本文選題：低熱膨脹系數(shù) + LTCC基板材料��； 參考：《電子科技大學(xué)》2016年博士論文

【摘要】：隨著技術(shù)的進(jìn)步,微電子器件向著高度集成化、小型化方向發(fā)展,這對基板材料提出了新的要求。經(jīng)過多年研究,國外的一些科研機(jī)構(gòu)已經(jīng)實(shí)現(xiàn)了LTCC基板材料的商用化,但是國內(nèi)在這一領(lǐng)域仍然處于追趕狀態(tài)。因此,制備出滿足LTCC基板要求的材料并研究其機(jī)理,已經(jīng)成為了一個(gè)極為重要的課題。Li2O-Al2O3-SiO2(LAS)和CaO-Al2O3-SiO2(CAS)微晶玻璃具有低熱膨脹系數(shù)、低介電常數(shù)的特點(diǎn),具有應(yīng)用于LTCC基板材料領(lǐng)域的潛力。因此本文采用玻璃熔融法和固相反應(yīng)法分別制備了LAS微晶玻璃和CAS微晶玻璃,并研究了玻璃組成、燒結(jié)制度對其晶體析出、微觀結(jié)構(gòu)、燒結(jié)及性能的影響,主要獲得了如下成果:一、LAS微晶玻璃1)MgO的添加可以降低微晶玻璃的析晶溫度,有利于致密化燒結(jié),并能促進(jìn)透輝石晶相析出,并使得材料的抗彎強(qiáng)度由75 MPa提高到155 MPa。通過調(diào)節(jié)MgO的摻雜量及燒結(jié)制度,可以改變其中的晶相種類和含量,進(jìn)而實(shí)現(xiàn)熱膨脹系數(shù)可在0.5~4.3×10-6·K-1之間調(diào)節(jié)。2)微晶玻璃的玻璃化轉(zhuǎn)變溫度和析晶溫度隨著ZnO含量的增大而降低。過量的ZnO添加會(huì)導(dǎo)致ZnAl2O4晶相析出。適量添加ZnO會(huì)增大材料密度,有利于材料燒結(jié)致密化,最佳燒結(jié)溫度為800℃,保溫時(shí)間是30 min。由于Zn2+離子半徑大,阻礙堿金屬離子的移動(dòng),其含量的增大會(huì)使材料的介電損耗降低。微晶玻璃的抗彎強(qiáng)度受到晶相性能的影響,具有較大彈性模量的ZnAl2O4晶相的析出使得材料的抗彎強(qiáng)度增大,同時(shí)由于較大熱膨脹系數(shù)的晶相析出,體系的熱膨脹系數(shù)隨著ZnO含量的增大而升高。3)由于CaO的解聚作用,其含量的增大會(huì)導(dǎo)致體系析晶傾向增大,并促進(jìn)透輝石相析出。CaO的添加會(huì)降低玻璃的粘度,使得液相含量增多,這有利于致密化燒結(jié)。由于析出的透輝石晶相與主晶相的介電常數(shù)相差不大,CaO的添加對材料的介電常數(shù)影響較小,因此介電常數(shù)主要取決于材料的致密化程度。透輝石含量的增大也會(huì)導(dǎo)致材料熱膨脹系數(shù)的增大。4)利用氧化物摻雜和燒結(jié)制度的調(diào)節(jié),實(shí)現(xiàn)了LAS微晶玻璃熱膨脹系數(shù)在較大范圍內(nèi)可調(diào)。在800℃保溫?zé)Y(jié)30 min的微晶玻璃樣品獲得了最佳的性能:高的抗彎強(qiáng)度(155 MPa),介電常數(shù)較低(7.2),介電損耗較低(2×10-3),低的熱膨脹系數(shù)(3.2×10-6·K-1)。具有這些優(yōu)秀性能的LAS微晶玻璃可以滿足LTCC基板材料的要求。二、LAS微晶玻璃+Al2O3陶瓷復(fù)合材料文獻(xiàn)指出,在低熱膨脹系數(shù)體系中引入高熱膨脹系數(shù)晶相,會(huì)增大微晶玻璃抗彎強(qiáng)度。出于提高材料抗彎強(qiáng)度的目的,將具有較大熱膨脹系數(shù)的Al2O3陶瓷添加到LAS微晶玻璃中,制備了LAS微晶玻璃+Al2O3陶瓷復(fù)合材料。由于來源于玻璃的液相對致密化燒結(jié)有利,玻璃的減少會(huì)增大材料的析晶溫度,使得燒結(jié)溫度增大。Al2O3陶瓷含量的增大會(huì)導(dǎo)致具有大介電常數(shù)和熱膨脹系數(shù)的Al2O3晶相的析出,并使得材料的抗彎強(qiáng)度、介電常數(shù)和熱膨脹系數(shù)均出現(xiàn)增大。Al2O3含量為20 wt%的材料樣品具有最佳的性能:高的抗彎強(qiáng)度(173 MPa),低的介電常數(shù)(8),低的介電損耗(2.4×10-3),低的熱膨脹系數(shù)(2.9×10-6·K-1),可以滿足LTCC基板材料的要求。三、CAS微晶玻璃1)Al2O3/SiO2比的增大會(huì)連接玻璃中的斷網(wǎng),使得析晶變得困難,并降低玻璃的粘度,使得材料的收縮率下降。材料的組成和燒結(jié)制度的變化會(huì)使得體系中的晶相含量和種類發(fā)生變化,從而影響材料的性能。2)調(diào)整氧化物ZnO的添加會(huì)削弱了網(wǎng)絡(luò)結(jié)構(gòu),從而降低玻璃的玻璃化轉(zhuǎn)變溫度和析晶溫度,并導(dǎo)致石英和鈣長石晶相析出量增大。ZnO增大導(dǎo)致高熱膨脹系數(shù)的晶相析出,使得材料的熱膨脹系數(shù)增大。3)通過改變玻璃組成和燒結(jié)制度,可以調(diào)節(jié)玻璃中晶相的種類與含量,并獲得不同的性能。在900℃保溫?zé)Y(jié)2 h的CAS微晶玻璃樣品具有最佳的性能:高的抗彎強(qiáng)度(145 MPa),低的介電常數(shù)(5.5),低的介電損耗(3.4×10-3)以及低的熱膨脹系數(shù)(5.3×10-6·K-1),可以滿足LTCC基板材料的要求。四、熱膨脹系數(shù)計(jì)算和析晶動(dòng)力學(xué)的研究1)通過XRD法測試微晶玻璃中晶相和玻璃相的含量,并以此計(jì)算材料的熱膨脹系數(shù),結(jié)果表明,計(jì)算值和實(shí)測值大體吻合。這說明微晶玻璃的熱膨脹系數(shù)主要取決于其晶相的熱膨脹系數(shù),控制晶體析出即可獲得想要的熱膨脹系數(shù)。2)ZnO摻雜使LAS微晶玻璃的析晶活化能由219.5 kJ/mol降到143.1 kJ/mol,LAS微晶玻璃的析晶指數(shù)n值在3.1~3.5之間,說明該玻璃析晶機(jī)制為整體析晶。ZnO摻雜使CAS微晶玻璃的析晶活化能由339 kJ/mol降到275 k J/mol,CAS微晶玻璃的析晶指數(shù)n值在1.41~1.82之間,說明該玻璃析晶機(jī)制為表面析晶。
[Abstract]:With the progress of technology, microelectronic devices are becoming highly integrated and miniaturized. This has put forward new requirements for substrate materials. After years of research, some research institutions abroad have realized the commercialization of LTCC substrate materials, but in this field the domestic pursuit state is still in the field. Therefore, to prepare the LTCC substrate to meet the requirements. The material obtained and the study of its mechanism have become a very important subject,.Li2O-Al2O3-SiO2 (LAS) and CaO-Al2O3-SiO2 (CAS) glass ceramics have low thermal expansion coefficient, low dielectric constant, and have the potential to be applied in the field of LTCC substrate materials. Therefore, the glass melting method and solid state reaction method have been used to prepare LAS micro respectively. Glass and CAS glass ceramics, and study the composition of glass, the influence of the sintering system on its crystal precipitation, microstructure, sintering and properties, mainly obtained the following results: the addition of LAS microcrystalline glass 1) MgO can reduce the crystallization temperature of glass ceramics, is beneficial to the dense sintering, and can promote the precipitation of diopside crystal phase, and make the material The bending strength is increased from 75 MPa to 155 MPa. by adjusting the doping amount and sintering system of MgO, the type and content of crystalline phase can be changed, and then the thermal expansion coefficient can be adjusted to.2 between 0.5~4.3 * 10-6. K-1. The glass transition temperature and crystallization temperature of glass ceramics can be reduced with the increase of ZnO content. The excess ZnO addition will be added. The ZnAl2O4 crystal phase precipitates. Proper addition of ZnO will increase the density of the material, which is beneficial to the densification of the material, the optimum sintering temperature is 800 C, the holding time is 30 min. because of the large radius of the Zn2+ ion, which hinders the movement of alkali metal ions. The increase of the content will reduce the dielectric loss of the material. The bending strength of the glass ceramics is subjected to the crystalline phase properties. The effect of the precipitation of ZnAl2O4 crystal phase with larger modulus of elasticity increases the bending strength of the material. At the same time, the thermal expansion coefficient of the system increases with the increase of the content of ZnO because of the crystallization of the larger thermal expansion coefficient. Because of the depolymerization of CaO, the increase of the content of the system will lead to the increase of the crystallization tendency of the system and promote the diopside. The addition of.CaO will reduce the viscosity of the glass and increase the content of the liquid phase, which is beneficial to the densification and sintering. As the precipitated diopside crystal phase differs little from the permittivity of the main crystal phase, the addition of CaO has little influence on the dielectric constant of the material, so the dielectric constant is mainly determined by the densification degree of the material. The thermal expansion coefficient of material is increased by.4). Using the regulation of oxide doping and sintering, the thermal expansion coefficient of LAS glass ceramics can be adjusted in a larger range. The optimum performance of the glass ceramics samples at 800 C for 30 min is obtained: high flexural strength (155 MPa), low dielectric constant (7.2) and dielectric loss Low (2 * 10-3), low thermal expansion coefficient (3.2 x 10-6. K-1). The LAS glass ceramics with these excellent properties can meet the requirements of LTCC substrate materials. Two, LAS glass ceramics +Al2O3 ceramic composite materials indicate that the introduction of high thermal expansion coefficient crystal phase in the low thermal expansion coefficient system will increase the flexural strength of glass ceramics. For the purpose of bending strength, the Al2O3 ceramics with large thermal expansion coefficient were added to LAS glass ceramics to prepare LAS glass ceramics +Al2O3 ceramic composites. The crystallization temperature of the materials will be increased because of the relative densification of the liquid source from the glass, and the sintering temperature increases the content of.Al2O3 ceramics. It will lead to the precipitation of Al2O3 crystalline phase with large dielectric constant and thermal expansion coefficient, and the material samples with increased flexural strength, dielectric constant and thermal expansion coefficient that increase.Al2O3 content to 20 wt% have the best properties: high bending strength (173 MPa), low dielectric constant (8), low dielectric loss (2.4 x 10-3), low thermal expansion. The expansion coefficient (2.9 x 10-6. K-1) can meet the requirements of the LTCC substrate material. Three, CAS glass 1) the increase of the Al2O3/SiO2 ratio will connect the broken net in the glass, make the crystallization difficult, reduce the viscosity of the glass, and reduce the shrinkage of the material. The composition of the material and the change of the sintering system will make the crystal phase content and type in the system The addition of ZnO will weaken the network structure, thus reduce the glass transition temperature and crystallization temperature, and lead to the increase of the precipitation of quartz and calcite crystal phase and the increase of.ZnO, resulting in the crystallization of the high thermal expansion coefficient and the increase of the thermal expansion coefficient of the material by the modification of the crystal phase, and the increase of the thermal expansion coefficient of the material by the modification of the crystal phase, and the increase of the thermal expansion coefficient of the material by the modification of the crystal phase, and the increase of the thermal expansion coefficient of the material by the modification of the crystal phase, and the increase of the thermal expansion coefficient of the material by the modification of the crystal phase, and the increase of the thermal expansion coefficient of the material by the modification of the crystal phase. The variable glass composition and sintering system can adjust the type and content of glass MICROTEK phase and obtain different properties. The CAS glass ceramics samples of 2 h heat preservation and sintering at 900 C have the best properties: high bending strength (145 MPa), low dielectric constant (5.5), low dielectric loss (3.4 * 10-3) and low thermal expansion coefficient (5.3 * 10-6. K-1), It can meet the requirements of LTCC substrate materials. Four, thermal expansion coefficient calculation and Crystallization Kinetics Study 1) test the content of glass phase and MICROTEK phase in glass ceramics by XRD method, and calculate the thermal expansion coefficient of the material. The results show that the calculated value is in agreement with the measured value. This shows that the thermal expansion coefficient of glass ceramics depends mainly on the thermal expansion coefficient of glass ceramics. The thermal expansion coefficient of crystal phase can be obtained by controlling the crystal precipitation. The desired thermal expansion coefficient.2) ZnO doping can reduce the crystallization activation energy of LAS glass ceramics from 219.5 kJ/mol to 143.1 kJ/mol, and the crystallization exponent n value of LAS glass ceramics is between 3.1~3.5. It shows that the crystallization mechanism of the glass is the crystallization of.ZnO doped CAS microcrystalline glass. It can be reduced from 339 kJ/mol to 275 K J/mol, and the crystallization index n value of CAS glass ceramics is between 1.41~1.82, indicating that the crystallization mechanism of the glass is surface crystallization.
【學(xué)位授予單位】：電子科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TN405;TQ171.733

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