低温共烧陶瓷（LTCC）内电极银浆的制备及其性能研究
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摘要
近二十年来,随着新技术、新材料和新工艺的迅速发展,微电子材料在各个方面都得到了蓬勃的发展。低温共烧陶瓷(Low Temperature Co-fired Ceramic)技术由于其优异的热学、电学、机械及其工艺特性,将成为未来电子器件模块化、集成化的首选方式以及元器件产业新的经济增长点。国内LTCC技术的开发及产业化较发达国家晚,生产的浆料质量较差、品种少,仍然没有摆脱国外产品价高、受控制的局面。本论文以LTCC蓝牙天线内电极用银浆为研究对象,研究了化学还原沉淀法制备高分散高振实的超细结晶型银粉,设计和优化了玻璃粉的配方以及玻璃粉的制备工艺,通过添加助剂改性,制备了有机载体,将各组成相进行系统优化后,最后制备成LTCC内电极印刷电路用银浆。借助环境扫描电子显微镜、激光粒度分析仪、PF-100B型振实密度测试仪、Netzsch DTA 449PC示差扫描量热仪和D/Max 2500 X射线衍射仪对制得银粉的形貌、粒径和振实密度、玻璃粉的软化温区和析晶情况进行检测和分析；通过粘度仪和细度计测定了浆料的粘度和细度；利用SEM分析了浆料烧结膜的微观形貌；采用四探针测试仪和测力计测定了烧结膜的电性能和附着力,主要研究结果如下：
(1)采用化学沉淀法从硝酸银溶液中沉淀出银粉,用反应速率适中的抗坏血酸作为还原剂,明胶作为分散剂,可以制得分散性良好的银粉。当硝酸银与抗坏血酸的浓度比为2：1,明胶为硝酸银质量的2wt%时,用激光粒度分析仪测得银粉的平均粒径为2.68μm；化学反应溶液的pH为2时,可以制得所需结晶性银粉,当反应滴液速度控制在200mL/min,反应温度为50℃时,可以得到平均粒径为2.46μm的结晶性高分散类球状银粉。
(2)适于LTCC天线内电极浆料优化后的粘度为120Pa·s；用平均粒径为2.46μm的类球状高分散银粉制得浆料,浆料的丝网印刷性能和触变性良好,其烧结膜方阻为1.40mΩ/□；随着银粉振实密度的提高,烧结膜越致密,导电性越好,当用振实密度为5.1g/mL,平均粒径为2.25μm的银粉时,制得烧结膜的方阻可达1.35mΩ/□；当固粉中银粉与玻璃粉的质量比为82：3时,可以使烧结膜导电性能最好,为1.22 mΩ/□；当载体在浆料中的含量为15wt%时,电性能良好,方阻为1.02 mΩ/□。
(3)通过对3个体系6种不同玻璃粉进行比较分析,优选出的C系玻璃粉,其软化温度为650℃左右,长时间保温不会有析晶的情况,根据Turner模型计算得出其烧结膜的线膨胀系数与基片生瓷最为匹配；当C系玻璃粉中Li20含量为2wt%时,烧结厚膜与基片的线膨胀匹配性良好；当浆料中玻璃粉含量为8%时,烧结膜与基片的附着力最佳,为16.8N/mm2。
(4)将陶瓷生瓷片料作为添加剂加入到银浆中,可以抑制因浆料和生瓷片共烧时线膨胀系数不匹配而导致的翘曲现象；随着生瓷片料在浆料中添加量的增加,所得天线的中心频率先增加后迅速减小,当添加量为0.6wt%时,中心频率与设计值最接近,为2.44GHz；加入表面活性剂卵磷脂和蓖麻油对浆料流平性有一定的改善作用。通过提高烧结膜的高宽比来减少共烧后的翘曲现象,在浆料中加入丁基卡必醇有效提高浆料的触变性,当加入量为12wt%时,高宽比可以达到0.32。
As the rapid development of advanced material, new process and neoteric technique, microelectronic material got a booming market in the last 20 years. Technique of Low Temperature Co-fired Ceramic will become the top choice of modularization and a new economic growth point, because of its excellent character in electricity, machinery, thermology and craft. The domestic development and industrialization of LTCC lags behind that in developed countries, expecially in integrating module. We are unable to break loose from the high price and control of the foreign offerings for the scarce assortment and bad quality. In this thesis, taking the silver paste of LTCC bluetooth antenna inner electrode as the research objective, we researched the preparation method of high dispersing silver powder by chemical deposition, designed the ingredient and preparation process of glass frits, prepared organic vehicles though adding modifier, and optimized the constitutions of the goal silver paste. With the help of scanning electron microscope, laser scattering particle analyzer, PF-100B vibration solid density spectrometer, Netzsch DTA 449PC DSCmeter and D/Max 2500XRD,we observed and analysed the morphologies, mean grain sizes, tap density of silver powder, and the themal features of glass frits. By Viscometer and Fineness dispersion meter, the viscocity and fineness had been measured. Through SEM, we surveyed the morphology of sintered film. Four point probe meter and forcemeter measured the electroconductibility and adhesion of the sintered film. The results are as follows:
(1) Selecting ascorbic acid as reducing agent and gelatine as dispersing agent,we got the fine dispersing silver powder though chemical reduction method. When C(AgNO3):C(Vc)=2:1 and m(gelatin):m(AgNO3)=2:100,the mean grain sizes of fine dispersing silver powder is 2.68μm. When acidity of solution is 2, the drop rate is 200mL/min and temperature is 50℃, we can got crystalline silver powder of which the mean grain sizes is 2.46μm.
(2) The viscocity of LTCC paste optimised for inner electron is 120 Pa-s. The paste prepared by silver powder of 2.46μm could get fine screen printing and the resistance of its sinterd film could reach 1.40 mΩ/□. The higher the tap density of silver powder is, the finer the conductivity of sinterd film is. When the tap density of silver powder is 5.1 mΩ/□, the conductivity of its sinterd film was 1.02mΩ/□. When m(Ag):m(glass frits)=82:3, the sintered film obtains the best electronic property,1.22 mΩ/□. From the TG graph of organic vehical,1# vehical is much suitable to the LTCC sinter process and the residul is only 0.03%. When the content of vehical is 15wt%, the resistance of the sinterd film was 1.45 mΩ/□.
(3) The soften temperature of glass C which is not devitrification optimized from six kinds glass frits is about 650℃. The TEC of glass C calculated by Turner model can match that of the green tape. In addition, when the content of Li2O is 2wt% in glass, the coordination is fine between sinterd film and substrate with good electroconductivity. The adhesive of the sintered film can reach 16.8N/mm with 8wt% of glass frits in the paste.
(4) If the ceramic green tape is added into the silver paste as the addition,it can restrain the mismatch shrinkage and warpage due to the different materials in X and Y directions. With the increase of the green tape addtion content, the efficiency of the bluetooth antenna is first increased and then rapid decreased. When the content of addtion is 0.6wt%, it can approach to the designed velue,2.44GHz. Lecithin and castor oil as the surfactant of paste can improve the levelling property. For enhancing the aspect ratio of sintered film, dibutyl phthalate in the paste can increase the thixotropism. When the content of dibutyl phthalate is 12wt%, the aspect ratio of sintered film can reach 0.32.
(1)采用化学沉淀法从硝酸银溶液中沉淀出银粉,用反应速率适中的抗坏血酸作为还原剂,明胶作为分散剂,可以制得分散性良好的银粉。当硝酸银与抗坏血酸的浓度比为2：1,明胶为硝酸银质量的2wt%时,用激光粒度分析仪测得银粉的平均粒径为2.68μm；化学反应溶液的pH为2时,可以制得所需结晶性银粉,当反应滴液速度控制在200mL/min,反应温度为50℃时,可以得到平均粒径为2.46μm的结晶性高分散类球状银粉。
(2)适于LTCC天线内电极浆料优化后的粘度为120Pa·s；用平均粒径为2.46μm的类球状高分散银粉制得浆料,浆料的丝网印刷性能和触变性良好,其烧结膜方阻为1.40mΩ/□；随着银粉振实密度的提高,烧结膜越致密,导电性越好,当用振实密度为5.1g/mL,平均粒径为2.25μm的银粉时,制得烧结膜的方阻可达1.35mΩ/□；当固粉中银粉与玻璃粉的质量比为82：3时,可以使烧结膜导电性能最好,为1.22 mΩ/□；当载体在浆料中的含量为15wt%时,电性能良好,方阻为1.02 mΩ/□。
(3)通过对3个体系6种不同玻璃粉进行比较分析,优选出的C系玻璃粉,其软化温度为650℃左右,长时间保温不会有析晶的情况,根据Turner模型计算得出其烧结膜的线膨胀系数与基片生瓷最为匹配；当C系玻璃粉中Li20含量为2wt%时,烧结厚膜与基片的线膨胀匹配性良好；当浆料中玻璃粉含量为8%时,烧结膜与基片的附着力最佳,为16.8N/mm2。
(4)将陶瓷生瓷片料作为添加剂加入到银浆中,可以抑制因浆料和生瓷片共烧时线膨胀系数不匹配而导致的翘曲现象；随着生瓷片料在浆料中添加量的增加,所得天线的中心频率先增加后迅速减小,当添加量为0.6wt%时,中心频率与设计值最接近,为2.44GHz；加入表面活性剂卵磷脂和蓖麻油对浆料流平性有一定的改善作用。通过提高烧结膜的高宽比来减少共烧后的翘曲现象,在浆料中加入丁基卡必醇有效提高浆料的触变性,当加入量为12wt%时,高宽比可以达到0.32。
As the rapid development of advanced material, new process and neoteric technique, microelectronic material got a booming market in the last 20 years. Technique of Low Temperature Co-fired Ceramic will become the top choice of modularization and a new economic growth point, because of its excellent character in electricity, machinery, thermology and craft. The domestic development and industrialization of LTCC lags behind that in developed countries, expecially in integrating module. We are unable to break loose from the high price and control of the foreign offerings for the scarce assortment and bad quality. In this thesis, taking the silver paste of LTCC bluetooth antenna inner electrode as the research objective, we researched the preparation method of high dispersing silver powder by chemical deposition, designed the ingredient and preparation process of glass frits, prepared organic vehicles though adding modifier, and optimized the constitutions of the goal silver paste. With the help of scanning electron microscope, laser scattering particle analyzer, PF-100B vibration solid density spectrometer, Netzsch DTA 449PC DSCmeter and D/Max 2500XRD,we observed and analysed the morphologies, mean grain sizes, tap density of silver powder, and the themal features of glass frits. By Viscometer and Fineness dispersion meter, the viscocity and fineness had been measured. Through SEM, we surveyed the morphology of sintered film. Four point probe meter and forcemeter measured the electroconductibility and adhesion of the sintered film. The results are as follows:
(1) Selecting ascorbic acid as reducing agent and gelatine as dispersing agent,we got the fine dispersing silver powder though chemical reduction method. When C(AgNO3):C(Vc)=2:1 and m(gelatin):m(AgNO3)=2:100,the mean grain sizes of fine dispersing silver powder is 2.68μm. When acidity of solution is 2, the drop rate is 200mL/min and temperature is 50℃, we can got crystalline silver powder of which the mean grain sizes is 2.46μm.
(2) The viscocity of LTCC paste optimised for inner electron is 120 Pa-s. The paste prepared by silver powder of 2.46μm could get fine screen printing and the resistance of its sinterd film could reach 1.40 mΩ/□. The higher the tap density of silver powder is, the finer the conductivity of sinterd film is. When the tap density of silver powder is 5.1 mΩ/□, the conductivity of its sinterd film was 1.02mΩ/□. When m(Ag):m(glass frits)=82:3, the sintered film obtains the best electronic property,1.22 mΩ/□. From the TG graph of organic vehical,1# vehical is much suitable to the LTCC sinter process and the residul is only 0.03%. When the content of vehical is 15wt%, the resistance of the sinterd film was 1.45 mΩ/□.
(3) The soften temperature of glass C which is not devitrification optimized from six kinds glass frits is about 650℃. The TEC of glass C calculated by Turner model can match that of the green tape. In addition, when the content of Li2O is 2wt% in glass, the coordination is fine between sinterd film and substrate with good electroconductivity. The adhesive of the sintered film can reach 16.8N/mm with 8wt% of glass frits in the paste.
(4) If the ceramic green tape is added into the silver paste as the addition,it can restrain the mismatch shrinkage and warpage due to the different materials in X and Y directions. With the increase of the green tape addtion content, the efficiency of the bluetooth antenna is first increased and then rapid decreased. When the content of addtion is 0.6wt%, it can approach to the designed velue,2.44GHz. Lecithin and castor oil as the surfactant of paste can improve the levelling property. For enhancing the aspect ratio of sintered film, dibutyl phthalate in the paste can increase the thixotropism. When the content of dibutyl phthalate is 12wt%, the aspect ratio of sintered film can reach 0.32.
引文
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