铜浆料用ZnO-B_(2)O_(3)-SiO_(2)-BaO玻璃的结构和性能

Structure and Properties of ZnO-B_(2)O_(3)-SiO_(2)-BaO Glass for Copper Paste

本文以铜浆料用ZnO-B_(2)O_(3)-SiO_(2)-BaO玻璃为对象,通过X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、拉曼光谱(Raman)、核磁共振铝谱(27Al NMR)、差示扫描量热(DSC)和扫描电子显微镜(SEM)等表征方法,研究了ZnO含量对其结构和性能的影响。结果表明,随着ZnO含量的增加,玻璃试样中BO/NBO(摩尔比)、玻璃试样的平均桥氧数和[ZnO_(4)]/[ZnO_(6)]摩尔比均先增大后减小,[BO_(4)]/[BO_(3)]摩尔比增大,[AlO_(6)]和[AlO_(5)]摩尔占比增大,[AlO_(4)]摩尔占比降低。玻璃试样网络结构连接度整体先致密后疏松,且当ZnO的质量分数为36%时玻璃试样网络结构最为致密。当ZnO质量分数从32%增加到42%时,玻璃试样的DSC曲线中玻璃化转变温度T_(g)、起始烧结温度T_(S1)和热膨胀系数(CTE)均先降低后升高,CTE数值范围为6.0×10^(-6)~6.3×10^(-6)K^(-1),符合铜浆料与Ca_(1-x)Sr_(x)ZrO_(3)陶瓷基板封接时的热膨胀与烧结温度等要求。

The effect of ZnO content on structure and properties of ZnO-B_(2)O_(3)-SiO_(2)-BaO glass as a research object for copper paste was studied by X-ray diffraction(XRD),fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),raman spectroscopy(Raman),27 Al nuclear magnetic resonance aluminum spectroscopy(27 Al NMR),differential scanning calorimetry(DSC)and scanning electron microscopy(SEM).The results show that with the increase of ZnO content,the molar ratio of BO/NBO,the average bridge oxygen number and the molar ratio of[ZnO_(4)]/[ZnO_(6)]all increases first and then decreases,the molar ratio of[BO_(4)]/[BO_(3)]increases,the molar proportion of[AlO_(6)]and[AlO_(5)]increases and the molar proportion of[AlO_(4)]decreases in glass samples,which results in the trend first dense and then loose in the connection degree of network structure of glass samples.Among them,the network structure is the densest when the ZnO content is 36%(mass fraction).With the increase of ZnO content from 32%to 42%(mass fraction),the glass transition temperature T_(g),initial sintering temperature T_(S1)and the coefficient of thermal expansion(CTE)decrease first and then increase,and the CTE value range is 6.0×10^(-6)~6.3×10^(-6)K^(-1).It meets the requirements of thermal expansion and sintering temperature for sealing copper paste with Ca_(1-x)Sr_(x)ZrO_(3)ceramic substrate.