Determination of oxygen mass fraction and distribution in aluminum nitride ceramics
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摘要: 氮化铝陶瓷以其优异的导热性能成为集成电路、半导体及大功率器件的重要封装材料，然而杂质氧含量（质量分数）直接影响着氮化铝陶瓷的导热性能。准确测定氮化铝陶瓷内氧含量（质量分数）及其分布十分重要。在惰性熔融红外吸收法基础上，对氮化铝陶瓷中不同形式氧含量分析方法进行了研究。通过步进式升温模式对样品中的表面吸附氧、晶界氧和晶格氧的氧含量进行分开测定，探讨了坩埚、裕料的选择及测试过程对结果的影响，分析了石墨粉含量对晶界氧的释放作用，最终优化了升温程序、加粉顺序以及称样量。通过氮化铝陶瓷样品多次平行试验对测定方法的准确性进行了验证，实测晶界氧和晶格氧含量的相对标准偏差分别为4.5%、8.5%，能够满足相关科研要求。Abstract: Aluminum nitride ceramics have become the important packaging materials for integrated circuits, semiconductors, and high-power devices due to the excellent thermal conductivity. The oxygen impurities in aluminum nitride ceramics directly affect the thermal conductivity. Thus, it is important to accurately determine the oxygen content (mass fraction) and distribution in aluminum nitride ceramics. Based on the inert melting infrared absorption method, the analysis methods of oxygen mass fraction in different forms in the aluminum nitride ceramics were studied. The mass fraction of surface adsorption oxygen, grain boundary oxygen, and lattice oxygen in the nitride ceramics was measured separately by the stepped heating method. The influence of crucible and auxiliary material selection on the measurement process and test results was discussed. The effect of graphite powder content on the release of grain boundary oxygen was analyzed. Finally, the heating program, the order of adding powder, and weight were optimized. The measurement method accuracy was verified by the multiple parallel tests on the aluminum nitride ceramics. In the results, the relative standard deviations of the measured grain boundary oxygen and lattice oxygen content are 4.5% and 8.5%, respectively, meeting the requirements of the relevant scientific research.
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Key words:
- aluminum nitride /
- oxygen distribution /
- inert melting /
- infrared absorption method
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图 1 氮化铝中氧信号分离示意图
Figure 1. Schematic diagram of the oxygen signal separation in aluminum nitride
图 3 氮化铝陶瓷微观形貌（a）与物相分析（b）
Figure 3. Microstructure (a) and phase composition (b) of the AlN ceramics
图 4 坩埚外观结构：（a）套坩埚；（b）标准坩埚；（c）高温坩埚
Figure 4. Crucible appearance structure: (a) set of internal and external crucible; (b) standard crucible; (c) high temperature crucible
图 5 三种坩埚所用功率及对应温度曲线：（a）套坩埚；（b）标准坩埚；（c）高温坩埚
Figure 5. Power and the corresponding temperature curves of three type crucibles: (a) set of internal and external crucible; (b) standard crucible; (c) high temperature crucible
图 6 中温段功率对氧氮释放曲线的影响：（a）2300 W；（b）2500 W；（c）2800 W
Figure 6. Effect of power on the oxygen and nitrogen release curves at the medium temperature: (a) 2300 W; (b) 2500 W; (c) 2800 W
图 7 低晶格氧试样高温段氧氮释放曲线：（a）4000 W氧释放曲线；（b）4000 W氮释放曲线；（c）4500 W氧释放曲线；（d）4500 W氮释放曲线
Figure 7. Oxygen and nitrogen release curves of the low lattice oxygen samples at the high temperature: (a) oxygen release curve at 4000 W; (b) nitrogen release curve at 4000 W; (c) oxygen release curve at 4500 W; (d) nitrogen release curve at 4500 W
图 8 加入镍助熔剂时氧氮释放曲线：（a）步进式升温氧释放曲线；（b）步进式升温氮释放曲线；（c）斜率升温氧释放曲线；（d）斜率升温氮释放曲线
Figure 8. Oxygen and nitrogen release curve when adding nickel flux: (a) oxygen release curve with the step-up temperature rise; (b) nitrogen release curve with the step-up temperature rise; (c) oxygen release curve with the slope temperature rise; (d) nitrogen release curve with the slope temperature rise
图 9 无裕料时氧氮释放曲线及坩埚状态：（a）氧；（b）氮；（c）坩埚状态
Figure 9. Oxygen and nitrogen release curves and the crucible state without auxiliary materials: (a) oxygen; (b) nitrogen; (c) crucible state
图 10 裕料选择对氮释放曲线的影响：（a）不加入裕料；（b）加入锡裕料；（c）加入锡铜二元裕料
Figure 10. Effect of the auxiliary materials selection on the nitrogen release curves: (a) without auxiliary; (b) with tin auxiliary; (c) with tin and copper auxiliary
图 11 裕料选择对氧释放曲线的影响及坩埚状态：（a）不加入裕料；（b）加入石墨粉；（c）加入石墨粉与锡铜裕料；（d）坩埚状态
Figure 11. Effect of the auxiliary materials selection on the oxygen release curves and the crucible state: (a) without auxiliary; (b) with graphite powder; (c) with graphite powder, tin, and copper auxiliary; (d) crucible state
图 12 不同裕料加入顺序下的氮分峰曲线：：（a）石墨粉-试样-铜锡裕料；（b）试样-石墨粉-铜锡裕料
Figure 12. Nitrogen peak curves added with the auxiliary materials in different order: (a) graphite powder-samples-auxiliary; (b) samples-graphite powder-auxiliary
图 13 氮化铝试样总氧含量（质量分数）测定曲线
Figure 13. Total oxygen content (mass fraction) measurement curve of the AlN samples
图 14 氮化铝陶瓷样品氧含量（质量分数）释放曲线
Figure 14. Oxygen content (mass fraction) release curves of the aluminum nitride ceramic samples
表 1 实验所用设备及辅料信息
Table 1. Equipments and the auxiliary materials used in the experiments
名称 型号 制造商或品牌 分析仪 TCH600 美国LECO 分析软件 Version4.15 美国LECO 计算机 Optiplex 330 联想 稳压电源 CWY型10KVA交流 铁塔 电子天平 — 赛得利斯 外部冷却水 RW-5000F 泰州郁金香 助熔剂 镍篮（502-344） 美国LECO 助熔剂 铜屑（9T-1362） 美国WELL GROUP 助熔剂 锡屑（9T-1076） 美国WELL GROUP 助熔剂 锡片（761-739） 美国WELL GROUP 助熔剂 石墨粉（501-073） 美国LECO 试样 氮化铝粉末（粒度小于75 μm） 北京科技大学新材料技术研究院 
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表 2 石墨粉对氧氮质量分数的影响
Table 2. Influence of graphite powder on the mass fraction of oxygen and nitrogen
石墨粉量 / g 称样量 / g 石墨粉与称样量质量比 元素质量分数 / % 表面氧 晶界氧 晶格氧 氮 0.0905 0.0247 3.6 0.52194 0.51674 0.03472 26.4160 0.0372 0.0255 1.5 0.43488 0.58182 0.03909 25.3210 0.0314 0.0248 1.3 0.42869 0.52170 0.03550 31.0100 0.0285 0.0252 1.1 0.41158 0.56148 0.03914 31.6160 0.0214 0.0246 0.9 0.39485 0.41520 0.10998 30.2350
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表 3 称样量对氧氮质量分数的影响
Table 3. Effect of weighing sample on the mass fraction of oxygen and nitrogen
称样量 / g 元素质量分数 / % 总氧 氮 晶格氧 0.0104 1.4102 34.5970 0.0457 0.0153 1.5647 34.2720 0.0657 0.0205 1.6099 32.5520 0.0735 0.0250 1.6388 32.9300 0.0767 0.0287 1.6234 33.2630 0.0721 0.0301 1.7011 30.5090 0.0835 0.0347 1.7782 27.8130 0.0894
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表 4 氮化铝试样氧含量（质量分数）分布测定结果
Table 4. Measurement results of the oxygen content distribution (mass fraction) for the AlN samples
氧质量分数 / % 相对标准偏差，RSD / % 表面吸附氧 晶界氧 晶格氧 表面吸附氧 晶界氧 晶格氧 0.0404 0.6117 0.1369 86.0 4.5 8.5 0.0159 0.5965 0.1618 0.0133 0.6231 0.1291 0.0099 0.6591 0.1454 0.0030 0.5891 0.1484 平均值0.0165 平均值0.6159 平均值0.1443
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