度を有していることが分かる。
【０１３９】
＜実施例８＞
導体ペーストに銅粉末の代わりに銀−パラジウムペーストを用いて、導体パターンをスクリーン印刷にて形成した。導体ペーストとしては、Ａｇ：Ｐｄが質量比で85：15である合金粉末（平均粒径1.0μｍ）100質量部に対して、Ａｌ₂Ｏ₃粉末２質量部および前記ガラスと同組成のガラス粉末２質量部、さらにビヒクル成分として、所定量のエチルセルロース系樹脂，テルピネオールを加え３本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。
【０１４０】
また、焼成用積層体としては、導体ペースト以外は、実施例１と同様の条件で加工を行なった。
【０１４１】
これをマイクロ波によって自己発熱するアルミナ系材料の内殻に載置し、2.45ＧＨｚのマイクロ波を照射し大気中400℃で２時間加熱して有機成分を除去した後、850℃で１時間焼成した以外は実施例４と同様にしてガラスセラミック基板を得た。
【０１４２】
また、炭化珪素系材料で作製した筐体を使用し、焼成雰囲気ガスとしては大気中で焼成を行なった。
【０１４３】
また、実施例４と同様に積層面内での収縮が0.5％以下（すなわち、収縮率99.5％以上）であり、セラミック成形体中に金属粉体が酸化、拡散はなく製品の絶縁性劣化はなく基板に反りや変形は認められなかった。
【０１４４】
＜実施例９＞
拘束グリーンシートの無機成分としてＡｌ₂Ｏ₃粉末95質量％の代わりにマイクロ波に対する誘電正接がより大きいＳｉＣ粉末95質量％を用いた以外は実施例１と同様にしてガラスセラミック基板を得た。
【０１４５】
得られたガラスセラミック基板は実施例１と同様に、積層面内での収縮は0.5％以下であり、基板に反りや変形も認められない良好なものであり、さらに実施例１のガラスセラミック基板に比較して収縮ばらつきがより小さく、一層良好なものであった。
【０１４６】
＜実施例10〜13＞
焼成雰囲気ガスの供給量を１分間あたり筐体の容積の１倍，５倍，10倍，15倍の体積の量とした以外は、実施例１と同様にしてガラスセラミック基板20個を得た。
【０１４７】
得られたガラスセラミック基板は、実施例１と同様に積層面内での焼成収縮のばらつきは0.1％以下であり、基板に反りや変形も認められない良好なものであった。
【０１４８】
＜実施例14〜16＞
ガラスセラミック・グリーンシートの引張り伸度を10％，30％，40％とした以外は、実施例１と同様にしてガラスセラミック基板20個を得た。
【０１４９】
得られたガラスセラミック基板は、実施例１と同様に積層面内での焼成収縮のばらつきは0.1％以下であり、基板に割れ・クラック・反り・変形も認められない良好なものであった。
【０１５０】
＜比較例５＞
焼成雰囲気ガスの供給量を１分間あたり筐体の容積の0.5倍の体積の量とした以外は、実施例１と同様にしてガラスセラミック基板20個を得た。
【０１５１】
＜比較例６＞
焼成雰囲気ガスの供給量を１分間あたり筐体の容積の17倍の体積の量とした以外は実施例１と同様にしてガラスセラミック基板20個を得た。
【０１５２】
その結果、焼成雰囲気ガスの供給量を１分間あたり筐体の容積の0.5倍の体積の量とした比較例５で得たガラスセラミック基板は、焼成雰囲気ガスの供給量が十分に均一な雰囲気を形成するのに必要な量より少なくなることから、焼成収縮のばらつきが0.2％となり問題ない範囲内ではあったが、若干劣化する傾向にあった。
【０１５３】
また、焼成雰囲気ガスの供給量を１分間あたり筐体の容積の17倍の体積の量とした比較例６で得たガラスセラミック基板は、拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層体の近傍において局部的に温度が低くなり所望の温度範囲で一定な状態とすることが困難となることから、焼成収縮のばらつきが0.15％となり問題ない範囲内ではあったが、若干劣化する傾向にあった。
【０１５４】
＜実施例17＞
ガラスセラミック・グリーンシートの引張り伸度を８％とした以外は、実施例１と同様にしてガラスセラミック基板20個を得た。
【０１５５】
＜実施例18＞
ガラスセラミック・グリーンシートの引張り伸度を42％とした以外は、実施例１と同様にしてガラスセラミック基板20個を得た。
【０１５６】
その結果、ガラスセラミック・グリーンシートの引張り伸度を８％とした実施例17で得たガラスセラミック基板は、積層面内での焼成収縮のばらつきは0.1％以下であったが、ガラスセラミック・グリーンシートが硬くなりすぎる傾向にあるため、微細な割れやクラックが発生する傾向にあった。
【０１５７】
また、ガラスセラミック・グリーンシートの引張り伸度を42％とした実施例18で得たガラスセラミック基板は、積層圧力や温度によりガラスセラミック・グリーンシートが塑性変形を生じ易いものとなり焼成収縮のばらつきが0.15％となり問題ない範囲内ではあったが、若干劣化する傾向にあった。
【０１５８】
＜試験例１＞
（拘束グリーンシートの収縮試験）
無機成分としてＡｌ₂Ｏ₃粉末と軟化点720℃のＳｉＯ₂−ＭｇＯ−ＣａＯ−Ａｌ₂Ｏ₃系ガラス粉末とをそれぞれ所定の割合で使用し、さらに有機バインダとしてアクリル樹脂9.0質量部，フタル酸系可塑剤4.5質量部および溶剤としてトルエン30質量部を加え、これらをボールミルにて混合しスラリーとした。このスラリーをドクターブレード法により厚さ250μｍの拘束グリーンシートを成形した。
【０１５９】
この拘束グリーンシートを単独でアルミナセッターに載置し、大気中500℃で２時間加熱して有機成分を除去した後、850℃で１時間焼成した。
【０１６０】
得られた拘束シートの平面内での収縮率とガラス添加量との関係を図２に示す。なお、収縮率は拘束シートの厚さ方向を除く幅方向および流れ方向の各収縮率の平均値（ｎ＝５）とばらつきを示しており、式：（焼成後寸法）×100／（焼成前寸法）にて求めたものである。また、流れ方向はグリーンシートの造膜方向を、幅方向は造膜方向に直交する方向をそれぞれ意味する。
【０１６１】
図２に示すように、収縮率を99.5％以上とする、すなわち拘束シートの収縮を0.5％以下に抑えるには、拘束グリーンシート内へのガラス添加量は約15質量％以下とするのが望ましいことがわかる。また、ガラス添加量が15質量％を超えると、収縮率のばらつきも大きくなる傾向にある。ただし、ガラス添加量が少なくなると、拘束グリーンシートによるガラスセラミック・グリーンシートの拘束性が低下するので（前記の比較例１を参照）、拘束性が低下しないガラス添加量を決定する必要があり、本発明では0.5〜15質量％を好適範囲としている。
【０１６２】
＜試験例２＞
ガラスとしてＳｉＯ₂−Ａｌ₂Ｏ₃−ＭｇＯ−Ｂ₂Ｏ₃−ＺｎＯ系ガラス粉末を用いた以外は試験例１と同様にして、ガラス添加量と収縮率との関係を調べたところ、ガラス添加量が15質量％以下では拘束グリーンシートの収縮率は99.5％以上であり、ガラス添加量が10質量％以下では約99.8％程度を維持していた。
【０１６３】
【発明の効果】
本発明のガラスセラミック基板の製造方法によれば、拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層体をマイクロ波吸収性の筐体で囲うとともにこの筐体を通して積層体にマイクロ波を照射することにより、有機成分を除去するとともに焼成することによって、拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層体の内部と表面との温度差を効果的に抑えて焼成することが可能となることから、積層体の焼成収縮のばらつきを極めて小さなものに抑制することができ、寸法精度の高い高信頼性のガラスセラミック基板を得ることができる。
【０１６４】
これは、積層体を囲うマイクロ波吸収性の筐体に吸収されて発生した熱が積層体の表面を加熱することとなり、その結果、表面からの熱放散によって内部に比べて温度が低くなりがちな積層体の表面と、積層体の内部との温度勾配を効果的に極めて小さなものに効果的に抑制することができるからである。
【０１６５】
また、本発明のガラスセラミック基板の製造方法によれば、拘束グリーンシートの難焼結性無機材料のマイクロ波に対する誘電正接がガラスセラミック・グリーンシート積層体よりも大きいものとしたときには、マイクロ波による拘束グリーンシートの発熱がガラスセラミック・グリーンシート積層体の発熱より大きくなることにより、表面からの熱放散によって内部に比べて温度が低くなりがちな積層体の表面と、積層体の内部との温度勾配をより一層効果的に極めて小さなものに抑制することができることから、積層体の焼成収縮のばらつきを極めて小さなものに抑制することができ、寸法精度の高い高信頼性のガラスセラミック基板を得ることができる。
【０１６６】
さらに、本発明のガラスセラミック基板の製造方法によれば、筐体中に焼成雰囲気ガスを１分間当たり前記筺体の容積の１倍乃至15倍の体積の量で供給するようにしたときには、焼成雰囲気用ガスが例えば直方体状の筐体の開口部からこの筐体内に供給され、この筐体内の焼成雰囲気用ガス中に対して、拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層体が熱分解や解重合反応して発生した分解ガスが筐体内において滞留することなく連続的に対向する側面の開口部から排気されることとなり、濃度が均一な焼成雰囲気ガスの下で拘束グリーンシートとガラスセラミック・グリーンシート積層体を焼成することができることから、積層体の焼成収縮のばらつきを極めて小さなものに抑制することができ、寸法精度の高い高信頼性のガラスセラミック基板を得ることができる。
【０１６７】
さらに、本発明のガラスセラミック基板の製造方法によれば、拘束グリーンシート中に含有されるガラスの軟化点が、ガラスセラミック・グリーンシート積層体の焼成温度以下であるときには、ガラスセラミック・グリーンシート積層体の焼成が開始する前に拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層界面近傍においてガラス同士が加熱により溶着するようになることから、積層体の面内方向であるＸ−Ｙ方向には実質的に収縮させない焼成をより確実に行なうことが可能となり、ガラスセラミック・グリーンシート積層体を焼成して得られるガラスセラミック基板の寸法ばらつきを効果的に抑えることが可能となる。以上により、焼成途中で拘束グリーンシートのガラスセラミック・グリーンシート積層体からの剥離を効果的に抑えることが可能となるため、ガラスセラミック・グリーンシート積層体のＸ−Ｙ方向における焼結収縮を防止でき、ガラスセラミック基板の変形を抑えることが可能となる。
【０１６８】
さらに、本発明のガラスセラミック基板の製造方法によれば、拘束グリーンシート中に含有されるガラスの軟化点が、有機成分の揮発温度よりも高いものとしたときには、ガラスが軟化する前にガラスセラミック・グリーンシート積層体中の有機成分が揮発することによりガラスセラミック中に取り込まれることがなくなる。その結果、有機成分のガラスセラミック・グリーンシート積層体中における残存を効果的に防ぐことが可能となることから、有機成分の影響を受けることなく焼成ができることにより収縮ムラを防止すると同時に、ガラスセラミック基板の反り，変形等を効果的に抑えることが可能となる。
【０１６９】
さらに、本発明のガラスセラミック基板の製造方法によれば、拘束グリーンシート中のガラス含有量が、この拘束グリーンシート中の全無機成分の0.5〜15質量％であるものとしたときには、拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層界面近傍におけるガラス同士が熱により溶着することによりガラスセラミック・グリーンシートの積層面内での焼結収縮を確実に拘束することが可能となる。これにより、焼成途中における拘束グリーンシートの剥離を効果的に防ぐことが可能となり、ガラスセラミック・グリーンシート積層体の焼結収縮を抑えることができる。その結果、ガラスセラミック基板の反り，変形等の発生を効果的に防ぐことが可能となることから、ガラスセラミック・グリーンシート積層体の収縮を確実に抑えることができ、寸法精度の高いガラスセラミック基板を得ることができる。
【０１７０】
さらに、本発明のガラスセラミック基板の製造方法によれば、拘束グリーンシートの厚さが片面でガラスセラミック・グリーンシート積層体の厚さに対して10％以上であるものとしたときには、ガラスセラミック・グリーンシートの積層面内で焼結収縮が開始する際に、ガラスセラミック・グリーンシート積層体がＸ−Ｙ方向への焼成焼成収縮しようとする駆動力を拘束グリーンシートで効果的に抑えることが可能となる。その結果、ガラスセラミック基板の反り，変形等の発生を効果的に防ぐことが可能となることからガラスセラミック・グリーンシート積層体の収縮を確実に抑えることが可能となり、寸法精度の高いガラスセラミック基板を得ることができる。
【０１７１】
本発明のガラスセラミック基板の製造方法によれば、ガラスセラミック・グリーンシートの引張り伸度が10乃至40％であるときには、ガラスセラミック・グリーンシートが積層圧力や温度による塑性変形を起こし難くなって一時的に伸びても元の位置に復元可能な弾性体として機能するため、積層時のガラスセラミック・グリーンシートの変形のばらつきを効果的に抑えることが可能となる。また、ガラスセラミック・グリーンシートが適度に軟らかいため、ガラスセラミック・グリーンシートに割れやクラックが発生するのを効果的に防ぐことが可能となる。その結果、より一層寸法精度に優れた配線導体を有するガラスセラミック基板を作製することができる。
【０１７２】
以上により、本発明のガラスセラミック基板の製造方法によれば、ガラスセラミック・グリーンシート積層体の積層面内での焼結収縮を確実に拘束して、さらに、ガラスセラミック成形体中の金属粉体が酸化熱膨張することにより製品の内部構造における欠陥や金属粉体が酸化し、かつ拡散することによる製品の絶縁性劣化を効果的に抑え、かつ寸法精度の高い高信頼性のガラスセラミック基板を得る方法を提供することが可能となる。
【図面の簡単な説明】
【図１】（ａ）は本発明のガラスセラミック基板の製造方法の実施の形態の一例を示す平面図であり、本発明のガラスセラミック基板の製造方法において使用するマイクロ波照射焼成炉の平面図を示している。（ｂ）はそのＡ−Ａ’線断面図、（ｃ）はそのＢ−Ｂ’線断面図である。
【図２】本発明の実験例を示し、拘束シートの平面内での収縮率とガラス添加量との関係を示す線図である。
【符号の説明】
１・・・拘束グリーンシートとガラスセラミック・グリーンシート積層体との積層体
２・・・筐体
10・・・焼成雰囲気ガス[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a multilayer glass ceramic substrate for mounting semiconductor LSIs, chip parts, and the like and interconnecting them.
[0002]
[Prior art]
In recent years, semiconductor LSIs, chip parts, and the like have been reduced in size and weight, and a wiring board on which these are mounted is also desired to be reduced in size and weight. In response to such demands, multilayer ceramic substrates with internal electrodes and the like arranged in the substrate are required in today's electronics industry because they enable the required high-density wiring and can be made thinner. Yes.
[0003]
As a multilayer ceramic substrate, an insulating substrate made of an alumina sintered body and having a wiring layer made of a refractory metal such as tungsten or molybdenum formed on the surface or inside thereof has been widely used.
[0004]
On the other hand, with the recent advanced information age, the frequency band used is increasingly shifting to the high frequency band. In a high-frequency wiring board that transmits such a high-frequency signal, the resistance of the conductor forming the wiring layer is required to be small in order to transmit the high-frequency signal at high speed, and the insulating substrate also has a lower dielectric constant. Required.
[0005]
However, conventional refractory metals such as tungsten and molybdenum have high conductor resistance, slow signal propagation speed, and difficult signal propagation in a high frequency region of 30 GHz or more. It is necessary to use low resistance metals such as copper, silver and gold. However, since the low resistance metal as described above has a low melting point, it is necessary to fire at a low temperature of about 800 to 1000 ° C. Therefore, the wiring layer made of this low resistance metal is made of alumina that requires high temperature firing. Simultaneous firing was not possible. In addition, since the alumina substrate has a high dielectric constant, it is difficult to apply it to a high-frequency circuit substrate.
[0006]
For this reason, recently, attention has been focused on using glass ceramics obtained by firing a mixture of glass and ceramics (inorganic filler) as an insulating substrate. That is, glass ceramics are suitable as high-frequency insulating substrates because of their low dielectric constant, and glass ceramics can be fired at a low temperature of 800 to 1000 ° C., so low resistance metals such as copper, silver, and gold are used as wiring layers. As an advantage.
[0007]
Multi-layer glass ceramic substrates are made by adding organic binder, plasticizer, solvent, etc. to a mixture of glass and filler to form a slurry, and after forming glass ceramic green sheets by the doctor blade method, etc. A conductor pattern containing a resistance metal powder is printed to form a conductor pattern on the green sheet, and then a plurality of green sheets are laminated and fired at a temperature of 800 to 1000 ° C.
[0008]
However, the multi-layer glass ceramic substrate has a problem that shrinkage occurs during sintering during sintering. The degree of such shrinkage is not uniform, and the shrinkage rate and shrinkage direction vary depending on the inorganic material for the substrate to be used, the green sheet composition, the variation in the particle size of the raw material powder, the conductor pattern, the internal electrode material, and the like. This causes several problems in the production of multilayer glass ceramic substrates.
[0009]
First, when producing a screen plate for internal electrode printing, the size of the screen plate must be determined by calculating backward from the shrinkage rate of the substrate, but the shrinkage rate and shrinkage direction of the substrate are constant as described above. Therefore, the screen plate must be remade for each substrate production lot, which is uneconomical and impractical. Furthermore, in the multilayer glass ceramic substrate produced by the green sheet laminating method as described above, the shrinkage rate in the vertical direction and the horizontal direction in the laminated surface differs depending on the film forming direction of the green sheet. It becomes even more difficult.
[0010]
On the other hand, when forming an electrode having an area larger than necessary so as to allow shrinkage error, there is a problem that high-density wiring cannot be made.
[0011]
In order to reduce these shrinkage changes, the trend of substrate shrinkage due to circuit design and management of substrate materials and green sheet composition, variation in powder particle size, lamination conditions such as press pressure and temperature in the manufacturing process are adequately managed. There is a need to. However, it is generally said that an error of about ± 0.5% is generally generated as an error in contraction rate.
[0012]
This is a problem common to those accompanied by sintering of ceramics, glass ceramics and the like regardless of the multilayer glass ceramic substrate. In order to solve such a problem, Japanese Patent Laid-Open No. 4-243978, Japanese Patent Laid-Open No. 5-28867, and Japanese Patent Laid-Open No. 5-102666 disclose a substrate including the following steps (1) to (4). Manufacturing methods have been proposed.
(1) Laminate a desired number of glass ceramic green sheets containing a glass ceramic component and organic components such as a binder and a plasticizer in which a conductor pattern is formed,
(2) A constrained green sheet containing an inorganic material that does not sinter at the firing temperature of the glass ceramic component and an organic component such as a binder and a plasticizer is laminated on both sides or one side of the obtained glass ceramic / green sheet laminate. And
(3) The laminated body of these glass ceramic green sheet laminates and constrained green sheets is heated to first remove organic components and then fired to form glass ceramic substrates and restraint sheets, respectively.
(4) Finally, the restraint sheet is removed from the glass ceramic substrate.
[0013]
According to this method, the constraining green sheet constrains the shrinkage during firing of the glass ceramic green sheet, so that the shrinkage occurs only in the thickness direction of the laminate, and the shrinkage does not occur in the longitudinal and lateral directions of the laminate surface. It is considered that the dimensional accuracy of the glass ceramic substrate is improved.
[0014]
[Patent Document 1]
JP-A-4-243978
[Patent Document 2]
JP-A-5-28867
[Patent Document 3]
Japanese Patent Laid-Open No. 5-102666
[Patent Document 4]
Japanese Unexamined Patent Publication No. 7-196368
[0015]
[Problems to be solved by the invention]
In the above method, the glass ceramic green sheet and the constrained green sheet are bonded by an organic component such as a binder contained in the green sheet. However, in the firing step (3), after organic components such as binders and plasticizers decompose and volatilize, the powder in the constrained green sheet and the powder in the glass ceramic green sheet are simply in close contact with each other. Only weak bonds due to van der Waals forces are working between the sheets.
[0016]
Such weak bonds may cause the constrained green sheets to be inadvertently peeled from the glass ceramic / green sheet laminate in the firing step (3) due to their thermal expansion difference or the like.
[0017]
If the constrained green sheet peels during firing, sintering shrinkage of the glass ceramic green sheet cannot be prevented. Further, even if the constrained green sheet is partially peeled, there is a problem in that the glass ceramic substrate is deformed because contraction occurs in these portions.
[0018]
Also, since the glass ceramic / green sheet laminate and the constrained green sheet have a low bonding force, the glass component in the constrained green sheet in the glass ceramic / green sheet depends on the state of adhesion before firing and the type of glass ceramic component. Depending on the penetrability, the bonding force tends to be uneven. If the bonding force is uneven, the force that restrains the sintering shrinkage of the glass ceramics is uneven, causing unevenness of the shrinkage, and warping or deformation of the glass ceramic substrate. As a result, there is a problem that a substrate with high dimensional accuracy cannot be obtained.
[0019]
Furthermore, in the degreasing method for the glass ceramic / green sheet laminate, when a low resistance metal such as silver or gold is used as the wiring layer, the atmosphere is usually used. When degreasing is performed using air, the organic binder may suddenly generate heat due to oxidative decomposition, causing thermal runaway, and the metal powder in the ceramic molded body may undergo thermal expansion due to oxidation. For this reason, there is a problem that defects are induced in the internal structure of the product. In addition, when using a copper low resistance metal as a wiring layer, in the degreasing treatment under a low oxygen partial pressure, an atmospheric gas having a dew point of 40 ° C. or more is used for the purpose of promoting thermal decomposition of the organic binder. There has been a problem in that the metal powder is oxidized and diffused in the ceramic molded body, resulting in deterioration of the insulating properties of the product.
[0020]
The object of the present invention is to reliably restrain the sintering shrinkage in the laminated surface of the glass ceramic green sheet, and further, in the internal structure of the product by the metal powder in the glass ceramic molded body being oxidized and thermally expanded. An object of the present invention is to provide a method for obtaining a highly reliable glass ceramic substrate with high dimensional accuracy, which effectively suppresses deterioration of product insulation due to oxidation and diffusion of defects and metal powder.
[0021]
[Means for Solving the Problems]
As a result of intensive research to solve the above problems, the present inventors have (I) a glass component contained in the constrained green sheet, and this glass component is constrained with the glass ceramic green sheet during the firing process. Since it acts as a binder to bond the green sheet, the bond strength between them can be increased, and the peeling of the constrained green sheet can be prevented. (II) The sintering shrinkage of the constrained green sheet itself during firing is the glass content. Can be substantially avoided by setting the value within a predetermined range, and as a result, (III) a glass ceramic substrate with high dimensional accuracy can be obtained by restraining the shrinkage of the glass ceramic / green sheet laminate by the constraining green sheet. And (IV) a laminate of a restrained green sheet and a glass ceramic / green sheet laminate. By irradiating the laminated body with microwaves through an enclosure that absorbs microwaves, the organic component is removed and fired by oxidizing the thermal expansion of the metal powder in the glass ceramic substrate. It is possible to effectively suppress the deterioration of the insulation of the glass ceramic substrate due to the occurrence of defects in the internal structure and the oxidation and diffusion of the metal powder, thereby enabling highly reliable glass with high dimensional accuracy. The present inventors have found a new fact that a method for obtaining a ceramic substrate can be provided, and have completed the present invention.
[0022]
  That is, the present inventionFirstThe manufacturing method of the glass ceramic substrate isA step of laminating a plurality of glass ceramic green sheets containing an organic binder to form a glass ceramic green sheet laminate, and a non-sinterable inorganic material and glass on both sides of the glass ceramic green sheet laminate Laminating a constrained green sheet containing an organic binder to obtain a green sheet laminate, enclosing the green sheet laminate in a microwave-absorbing casing, and irradiating the laminate with microwaves through the casing Thus, the method includes a step of firing the green sheet laminate to produce a glass ceramic substrate holding the restraint sheet, and a step of removing the restraint sheet from the glass ceramic substrate. In the first method for producing a glass ceramic substrate, the casing is preferably surrounded by a microwave absorbing member.
[0023]
  Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, in the first method for producing a glass ceramic substrate,Dissipation tangent to microwave of hard-to-sinter inorganic material of constrained green sheet is better than glass ceramic green sheet laminatelarge.
[0024]
  Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, in the first method for producing a glass ceramic substrate,The firing atmosphere gas in the case is 1 to 15 times the volume of the enclosure per minute.Supply.
[0025]
  Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, in the first method for producing a glass ceramic substrate,The softening point of the glass contained in the constrained green sheet is below the firing temperature of the glass ceramic green sheet laminate.is there. This glass ceramic substrate manufacturing method is referred to as a second glass ceramic substrate manufacturing method.
[0026]
  Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, in the method for manufacturing the first or second glass ceramic substrate,The softening point of the glass contained in the restraint green sheet isOrganic binderThan the volatilization temperature ofhigh.
[0027]
  Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, the manufacturing method of the 1st glass ceramic substrateIn the constrained green sheet, the glass content is 0.5 to 15% by mass of the total inorganic components in the constrained green sheet.Is.
[0028]
Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, in the first method for producing a glass ceramic substrate,In the above configuration, the thickness of the constraining green sheet is 10% or more with respect to the thickness of the glass ceramic / green sheet laminate on one side.is there.
[0029]
Moreover, the method for producing the glass ceramic substrate of the present invention comprises:Preferably, in the first method for producing a glass ceramic substrate,The glass ceramic green sheet has a tensile elongation of 10 to 40%is there.
[0030]
Of the present inventionAccording to one aspectAccording to the method for manufacturing a glass ceramic substrate, a laminate of a constrained green sheet and a glass ceramic / green sheet laminate is surrounded by a microwave-absorbing casing, and the laminate is irradiated with microwaves through the casing. By removing the organic components and firing, it is possible to effectively suppress the temperature difference between the inside and the surface of the laminate of the constrained green sheet and the glass ceramic / green sheet laminate, thereby firing. Thus, the variation in the firing shrinkage of the laminate can be suppressed to an extremely small value, and a highly reliable glass ceramic substrate with high dimensional accuracy can be obtained.
[0031]
This is because the heat generated by absorption by the microwave-absorbing casing surrounding the laminate heats the surface of the laminate, and as a result, the temperature is lower than the inside due to heat dissipation from the surface. This is because the temperature gradient between the surface of the laminated body and the inside of the laminated body can be effectively suppressed to an extremely small one.
[0032]
  In addition, the present inventionAccording to one aspectAccording to the manufacturing method of the glass ceramic substrate, when the dielectric loss tangent to the microwave of the hard-to-sinter inorganic material of the constrained green sheet is larger than that of the glass ceramic / green sheet laminate, the heat generated by the constrained green sheet by the microwave Is more effective than the heat generation of the glass ceramic / green sheet laminate, and the temperature gradient between the laminate surface and the inside of the laminate, where the temperature tends to be lower than the interior due to heat dissipation from the surface, is even more effective. Therefore, the variation in firing shrinkage of the laminate can be suppressed to a very small size, and a highly reliable glass ceramic substrate with high dimensional accuracy can be obtained.
[0033]
  Furthermore, the present inventionAccording to one aspectAccording to the method for manufacturing a glass ceramic substrate, when the firing atmosphere gas is supplied into the housing at a volume of 1 to 15 times the volume of the casing per minute, the firing atmosphere gas is, for example, a rectangular parallelepiped. A laminate of a constrained green sheet and a glass ceramic / green sheet laminate is generated by pyrolysis and depolymerization reaction in the firing atmosphere gas supplied from the opening of the cabinet into the casing. The decomposed gas is exhausted from the openings on the side surfaces facing each other without staying in the housing, and the constrained green sheet and the glass ceramic / green sheet laminate are fired under a firing gas with a uniform concentration. Therefore, the variation in firing shrinkage of the laminate can be suppressed to an extremely small size, and a highly reliable glass ceramic with high dimensional accuracy. Tsu can be obtained click substrate.
[0034]
  Furthermore, the present inventionAccording to one aspectAccording to the glass ceramic substrate manufacturing method, when the softening point of the glass contained in the constrained green sheet is equal to or lower than the firing temperature of the glass ceramic / green sheet laminate, firing of the glass ceramic / green sheet laminate is started. Since glass is welded by heating in the vicinity of the lamination interface between the constrained green sheet and the glass ceramic / green sheet laminate before heating, it is substantially in the XY direction which is the in-plane direction of the laminate. Firing without shrinking can be performed more reliably, and dimensional variations of the glass ceramic substrate obtained by firing the glass ceramic / green sheet laminate can be effectively suppressed. As described above, it becomes possible to effectively suppress peeling of the constrained green sheet from the glass ceramic / green sheet laminate during firing, thus preventing sintering shrinkage in the XY direction of the glass ceramic / green sheet laminate. It is possible to suppress the deformation of the glass ceramic substrate.
[0035]
  Furthermore, the present inventionAccording to one aspectAccording to the method for producing a glass ceramic substrate, when the softening point of the glass contained in the constrained green sheet is higher than the volatilization temperature of the organic component, the glass ceramic / green sheet laminate is formed before the glass is softened. Volatile organic components are not taken into glass ceramics due to volatilization. As a result, it is possible to effectively prevent the organic component from remaining in the glass ceramic / green sheet laminate, so that it can be fired without being affected by the organic component, thereby preventing shrinkage unevenness and at the same time glass ceramic. It is possible to effectively suppress the warpage and deformation of the substrate.
[0036]
Furthermore, according to the method for producing a glass ceramic substrate of the present invention, when the glass content in the constrained green sheet is 0.5 to 15% by mass of the total inorganic components in the constrained green sheet, the constrained green sheet The glass in the vicinity of the lamination interface between the glass ceramic and green sheet laminate is welded by heat, so that sintering shrinkage within the laminated surface of the glass ceramic and green sheet can be reliably restrained. This makes it possible to effectively prevent peeling of the constrained green sheet during firing, and to suppress sintering shrinkage of the glass ceramic / green sheet laminate. As a result, it is possible to effectively prevent the warp, deformation, etc. of the glass ceramic substrate, so that the shrinkage of the glass ceramic / green sheet laminate can be surely suppressed, and the glass ceramic substrate with high dimensional accuracy. Can be obtained.
[0037]
Furthermore, according to the method for producing a glass ceramic substrate of the present invention, when the thickness of the constrained green sheet is 10% or more with respect to the thickness of the glass ceramic green sheet laminate on one side, When sintering shrinkage starts within the lamination surface of the green sheet, it is possible to effectively suppress the driving force that the glass ceramic green sheet laminate tries to shrink by firing in the XY direction with the restraint green sheet. It becomes. As a result, it is possible to effectively prevent the occurrence of warpage, deformation, etc. of the glass ceramic substrate, so that the shrinkage of the glass ceramic / green sheet laminate can be surely suppressed, and the glass ceramic substrate with high dimensional accuracy. Can be obtained.
[0038]
According to the method for producing a glass-ceramic substrate of the present invention, when the tensile elongation of the glass-ceramic green sheet is 10 to 40%, the glass-ceramic green sheet is less likely to cause plastic deformation due to lamination pressure or temperature, and temporarily. Therefore, even if it stretches, it functions as an elastic body that can be restored to its original position, so that it is possible to effectively suppress variation in the deformation of the glass ceramic green sheet during lamination. Further, since the glass ceramic green sheet is moderately soft, it is possible to effectively prevent the glass ceramic green sheet from being cracked or cracked. As a result, it is possible to produce a glass ceramic substrate having a wiring conductor with even better dimensional accuracy.
[0039]
As described above, according to the method for producing a glass ceramic substrate of the present invention, the sintering shrinkage in the laminated surface of the glass ceramic / green sheet laminate is surely restrained, and further the metal powder in the glass ceramic molded body Oxidation thermal expansion causes defects in the internal structure of the product and metal powders to oxidize and diffuse effectively to prevent deterioration of the product's insulation, and to provide a highly reliable glass ceramic substrate with high dimensional accuracy. It is possible to provide a method of obtaining.
[0040]
DETAILED DESCRIPTION OF THE INVENTION
Next, the manufacturing method of the glass ceramic substrate of this invention is demonstrated in detail based on an accompanying drawing.
[0041]
FIG. 1A is a plan view showing an example of an embodiment of a method for producing a glass ceramic substrate of the present invention, and shows a plan view of a microwave irradiation firing furnace used in the method for producing a glass ceramic substrate of the present invention. ing. 1B is a cross-sectional view taken along the line A-A ′, and FIG. 1C is a cross-sectional view taken along the line B-B ′.
[0042]
In these figures, 1 is a laminate of a constrained green sheet and a glass ceramic green sheet laminate, 2 is a microwave-absorbing casing, 3 is a microwave firing furnace, 4 is a furnace wall, 5 is a heat insulating wall, 6 is a microwave absorbing wall, 7 is a microwave-absorbing shelf, 8 is a pedestal, 9 is a firing atmosphere gas supply nozzle, 10 is a firing atmosphere gas, and 11 is an opening.
[0043]
As the glass ceramic green sheet in the present invention, a glass powder, a filler powder (ceramic powder), an organic binder, a plasticizer, an organic solvent and the like are used.
[0044]
Examples of glass components include SiO.₂-B₂O_ThreeSystem, SiO₂-B₂O_Three-Al₂O_ThreeSystem, SiO₂-B₂O_Three-Al₂O_Three-MO system (where M represents Ca, Sr, Mg, Ba or Zn), SiO₂-Al₂O_Three-M¹OM²O system (however, M¹And M²Are the same or different and represent Ca, Sr, Mg, Ba or Zn), SiO₂-B₂O_Three-Al₂O_Three-M¹OM²O system (however, M¹And M²Is the same as above), SiO₂-B₂O_Three-M^Three ₂O system (however, M^ThreeRepresents Li, Na or K), SiO₂-B₂O_Three-Al₂O_Three-M^Three ₂O system (however, M^ThreeIs the same as described above), Pb-based glass, Bi-based glass and the like.
[0045]
Moreover, as a filler, for example, Al₂O_Three, SiO₂, ZrO₂And TiO, a complex oxide of alkaline earth metal oxides₂Al oxide of alkaline earth metal oxide, Al₂O_ThreeAnd SiO₂And composite oxides containing at least one selected from (for example, spinel, mullite, cordierite).
[0046]
The mixing ratio of the glass and filler is preferably 40:60 to 99: 1 by mass ratio.
[0047]
As the organic binder blended in the glass ceramic green sheet, those conventionally used in ceramic green sheets can be used. For example, acrylic (acrylic acid, methacrylic acid or their homopolymers or copolymers). Polymer, specifically acrylic ester copolymer, methacrylic ester copolymer, acrylic ester-methacrylic ester copolymer, etc.), polyvinyl butyral, polyvinyl alcohol, acrylic-styrene, polypropylene carbonate , Cellulosic homopolymers or copolymers.
[0048]
The glass ceramic green sheet is obtained by adding a predetermined amount of plasticizer and solvent (organic solvent, water, etc.) to the glass powder, filler powder, and organic binder as necessary to obtain a slurry. It can be obtained by molding to a thickness of about 50 to 500 μm by a method, a calender roll method, a die press method or the like.
[0049]
The tensile elongation of the glass ceramic green sheet is preferably 10 to 40%. As a result, the glass ceramic green sheet is less likely to undergo plastic deformation due to lamination pressure and temperature and functions as an elastic body that can be restored to its original position even if temporarily stretched. Variations in deformation can be effectively suppressed. Further, since the glass ceramic green sheet is moderately soft, it is possible to effectively prevent the glass ceramic green sheet from being cracked or cracked.
[0050]
On the other hand, when the tensile elongation is less than 10%, the plastic deformation of the glass ceramic green sheet can be further reduced, and the deformation variation in the lamination process can be further suppressed. Since it tends to be too hard, it tends to be difficult to prevent the occurrence of cracks and cracks. Further, since the glass ceramic green sheet is hard, stacking misalignment tends to occur, and as a result, stacking reliability tends to decrease.
[0051]
On the other hand, when the tensile elongation exceeds 40%, the glass ceramic green sheet tends to be plastically deformed depending on the lamination pressure and temperature, and it tends to be difficult to suppress variation in deformation.
[0052]
A methacrylic binder such as isobutyl methacrylate, normal butyl methacrylate, or lauryl methacrylate is used as the binder for the glass ceramic green sheet that can have a tensile elongation of 10 to 40%. These are also excellent from the viewpoint of binder removal.
[0053]
The tensile elongation of the glass ceramic green sheet is adjusted by adding 1 to 6% by mass of a phthalate ester plasticizer such as dibutyl phthalate or dioctyl phthalate or an adipate plasticizer to the binder. can do.
[0054]
Such a glass ceramic green sheet having a tensile elongation of 10 to 40% is, for example, 70% by mass of borosilicate glass and 30% by mass of Al as glass powder.₂O_Three10-15 parts by weight of a methacrylic binder such as isobutyl methacrylate and 1-6 parts by weight of a plasticizer such as dibutyl phthalate is mixed with a filler powder such as a doctor blade method, rolling method, pressing method, etc. It is produced by forming into a sheet form.
[0055]
In order to form a conductor pattern on the surface of a glass ceramic green sheet, for example, a paste of a conductor material powder is printed by a screen printing method or a gravure printing method, or a metal foil having a predetermined pattern shape is transferred. A method is mentioned. Examples of the conductor material include one or more of Au, Ag, Cu, Pd, Pt, and the like. In the case of two or more, any form such as mixing, alloy, coating, etc. may be used.
[0056]
The conductor pattern on the surface includes a portion where a through conductor such as a via conductor or a through-hole conductor for connecting conductor patterns between upper and lower layers is exposed on the surface. These through conductors are formed by means such as embedding by printing a paste of conductive material powder (conductor paste) in a through hole formed in a glass ceramic green sheet by punching or the like.
[0057]
For the lamination of glass ceramic and green sheets, heat and pressure are applied to the stacked green sheets by heat and pressure, and an adhesive composed of an organic binder, plasticizer, solvent, etc. is applied between the sheets and thermocompression is applied. Can be adopted.
[0058]
The constrained green sheet in the present invention is obtained by molding a slurry in which an organic binder, a plasticizer, a solvent, and the like are added to an inorganic component composed of a hardly sinterable inorganic material and glass.
[0059]
Moreover, as a hardly sinterable inorganic material, Al₂O_ThreeAnd SiO₂Although at least 1 sort (s) chosen from these is mentioned, It is not restrict | limited to these.
[0060]
The glass added to the constraining green sheet is not particularly limited, and the same glass as that used in the glass ceramic green sheet can be used. The glass in the constrained green sheet may have the same composition as that of the glass in the glass ceramic green sheet or may have a different composition.
[0061]
According to the method for manufacturing a glass ceramic substrate of the present invention, a laminate 1 of a constrained green sheet and a glass ceramic / green sheet laminate is surrounded by a microwave-absorbing casing 2 and the laminate 2 is passed through the casing 2. It is important to irradiate microwaves. This makes it possible to fire while effectively suppressing the temperature difference between the inside and the surface of the laminate 1 of the constrained green sheet and the glass ceramic / green sheet laminate. The glass ceramic substrate can be obtained.
[0062]
Further, glass ceramics is a material that makes it difficult to control the dimensional accuracy after firing, for example, compared to alumina ceramics. This is because glass ceramic with a large amount of glass component added partially generates glass because heat during firing is not uniformly transmitted by the conventional firing method. Therefore, the firing method in the production method of the present invention using microwave irradiation capable of uniformly transferring heat during firing is suitable for firing glass ceramics.
[0063]
This is because the heat generated by the microwave generated in the microwave baking furnace 3 being absorbed by the microwave absorption wall 6 provided on the inner wall of the microwave baking furnace 3 heats the surface of the laminate 1. As a result, it is possible to effectively suppress the temperature gradient between the surface of the laminate 1 and the inside of the laminate 1 whose temperature tends to be lower than the inside due to heat dissipation from the surface, to an extremely small one effectively. Because it can.
[0064]
Further, as a material of the microwave-absorbing casing 2, a ceramic material having a large dielectric loss (tan δ) and a large microwave absorption is preferable. Examples of the ceramic material that constitutes the housing 2 include mullite-based materials, silicon carbide-based materials, and alumina-based materials.
[0065]
In addition, since the shrinkage of the constrained green sheet itself during firing can be substantially avoided by setting the glass content within a predetermined range, the constrained green sheet effectively contracts the glass ceramic / green sheet laminate. Therefore, a glass ceramic substrate with high dimensional accuracy can be obtained.
[0066]
Further, as the firing atmosphere gas 10, it is preferable to use nitrogen gas or argon gas which is an inert gas. From the viewpoint of preventing oxidation of the laminate 1, it is also preferable to use an appropriate amount of hydrogen gas, which is a reducing gas, mixed with these inert gases.
[0067]
Furthermore, when a copper low resistance metal is used as a wiring layer as a conventional technique, an atmospheric gas having a dew point of 40 ° C. or higher is used in the degreasing treatment under a low oxygen partial pressure in order to promote thermal decomposition of the organic binder. In that case, there has been a problem that the insulating property of the product is deteriorated by oxidation and diffusion of the metal powder in the ceramic molded body. On the other hand, the firing method of removing the organic components and firing by irradiating the laminate 1 of the constrained green sheet and the glass ceramic / green sheet laminate according to the present invention with microwave Since it is possible to perform degreasing and firing in an atmosphere containing only nitrogen, it is possible to reliably restrain the sintering shrinkage in the laminated surface of the glass ceramic / green sheet laminate, and further to glass ceramic. Since the metal powder in the substrate undergoes thermal expansion due to oxidation, it is possible to effectively suppress the occurrence of defects in the internal structure of the product and the deterioration of product insulation due to the oxidation and diffusion of the metal powder. It is possible to obtain a glass ceramic substrate with high dimensional accuracy and high reliability.
[0068]
The organic component is removed and baked by irradiating the laminate 1 of the constrained green sheet and the glass ceramic / green sheet laminate with microwaves through the housing 2. At this time, the organic component is removed by 100 to 800. It is performed by heating the laminated body 1 in a temperature range of ° C. to decompose and volatilize organic components. Moreover, although a calcination temperature changes with glass-ceramic compositions, it is in the range of about 800-1100 degreeC normally. Firing is usually performed in the air, but when copper is used as the conductor material, it is possible to perform the firing in an atmosphere containing only nitrogen without water vapor.
[0069]
Further, the frequency of the microwave used in the production method of the present invention is preferably 1 to 20 GHz, and particularly preferably 2.45 GHz. If the frequency is less than 1 GHz, the wavelength becomes too long and the microwave absorption rate by the laminate 1 and the housing 2 is lowered, which is not preferable. On the other hand, if the frequency exceeds 20 GHz, the microwave absorption rate becomes too high, and in particular, it becomes difficult to control the temperature of the temperature rise. In particular, when the frequency of the microwave to be used is 2.45 GHz, it is easy to control the temperature of the temperature rise because the microwave energy is easily controlled. Moreover, since it is permitted as an ISM band, a relatively small and inexpensive microwave oscillator can be used.
[0070]
When the above microwaves act on the laminate 1, the glass ceramic / green sheet laminate itself is dielectrically heated, so that the glass ceramic / green sheet laminate is rapidly heated from the inside, and the organic components are self-decomposed. Volatilization then proceeds with sintering.
[0071]
Conventionally, when copper low resistance metal is used as a wiring layer, degreasing treatment under a low oxygen partial pressure has required the use of an atmospheric gas having a dew point of 40 ° C. or higher for the purpose of promoting thermal decomposition of the organic binder. According to the method for producing a glass ceramic substrate of the present invention, when a large-scale or large-sized multilayer glass ceramic substrate is fired by irradiating microwaves, the microwaves are irradiated and the laminate 1 is paired with a pair. Surrounding by a microwave-absorbing casing 2 having openings 11 on the opposite side surfaces, and flowing a firing atmosphere gas 10 from one of the openings 11 of the casing 2 to remove organic components and firing. Because of this, the dipole or charge of the organic binder oscillates and rotates due to microwave irradiation, and self-heat is generated by the frictional heat and decomposes. Introduction of Una water vapor can be that there is no need.
[0072]
The microwave baking furnace 3 may be a batch furnace equipped with a microwave oscillator or a large continuous furnace.
[0073]
The furnace wall 4 of the microwave firing furnace 3 has a heat insulating wall 5 made of an alumina fiber, a foamed alumina material, or the like having heat insulating properties and microwave permeability, and a microwave provided inside thereof. It consists of a double structure with the microwave absorption wall 6 which becomes a heat generating inner shell. Examples of the material constituting the microwave absorbing wall 6 serving as the inner shell include mullite-based materials, silicon nitride-based materials, and alumina-based materials. Further, the microwave-absorbing casing 2 and the microwave-absorbing shelf 7 are appropriately selected from those materials according to the laminate 1 to be fired. It is desirable to use one having the same degree of microwave absorption. Thereby, in the case of microwave irradiation, heating nonuniformity does not occur and the laminated body 1 can be uniformly fired and sintered.
[0074]
Moreover, in the manufacturing method of the glass ceramic substrate of this invention, it is preferable that the dielectric loss tangent with respect to the microwave of the hard-sintering inorganic material of a restraint green sheet is larger than a glass ceramic green sheet laminated body. As the hardly sinterable inorganic material used for such a constrained green sheet, a material having a larger dielectric loss tangent than the glass powder and filler powder (ceramic powder) in the glass ceramic / green sheet laminate may be used.
[0075]
For example, the filler powder contained in the glass ceramic green sheet laminate is alumina (Al₂O_Three) When using a powder and using a glass having a dielectric loss tangent smaller than that of alumina as a glass powder, it is difficult to sinter silicon carbide (SiC) powder having a dielectric loss tangent greater than that of alumina as the glass powder or filler powder (ceramic powder). What is necessary is just to use as an inorganic material.
[0076]
In this way, by setting the dielectric loss tangent to the microwave of the hard-to-sinter inorganic material of the constrained green sheet to be larger than that of the glass ceramic / green sheet laminate, the constraint green sheet and the glass ceramic / green sheet laminate are The heat generated by absorption of the microwave-absorbing casing surrounding the laminate heats the surface of the laminate, and the constrained green sheet generates more heat than the glass ceramic / green sheet laminate. The temperature gradient between the surface of the laminate that tends to be lower than the inside due to heat dissipation from the inside and the inside of the laminate can be made even more effective and extremely small. As a result, variation in firing shrinkage of the laminate can be suppressed to an extremely small value, and a highly reliable glass ceramic substrate with high dimensional accuracy can be obtained.
[0077]
For example, the dielectric loss tangent of glass powder and filler powder (ceramic powder) in a glass ceramic / green sheet laminate is 2 × 10^-FourThe dielectric loss tangent of the hardly sinterable inorganic material used for constrained green sheets is 600 x 10^-FourThus, the temperature gradient between the surface of the laminate of the constrained green sheet and the glass ceramic / green sheet laminate and the inside of the laminate can be further effectively reduced.
[0078]
In the method for producing a glass ceramic substrate of the present invention, it is preferable to supply the firing atmosphere gas 10 into the housing 2 at a volume of 1 to 15 times the volume of the casing 2 per minute. A firing atmosphere gas 10 having a volume of 1 to 15 times the volume of the casing 2 per minute is supplied into the casing 2 from, for example, the opening 11 of the microwave-absorbing casing 2 having a rectangular parallelepiped shape. The decomposition atmosphere gas 10 and the decomposition gas generated by the thermal decomposition or depolymerization reaction of the laminate 1 of the constrained green sheet and the glass ceramic / green sheet laminate are not retained in the housing 2. It will exhaust continuously from the opening part (not shown) of the side surface which the housing | casing 2 opposes. For this reason, the laminate 1 of the constrained green sheet and the glass ceramic / green sheet laminate can be fired under a constant condition in the firing furnace gas 3 in the microwave firing furnace 3. It is possible to effectively suppress firing variations due to the difference in position and the difference in the preparation location of the laminate 1. Thereby, the dispersion | variation in the baking shrinkage of the laminated body 1 can be suppressed to a very small thing, and it becomes possible to obtain a highly reliable glass ceramic substrate with high dimensional accuracy.
[0079]
Further, the firing atmosphere gas 10 is supplied from one of the openings 11 of the housing 2 at a volume of 5 to 15 times the volume of the housing 2 per minute using the firing atmosphere gas supply nozzle 9. By doing so, the firing atmosphere gas 10 is supplied from the firing atmosphere gas supply nozzle 9 to the laminate 1 of the constrained green sheet and the glass ceramic / green sheet laminate, and the flow rate is always uniformly contacted at a constant rate. By doing so, since the organic binder contained in this laminated body 1 is uniformly thermally decomposed and removed, uneven distribution of the organic binder remaining as undecomposed in the laminated body 1 can be effectively suppressed.
[0080]
Furthermore, the laminate 1 can be fired under the firing atmosphere gas 10 in which the concentration of the firing atmosphere gas 10 is constant inside the housing 2 and the flow rate is always constant. It becomes possible to effectively suppress the firing variation due to the difference in position of the single body and the difference in the charging location of the laminate 1.
[0081]
As a result, variation in firing shrinkage of the laminate 1 can be suppressed to an extremely small value, and a highly reliable glass ceramic substrate with high dimensional accuracy can be obtained.
[0082]
When the firing atmosphere gas 10 is supplied in an amount less than one time the volume of the housing 2, the supply amount of the firing atmosphere gas 10 is less than the amount necessary to form a sufficiently uniform atmosphere. Therefore, the concentration of the decomposition gas generated by the thermal decomposition or depolymerization reaction of the laminate 1 is locally increased in the vicinity of the laminate 1, and the composition of the atmospheric gas is not uniform in the vicinity of the laminate 1. Tend.
[0083]
Therefore, it is difficult to effectively suppress the retention of the decomposition gas generated by the thermal decomposition or depolymerization reaction of the laminate 1 in the housing 2 by continuously exhausting from the opening 11 on the opposite side surface. Tend to be. As a result, the laminate 1 is fired in a state in which the concentration of the firing atmosphere gas 10 is not constant inside the casing 2 in the microwave firing furnace 3, so that the organic binder and the like are effectively and uniformly removed. When it becomes difficult to do, there exists a tendency for the possibility that the dispersion | variation of the baking shrinkage of the laminated body 1 will occur becomes high.
[0084]
Further, when the supply amount of the firing atmosphere gas 10 is less than one volume of the volume of the housing 2, the decomposition gas generated by the thermal decomposition or depolymerization reaction of the laminate 1 in the housing 2 is generated. It is difficult to effectively suppress the retention by continuously exhausting from the opening 11 on the opposite side surface. The narrow casing 2 in which a gas such as the firing atmosphere gas 10 is charged is the laminated body 1. This is because it is difficult to flow through the gap in the inside with a substantially uniform distribution, and there is a possibility that a part of the backflow phenomenon of the supplied firing atmosphere gas 10 may occur. Since there is a tendency to generate remarkably under the condition where the supply amount of the gas 10 is small, firing variation occurs under this condition, and this causes variation in firing shrinkage of the laminate 1. There is a tendency to be more likely.
[0085]
On the other hand, in the supply amount of the firing atmosphere gas 10 that has a volume exceeding 15 times the volume of the housing 2, the firing atmosphere gas 10 is at room temperature. Since the temperature is locally lowered in the vicinity of 1, the temperature in the microwave baking furnace 3 tends to be difficult to be kept constant in a desired temperature range. Further, when the supply amount of the firing atmosphere gas 10 exceeds an amount of 15 times the volume of the housing 2, the organic binder of the laminate 1 is decomposed or decomposed during the firing process of the laminate 1. When the laminate 1 is removed by the polymerization reaction, the adhesion of the constrained green sheet to the glass ceramic / green sheet laminate in the laminate 1 is weakened, so a large amount of firing atmosphere gas is applied to the laminate 1 in such a state. When 10 hits, the constrained green sheet is peeled off from the interface with the glass ceramic / green sheet laminate and is not sufficiently adhered, and the firing shrinkage of the glass ceramic / green sheet laminate is sufficiently restrained. Tend to be difficult.
[0086]
As a result, variation in firing occurs, and there is a tendency that variation in firing shrinkage of the laminate 1 due to the variation is likely to occur.
[0087]
Moreover, according to the manufacturing method of the glass-ceramic board | substrate of this invention, it is preferable that the softening point of the glass contained in a restraint green sheet shall be below the firing temperature of the laminated body 1. FIG.
[0088]
This is because if the softening point of the glass contained in the constrained green sheet is set to be equal to or lower than the firing temperature of the laminate 1, the constrained green sheet and the glass ceramic green sheet before the glass ceramic / green sheet laminate starts to sinter Since the glass in the vicinity of the laminate interface with the laminate is welded by heat, the restraint green sheet and the glass ceramic green sheet laminate are integrated by the glass contained in the restraint green sheet, so that XY Because it is possible to perform firing that does not substantially shrink in the direction, it is possible to effectively suppress the dimensional variation of the glass ceramic green sheet laminate, and by the above, Because it is possible to effectively prevent peeling, glass ceramic grease Prevents sintering shrinkage of the sheet, This is because it is possible to suppress the deformation of the glass ceramic substrate.
[0089]
Moreover, according to the manufacturing method of the glass-ceramic board | substrate of this invention, it is preferable that the softening point of the glass contained in a restraint green sheet shall be higher than the volatilization temperature of the organic component of the laminated body 1. FIG.
[0090]
This is because the organic component in the glass ceramic green sheet laminate volatilizes before the glass of the constrained green sheet softens, so that it is not taken into the glass ceramic. Since it is possible to effectively prevent the remaining in the sheet laminate, it is possible to prevent shrinkage unevenness by firing without being affected by organic components, and at the same time, warp and deformation of the glass ceramic substrate. This is because it is possible to effectively suppress the above.
[0091]
The softening point of the glass in the constrained green sheet is preferably lower than the sintering temperature of the glass ceramic / green sheet laminate and higher than the decomposition / volatilization temperature of the organic component in the constrained green sheet. Specifically, the softening point of the glass in the constrained green sheet is preferably about 450 to 1100 ° C. This means that if the softening point of the glass is less than 450 ° C, the removal of the organic component from the glass ceramic green sheet will block the organic component removal path when the softened glass is decomposed and volatilized. This is because there is a tendency that it cannot be completely removed. On the other hand, when the softening point of the glass exceeds 1100 ° C., it tends to stop functioning as a binder to the green sheet under the normal firing conditions of the glass ceramic green sheet.
[0092]
The constrained green sheet is obtained by molding using an organic binder, a plasticizer, a solvent, and the like in the same manner as the production of the glass ceramic green sheet. As the organic binder, the plasticizer, and the solvent, the same materials as those used for the glass ceramic green sheet can be used. Here, the plasticizer is added in order to impart flexibility to the constraining green sheet and to enhance adhesion with the glass ceramic green sheet during lamination.
[0093]
Moreover, according to the manufacturing method of the glass-ceramic board | substrate of this invention, it is preferable that the glass content in a restraint green sheet shall be 0.5-15 mass% of all the inorganic components in this restraint green sheet.
[0094]
This is because the glass in the vicinity of the laminate interface between the constrained green sheet and the glass ceramic / green sheet laminate is welded by heat to reliably restrain the sintering shrinkage within the laminate surface of the glass ceramic / green sheet laminate. This makes it possible to effectively prevent peeling of the constrained green sheet during firing, and to suppress the sintering shrinkage of the glass ceramic green sheet. As a result, the glass ceramic -It is possible to reliably suppress the shrinkage of the green sheet laminate and to effectively prevent the occurrence of warpage, deformation, etc. of the glass ceramic substrate, thereby obtaining a glass ceramic substrate with high dimensional accuracy. Because.
[0095]
If the glass content in the constrained green sheet is less than 0.5% by mass of the total inorganic components in the constrained green sheet, the glass content in the laminated surface of the glass ceramic / green sheet laminate is insufficient. Therefore, before the glass ceramic / green sheet laminate starts to sinter, the glass in the vicinity of the lamination interface between the restraint green sheet and the glass ceramic / green sheet laminate is not welded by heat, and is contained in the restraint green sheet. This is because the constrained green sheet and the glass ceramic / green sheet laminate cannot be integrated by glass, and firing that does not substantially shrink in the XY directions cannot be performed. Therefore, it becomes impossible to effectively suppress peeling of the constrained green sheet during firing, and it becomes impossible to effectively suppress dimensional variations of the glass ceramic / green sheet laminate. This is because the sintering shrinkage of the glass ceramic substrate cannot be prevented, and the deformation of the glass ceramic substrate cannot be suppressed.
[0096]
On the other hand, when the glass content in the constrained green sheet exceeds 15% by mass of the total inorganic components in the constrained green sheet, the constrained green sheet is sintered during firing by the glass acting as a sintering aid. As a result, it becomes difficult to reliably suppress the shrinkage of the glass ceramic / green sheet laminate due to the constrained green sheet, resulting in a problem that a glass ceramic substrate with high dimensional accuracy cannot be obtained. Because it does.
[0097]
Also, before the sintering of the glass ceramic green sheet laminate starts within the laminated surface of the glass ceramic green sheet laminate, the glass in the vicinity of the laminate interface between the constrained green sheet and the glass ceramic green sheet laminate is welded by heat. The constrained green sheet and the glass ceramic / green sheet laminate can be integrated by the glass contained in the constrained green sheet, but in the vicinity of the lamination interface between the constrained green sheet and the glass ceramic / green sheet laminate. When the welding power between the glasses becomes too strong, the restraint sheet is integrated with the surface layer of the glass ceramic substrate after firing, which causes a problem that it becomes difficult to remove the restraint sheet. In this case, for example, when a method such as wet blasting (a method of spraying abrasive grains and water by air pressure) is used to remove the constraining sheet, it takes too much time to remove the glass and glass. There arises a problem that the surface layer of the ceramic substrate is damaged.
[0098]
Further, according to the method for producing a glass ceramic substrate of the present invention, the thickness of the constraining green sheet is preferably 10% or more with respect to the thickness of the glass ceramic / green sheet laminate on one side.
[0099]
This is because when the sintering shrinkage starts within the laminated surface of the glass ceramic / green sheet laminate, the driving force of the glass ceramic / green sheet laminate to sinter shrink in the XY direction is restricted by the green sheet. Since it can be effectively suppressed, sintering shrinkage of the glass ceramic / green sheet laminate can be surely suppressed, and the occurrence of warpage and deformation of the glass ceramic substrate can be effectively prevented. This is because a glass ceramic substrate with high dimensional accuracy can be obtained.
[0100]
On the other hand, when the thickness of the constrained green sheet is less than 10% of the thickness of the glass ceramic / green sheet laminate on one side, the glass ceramic / green sheet laminate will sinter and shrink in the XY direction. Therefore, it becomes difficult to suppress the shrinkage and shrinkage of the glass ceramic / green sheet laminate, resulting in warping and deformation of the glass ceramic substrate. It may become impossible to prevent effectively.
[0101]
Further, the thickness of the constrained green sheet laminated on both surfaces of the glass ceramic / green sheet laminate is preferably 10% or more with respect to the thickness of the glass ceramic / green sheet laminate on one side only. If the thickness is too thin, the restraining property of the restraining green sheet may be lowered. Also, considering the ease of volatilization of organic components and easy removal of the restraint sheet from the glass ceramic substrate, the thickness of the restraint green sheet is approximately 200% of the thickness of the glass ceramic / green sheet laminate. It should be: Further, the constrained green sheets to be laminated may be one sheet, or may be a plurality of sheets laminated to have a predetermined thickness.
[0102]
In order to laminate the formed constrained green sheet on both sides of the glass ceramic / green sheet laminate, a method of applying heat and pressure to the stacked constrained green sheet and the glass ceramic / green sheet laminate and applying thermocompression, or organic A method of applying an adhesive composed of a binder, a plasticizer, a solvent, or the like between the constrained green sheet and the glass ceramic / green sheet laminate and thermocompression bonding can be employed. When an adhesive layer is interposed between the constrained green sheet and the glass ceramic / green sheet laminate, the constrained green sheet and the glass ceramic / green sheet are made to contain the same glass component as the constrained green sheet. You may make it raise the coupling | bonding force between laminated bodies.
[0103]
After firing, the constraining sheet is removed. The removal method is not particularly limited as long as the constraining sheet bonded to the surface of the glass ceramic substrate can be removed. For example, ultrasonic cleaning, polishing, water jet, sand blasting, wet blasting (abrasive grains and water by air pressure) And the like).
[0104]
In the obtained multilayer glass ceramic substrate, the shrinkage during firing is suppressed only in the thickness direction by the constraining green sheet, so that the contraction in the laminated surface can be suppressed to about 0.5% or less.
[0105]
Note that the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention. For example, in the above example, the semiconductor LSI of the present invention, chip parts, etc. may be mounted and applied to other uses such as those relating to a method for manufacturing a glass ceramic substrate for interconnecting them.
[0106]
【Example】
EXAMPLES Hereinafter, although the method of this invention is demonstrated in detail, giving an Example, a comparative example, and a test example, this invention is not limited only to a following example.
[0107]
<Example 1>
As a glass ceramic component, SiO₂-Al₂O_Three-MgO-B₂O_Three-ZnO-based glass powder 60% by mass, CaZrO_Three20% by mass of powder, SrTiO_Three17% by weight of powder and Al₂O_Three3% by weight of powder was used. To 100 parts by mass of this glass ceramic component, 12 parts by mass of an acrylic resin as an organic binder, 6 parts by mass of a phthalic plasticizer and 30 parts by mass of toluene as a solvent were added and mixed by a ball mill method to form a slurry. Using this slurry, a glass ceramic green sheet having a thickness of 300 μm was formed by a doctor blade method.
[0108]
Next, a conductor pattern 2 was formed on the green sheet by screen printing using a copper paste. In addition, Al with respect to 100 parts by mass of powder (average particle size 1.0 μm)₂O_Three2 parts by mass of powder and 2 parts by mass of glass powder having the same composition as the glass, and a predetermined amount of ethyl cellulose resin and terpineol as vehicle components were added and mixed so as to have an appropriate viscosity using three rolls.
[0109]
As glass ceramic paste, as glass ceramic component, SiO₂-Al₂O_Three-MgO-B₂O_Three-ZnO-based glass powder 60% by mass, CaZrO_Three20% by mass of powder, SrTiO_Three17% by weight of powder and Al₂O_Three3% by weight of powder was used. To 100 parts by mass of this glass ceramic powder, 12 parts by mass of an acrylic resin as an organic binder, 2 parts by mass of a phthalic acid plasticizer, and terpineol as a solvent were added and mixed so as to obtain an appropriate viscosity using three rolls.
[0110]
Al as an inorganic component₂O_ThreeSiO with 95% by mass of powder and 720 ° C softening point₂-Al₂O_Three-MgO-B₂O_ThreeA slurry was prepared using 5% by mass of ZnO-based glass powder in the same manner as the glass ceramic green sheet, and then molded to obtain a constrained green sheet having a thickness of 250 μm. The dielectric loss tangent of this constrained green sheet to microwaves was almost the same as that of the glass ceramic / green sheet laminate.
[0111]
A glass ceramic green sheet laminate is obtained by stacking a predetermined number of glass ceramic green sheets for the surface layer and glass ceramic green sheets for the inner layer formed with a conductor pattern and a glass ceramic coating layer on the surface. The constrained green sheets were superposed and pressure-bonded at a temperature of 55 ° C. and a pressure of 20 MPa to obtain a laminate.
[0112]
The obtained laminate was placed on the inner shell of an alumina-based material that self-heated by microwaves, irradiated with 2.45 GHz microwaves and heated in a nitrogen atmosphere at 400 ° C. for 2 hours to remove organic components, and then 900 Baked at 1 ° C. for 1 hour. The supply amount of the firing atmosphere gas was 7 times the volume of the housing per minute.
[0113]
Moreover, the housing | casing produced with the silicon carbide type material was used, and it baked using nitrogen gas as baking atmosphere gas.
[0114]
After firing, constraining sheets were attached to both surfaces of the glass ceramic substrate. In this state, the restraint sheet did not peel off even when tapped lightly.
[0115]
The restraint sheet attached to the surface of the glass ceramic substrate is made of spherical Al.₂O_ThreeThe mixture of fine powder and water was removed by the wet blast method in which the mixture was projected with high pressure air pressure. The surface of the glass ceramic substrate after removing the restraint sheet was a smooth surface with a surface roughness Ra of 1 μm or less, and there was no problem with the solder wettability of the conductor. Further, no peeling or cracking occurred in the glass ceramic coating layer.
[0116]
Further, the shrinkage in the laminated surface of the obtained glass ceramic substrate was 0.5% or less, and no warpage or deformation was observed in the substrate.
[0117]
<Examples 2 and 3>
A glass ceramic substrate was obtained in the same manner as in Example 1 except that constrained green sheets were prepared using glasses having softening points of 600 ° C. and 700 ° C., respectively.
[0118]
When the constraining sheet was removed, no peeling or cracking occurred in the glass ceramic coating layer.
[0119]
<Comparative Example 1>
A glass ceramic substrate was obtained in the same manner as in Example 1 except that a casing made of an aluminum nitride-based material was used and firing was performed using nitrogen gas as the firing atmosphere gas.
[0120]
<Comparative Example 2>
A glass ceramic substrate was obtained in the same manner as in Example 1 except that a constrained green sheet containing no glass was produced.
[0121]
<Comparative Example 3>
A glass ceramic substrate was obtained in the same manner as in Example 1 except that a constrained green sheet was produced using glass having a softening point of 920 ° C.
[0122]
<Comparative example 4>
A glass ceramic substrate was obtained in the same manner as in Example 1 except that a constrained green sheet was produced using glass having a softening point of 400 ° C.
[0123]
As a result, the glass-ceramic substrate obtained in Examples 2 and 3 had a shrinkage within the laminated surface of 0.5% or less (that is, a shrinkage rate of 99.5% or more) as in Example 1, and the substrate was not warped or deformed. I was not able to admit. Further, no peeling or cracking occurred in the glass ceramic coating layer.
[0124]
On the other hand, the glass ceramic substrate obtained in Comparative Example 1 using a case made of an aluminum nitride-based material has a temperature between the inside and the surface of the laminate of the constrained green sheet and the glass ceramic / green sheet laminate. It became difficult to fire while effectively suppressing the difference, shrinkage was 0.7%, and the dimensional accuracy was poor. Further, a warp of the substrate of 200 μm occurred with respect to the substrate size of 150 mm × 120 mm. The warpage of the substrate was measured with a stylus type surface roughness meter.
[0125]
Further, the glass ceramic substrates obtained in Comparative Examples 2 and 3 contain either glass after the firing, since the constrained green sheet used does not contain glass or contains glass having a softening point higher than the firing temperature. The constrained green sheet easily peeled off from the glass ceramic substrate. Also, since the bonding force between the glass ceramic green sheet and the constraining green sheet is weak, the shrinkage rate within the laminated surface of the glass ceramic substrate is about 85%, or only a part of the substrate is bonded to the constraining sheet. As a result, the glass ceramic substrate was greatly deformed.
[0126]
On the other hand, in Comparative Example 4, since the softening point of the glass contained in the constrained green sheet is low, the organic component is not completely removed. Therefore, the shrinkage within the laminated surface of the glass ceramic substrate is as good as 0.5% or less. However, the color tone of the glass ceramic substrate turned gray.
[0127]
<Examples 4 to 7>
As a glass ceramic component, SiO₂-MgO-CaO-Al₂O_Three-Based glass powder 70% by mass, Al₂O_Three30% by weight of powder was used. To 100 parts by mass of the glass ceramic component, 9.0 parts by mass of an acrylic resin as an organic binder, 4.5 parts by mass of a phthalic acid plasticizer, and 30 parts by mass of toluene as a solvent were added and mixed by a ball mill method to obtain a slurry. Using this slurry, a glass ceramic green sheet having a thickness of 300 μm was formed by a doctor blade method.
[0128]
Next, a conductor pattern was formed on the green sheet by screen printing using the same copper paste as in Example 1.
[0129]
Moreover, the housing | casing produced with the silicon carbide type material was used, and it baked using nitrogen gas as baking atmosphere gas.
[0130]
Next, using the same glass ceramic paste as in Example 1, a glass ceramic coating layer having the same thickness was formed by screen printing.
[0131]
On the other hand, Al as an inorganic component₂O_ThreePowder and SiO with a softening point of 720 ° C₂-MgO-CaO-Al₂O_ThreeSlurry was prepared in the same manner as the glass ceramic green sheet using the glass glass powder in the ratio shown in Table 1, and then molded to obtain a constrained green sheet having a thickness of 250 μm.
[0132]
A glass ceramic green sheet laminate is obtained by stacking a predetermined number of glass ceramic green sheets for the surface layer and glass ceramic green sheets for the inner layer formed with a conductor pattern and a glass ceramic coating layer on the surface. The constrained green sheets were superposed and pressure-bonded at a temperature of 55 ° C. and a pressure of 20 MPa to obtain a laminate. This laminate was a rectangle having a size of 150 mm × 120 mm.
[0133]
The resulting laminate was placed on the inner shell of an alumina-based material that self-heated by microwaves, irradiated with 2.45 GHz microwaves and heated in a nitrogen atmosphere at 400 ° C. for 2 hours to remove organic components, and then 850 Baked at 1 ° C. for 1 hour.
[0134]
Moreover, the housing | casing produced with the silicon carbide type material was used, and it baked using nitrogen gas as baking atmosphere gas.
[0135]
After firing, constraining sheets were attached to both surfaces of the glass ceramic substrate. In this state, the restraint sheet did not peel off even when tapped lightly. Subsequently, the restraint sheet adhering to the surface of the glass ceramic substrate was removed. The surface of the obtained glass ceramic substrate was a smooth surface with a surface roughness Ra of 1 μm or less, and there was no problem with the solder wettability of the conductor. And, the organic binder suddenly generated heat due to oxidative decomposition and no swelling occurred in the laminate, and the metal powder in the ceramic molded body did not undergo thermal expansion due to oxidation, and there was no defect in the internal structure of the product. .
[0136]
In addition, Table 1 shows the shrinkage ratio in the laminated surface of the obtained glass ceramic substrate. Note that no warpage or deformation was observed in the glass ceramic substrate.
[0137]
[Table 1]

[0138]
From the results shown in Table 1, it can be seen that the glass ceramic substrates obtained by using the constrained green sheets of Examples 4 to 7 have high dimensional accuracy because shrinkage and warpage during firing are suppressed. .
[0139]
<Example 8>
A conductor pattern was formed by screen printing using silver-palladium paste instead of copper powder as the conductor paste. As the conductor paste, 100 parts by mass of an alloy powder (average particle size: 1.0 μm) having a mass ratio of Ag: Pd of 85:15,₂O_Three2 parts by weight of powder and 2 parts by weight of glass powder having the same composition as that of the glass were added, and further, as a vehicle component, a predetermined amount of ethyl cellulose resin and terpineol were added and mixed so as to have an appropriate viscosity by three rolls.
[0140]
Moreover, as a laminated body for baking, except the conductor paste, it processed on the conditions similar to Example 1. FIG.
[0141]
This was placed on the inner shell of an alumina material that self-heated by microwaves, irradiated with 2.45 GHz microwaves, heated in the atmosphere at 400 ° C for 2 hours to remove organic components, and then fired at 850 ° C for 1 hour. A glass ceramic substrate was obtained in the same manner as in Example 4 except that.
[0142]
Moreover, the housing | casing produced with the silicon carbide type material was used, and it baked in air | atmosphere as baking atmosphere gas.
[0143]
In addition, as in Example 4, the shrinkage in the laminated surface is 0.5% or less (that is, the shrinkage rate is 99.5% or more), and the metal powder is not oxidized or diffused in the ceramic molded body, so that the insulation deterioration of the product is not caused. No warpage or deformation was observed on the substrate.
[0144]
<Example 9>
Al as an inorganic component of restraint green sheet₂O_ThreeA glass ceramic substrate was obtained in the same manner as in Example 1 except that 95% by mass of SiC powder having a higher dielectric loss tangent to microwave was used instead of 95% by mass of powder.
[0145]
As in Example 1, the obtained glass ceramic substrate had a shrinkage in the laminated surface of 0.5% or less, and was excellent in that no warpage or deformation was observed. Further, the glass ceramic substrate of Example 1 The shrinkage variation was smaller and better.
[0146]
<Examples 10 to 13>
Twenty glass ceramic substrates were obtained in the same manner as in Example 1 except that the supply amount of the firing atmosphere gas was set to 1 time, 5 times, 10 times, and 15 times the volume of the casing per minute. .
[0147]
As in Example 1, the obtained glass ceramic substrate had a variation in firing shrinkage within the laminated surface of 0.1% or less, and was satisfactory without warping or deformation of the substrate.
[0148]
<Examples 14 to 16>
Twenty glass ceramic substrates were obtained in the same manner as in Example 1 except that the tensile elongation of the glass ceramic green sheet was 10%, 30%, and 40%.
[0149]
As in Example 1, the obtained glass ceramic substrate had a variation in firing shrinkage within the lamination plane of 0.1% or less, and was excellent in that no cracks, cracks, warpage or deformation was observed in the substrate.
[0150]
<Comparative Example 5>
Twenty glass ceramic substrates were obtained in the same manner as in Example 1 except that the supply amount of the firing atmosphere gas was changed to 0.5 times the volume of the casing per minute.
[0151]
<Comparative Example 6>
Twenty glass ceramic substrates were obtained in the same manner as in Example 1 except that the supply amount of the firing atmosphere gas was 17 times the volume of the casing per minute.
[0152]
As a result, the glass ceramic substrate obtained in Comparative Example 5 in which the supply amount of the firing atmosphere gas was 0.5 times the volume of the casing per minute had a sufficiently uniform atmosphere in which the supply amount of the firing atmosphere gas was sufficiently uniform. Since it was less than the amount necessary to form, the variation in firing shrinkage was 0.2%, which was within the range of no problem, but tended to deteriorate slightly.
[0153]
In addition, the glass ceramic substrate obtained in Comparative Example 6 in which the supply amount of the firing atmosphere gas is 17 times the volume of the housing per minute is the lamination of the constrained green sheet and the glass ceramic / green sheet laminate. Since the temperature is locally lowered in the vicinity of the body and it is difficult to maintain a constant state within a desired temperature range, the variation in firing shrinkage was within 0.15%, which was within a satisfactory range, but tends to deteriorate slightly. It was in.
[0154]
<Example 17>
Twenty glass ceramic substrates were obtained in the same manner as in Example 1 except that the tensile elongation of the glass ceramic green sheet was 8%.
[0155]
<Example 18>
Twenty glass ceramic substrates were obtained in the same manner as in Example 1 except that the tensile elongation of the glass ceramic green sheet was 42%.
[0156]
As a result, in the glass ceramic substrate obtained in Example 17 in which the tensile elongation of the glass ceramic green sheet was 8%, the variation in firing shrinkage within the laminated surface was 0.1% or less. Since the sheet tends to become too hard, fine cracks and cracks tend to occur.
[0157]
In addition, the glass ceramic substrate obtained in Example 18 in which the tensile elongation of the glass ceramic green sheet was 42%, the glass ceramic green sheet tends to be plastically deformed depending on the lamination pressure and temperature, and the variation of firing shrinkage is variable. Although it was 0.15%, which was within the range of no problem, it tended to deteriorate slightly.
[0158]
<Test Example 1>
(Restriction green sheet shrinkage test)
Al as an inorganic component₂O_ThreePowder and SiO with a softening point of 720 ° C₂-MgO-CaO-Al₂O_ThreeGlass powder is used at a predetermined ratio, 9.0 parts by weight of acrylic resin as organic binder, 4.5 parts by weight of phthalic acid plasticizer, and 30 parts by weight of toluene as solvent are mixed in a ball mill to obtain slurry. did. A constrained green sheet having a thickness of 250 μm was formed from this slurry by a doctor blade method.
[0159]
This constrained green sheet alone was placed on an alumina setter, heated in air at 500 ° C. for 2 hours to remove organic components, and then fired at 850 ° C. for 1 hour.
[0160]
FIG. 2 shows the relationship between the shrinkage rate in the plane of the obtained constraining sheet and the glass addition amount. In addition, the shrinkage ratio shows the average value (n = 5) of each shrinkage ratio in the width direction and the flow direction excluding the thickness direction of the constraining sheet and variation, and the formula is: (size after firing) × 100 / (before firing) Dimension). Moreover, the flow direction means the film forming direction of the green sheet, and the width direction means a direction perpendicular to the film forming direction.
[0161]
As shown in FIG. 2, in order to reduce the shrinkage rate to 99.5% or more, that is, to suppress the shrinkage of the constraining sheet to 0.5% or less, the amount of glass added to the constraining green sheet is desirably about 15% by mass or less. I understand that. Moreover, when the glass addition amount exceeds 15 mass%, the variation in shrinkage tends to increase. However, if the glass addition amount decreases, the glass ceramic green sheet restraint by the constrained green sheet decreases (see Comparative Example 1 above), so it is necessary to determine the glass addition amount that does not decrease the restraint, In this invention, 0.5-15 mass% is made a suitable range.
[0162]
<Test Example 2>
SiO as glass₂-Al₂O_Three-MgO-B₂O_ThreeWhen the relationship between the glass addition amount and the shrinkage rate was examined in the same manner as in Test Example 1 except that the ZnO-based glass powder was used, the shrinkage rate of the constrained green sheet was 99.5% when the glass addition amount was 15% by mass or less. Thus, about 99.8% was maintained when the glass addition amount was 10% by mass or less.
[0163]
【The invention's effect】
According to the method for producing a glass ceramic substrate of the present invention, a laminate of a constrained green sheet and a glass ceramic / green sheet laminate is surrounded by a microwave-absorbing casing, and the laminate is irradiated with microwaves through the casing. By removing the organic components and firing, it is possible to effectively suppress the temperature difference between the inside and the surface of the laminate of the constrained green sheet and the glass ceramic / green sheet laminate and to perform firing. Therefore, variation in firing shrinkage of the laminate can be suppressed to an extremely small value, and a highly reliable glass ceramic substrate with high dimensional accuracy can be obtained.
[0164]
This is because the heat generated by absorption by the microwave-absorbing casing surrounding the laminate heats the surface of the laminate, and as a result, the temperature is lower than the inside due to heat dissipation from the surface. This is because the temperature gradient between the surface of the laminated body and the inside of the laminated body can be effectively suppressed to an extremely small one.
[0165]
According to the method for producing a glass ceramic substrate of the present invention, when the dielectric loss tangent to the microwave of the hardly sinterable inorganic material of the constrained green sheet is larger than that of the glass ceramic green sheet laminate, The temperature of the surface of the laminate, which tends to be lower than the interior due to heat dissipation from the surface, due to the heat generation of the constrained green sheet being greater than that of the glass ceramic / green sheet laminate, and the temperature inside the laminate Since the gradient can be more effectively suppressed to a very small one, variation in the firing shrinkage of the laminate can be suppressed to a very small one, and a highly reliable glass ceramic substrate with high dimensional accuracy can be obtained. Can do.
[0166]
Furthermore, according to the method for manufacturing a glass ceramic substrate of the present invention, when the firing atmosphere gas is supplied into the housing at a volume of 1 to 15 times the volume of the casing per minute, For example, the working gas is supplied into the housing from the opening of the rectangular housing, and the laminate of the constrained green sheet and the glass ceramic / green sheet laminate is heated against the firing atmosphere gas in the housing. Decomposed gas generated by decomposition or depolymerization reaction is exhausted from the opening on the side surface facing each other without staying in the housing, and restrained green sheet and glass under a uniform concentration of firing atmosphere gas Since the ceramic green sheet laminate can be fired, the variation in firing shrinkage of the laminate can be suppressed to a very small size, and high dimensional accuracy can be achieved. It is possible to obtain a glass ceramic substrate of high reliability.
[0167]
Furthermore, according to the method for producing a glass ceramic substrate of the present invention, when the softening point of the glass contained in the constrained green sheet is equal to or lower than the firing temperature of the glass ceramic / green sheet laminate, the glass ceramic / green sheet lamination is performed. The glass is welded by heating in the vicinity of the laminate interface between the constrained green sheet and the glass ceramic / green sheet laminate before the body starts to be fired, so the XY direction which is the in-plane direction of the laminate Thus, firing without substantially shrinking can be performed more reliably, and dimensional variations of the glass ceramic substrate obtained by firing the glass ceramic / green sheet laminate can be effectively suppressed. As described above, it becomes possible to effectively suppress peeling of the constrained green sheet from the glass ceramic / green sheet laminate during firing, thus preventing sintering shrinkage in the XY direction of the glass ceramic / green sheet laminate. It is possible to suppress the deformation of the glass ceramic substrate.
[0168]
Furthermore, according to the method for manufacturing a glass ceramic substrate of the present invention, when the softening point of the glass contained in the constrained green sheet is higher than the volatilization temperature of the organic component, the glass ceramic is softened before the glass is softened. -Organic components in the green sheet laminate are not taken into glass ceramics due to volatilization. As a result, it is possible to effectively prevent the organic component from remaining in the glass ceramic / green sheet laminate, so that it can be fired without being affected by the organic component, thereby preventing shrinkage unevenness and at the same time glass ceramic. It is possible to effectively suppress the warpage and deformation of the substrate.
[0169]
Furthermore, according to the method for producing a glass ceramic substrate of the present invention, when the glass content in the constrained green sheet is 0.5 to 15% by mass of the total inorganic components in the constrained green sheet, the constrained green sheet The glass in the vicinity of the lamination interface between the glass ceramic and green sheet laminate is welded by heat, so that sintering shrinkage within the laminated surface of the glass ceramic and green sheet can be reliably restrained. This makes it possible to effectively prevent peeling of the constrained green sheet during firing, and to suppress sintering shrinkage of the glass ceramic / green sheet laminate. As a result, it is possible to effectively prevent the warp, deformation, etc. of the glass ceramic substrate, so that the shrinkage of the glass ceramic / green sheet laminate can be surely suppressed, and the glass ceramic substrate with high dimensional accuracy. Can be obtained.
[0170]
Furthermore, according to the method for producing a glass ceramic substrate of the present invention, when the thickness of the constrained green sheet is 10% or more with respect to the thickness of the glass ceramic green sheet laminate on one side, When sintering shrinkage starts within the lamination surface of the green sheet, it is possible to effectively suppress the driving force that the glass ceramic green sheet laminate tries to shrink by firing in the XY direction with the restraint green sheet. It becomes. As a result, it is possible to effectively prevent the occurrence of warpage, deformation, etc. of the glass ceramic substrate, so that the shrinkage of the glass ceramic / green sheet laminate can be surely suppressed, and the glass ceramic substrate with high dimensional accuracy. Can be obtained.
[0171]
According to the method for producing a glass-ceramic substrate of the present invention, when the tensile elongation of the glass-ceramic green sheet is 10 to 40%, the glass-ceramic green sheet is less likely to cause plastic deformation due to lamination pressure or temperature, and temporarily. Therefore, even if it stretches, it functions as an elastic body that can be restored to its original position, so that it is possible to effectively suppress variation in the deformation of the glass ceramic green sheet during lamination. Further, since the glass ceramic green sheet is moderately soft, it is possible to effectively prevent the glass ceramic green sheet from being cracked or cracked. As a result, it is possible to produce a glass ceramic substrate having a wiring conductor with even better dimensional accuracy.
[0172]
As described above, according to the method for producing a glass ceramic substrate of the present invention, the sintering shrinkage in the laminated surface of the glass ceramic / green sheet laminate is surely restrained, and further the metal powder in the glass ceramic molded body Oxidation thermal expansion causes defects in the internal structure of the product and metal powders to oxidize and diffuse effectively to prevent deterioration of the product's insulation, and to provide a highly reliable glass ceramic substrate with high dimensional accuracy. It is possible to provide a method of obtaining.
[Brief description of the drawings]
FIG. 1A is a plan view showing an example of an embodiment of a method for producing a glass ceramic substrate according to the present invention, and is a plan view of a microwave irradiation firing furnace used in the method for producing a glass ceramic substrate according to the present invention. Is shown. (B) is a sectional view taken along the line A-A ′, and (c) is a sectional view taken along the line B-B ′.
FIG. 2 is a diagram showing an experimental example of the present invention and showing a relationship between a shrinkage rate in a plane of a constraining sheet and a glass addition amount.
[Explanation of symbols]
1 ... Laminated body of restraint green sheet and glass ceramic / green sheet laminate
2 ... Case
10 ... Baking atmosphere gas

Claims (7)

A step of forming a glass ceramic green sheet laminate by laminating a plurality of glass ceramic green sheets including a glass, a filler, and an organic binder and having a conductor pattern formed on the surface;
Laminating a constrained green sheet containing a non-sinterable inorganic material, glass and an organic binder on both sides of the glass ceramic green sheet laminate;
The laminate of the constraining green sheet and the glass ceramic green sheet laminate with surrounding microwave absorbent chassis, by irradiating a microwave to the laminate through the housing to remove organic components And a step of firing together to produce a glass ceramic substrate holding a restraint sheet;
And a step of removing the constraining sheet from the glass ceramic substrate,
The content of the glass contained in the constraining green sheet, the do not substantially shrink firing said constraining green sheet is bonded to the glass-ceramic green sheets and the constraining green sheet during its lamination plane amounts der The
The dielectric loss tangent to the microwave of the hardly sinterable inorganic material contained in the constrained green sheet is larger than the dielectric loss tangent to the microwave of the glass and filler contained in the glass ceramic green sheet laminate. A method for manufacturing a ceramic substrate. It said supplying housing sintering atmosphere gas into body in an amount of 1 to 15 times the volume of the volume of natural Symbol housing 1 minute, process for producing a glass ceramic substrate according to claim 1. The softening point of the glass contained in the constraining green sheet, the less than or equal firing temperature of the glass ceramic green sheet laminate, a manufacturing method of a glass ceramic substrate according to claim 1. The softening point of the glass contained in the constraining green sheet, higher than said volatilization temperature of the organic component, process for producing a glass ceramic substrate according to claim 1. The content of the glass contained in the constraining green sheet is from 0.5 to 15% by weight of the inorganic components contained in the constraining green sheet, the manufacturing method of a glass ceramic substrate according to claim 1. The constraining green sheet thickness is at least 10% of the thickness of the glass ceramic green sheet laminate in simplex method for producing a glass ceramic substrate according to claim 1. The tensile elongation of the glass ceramic green sheet is 10 to 40% process for producing a glass ceramic substrate according to claim 1.

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