Preparation and purification of 6N electronic-grade deuterium gas

doi:10.11949/0438-1157.20230685

Abstract

Abstract:

Electronic-grade deuterium gas is of paramount importance in the integrated circuit industry during the high-temperature annealing process, the purity standard for deuterium gas reaches as high as 6N in the 7 nm and even more advanced processes. In this study, a comprehensive technological process for the electrolytic preparation and purification of 6N deuterium gas was proposed, including: (1) designing FeNi@ClBC as a highly efficient OER catalysts, surpassing the performance of the commercial catalyst (RuO₂), enhancing the catalytic efficiency while reducing the overall energy consumption; (2) introducing a gas stripping method using electrolytic anode oxygen to remove impurities such as nitrogen from heavy water, and by reducing impurities in heavy water, the purification difficulty of deuterium is significantly diminished; (3) proposing in-depth oxygen and moisture removal processes, screening the optimal catalyst and molecular sieve for the adsorption of oxygen and moisture, and the process parameters are optimized to achieve target oxygen and moisture contents (volume fraction) below 1×10^-8 and 1.65×10^-7, respectively. The ultra-high-purity deuterium gas product index obtained in the experiment reached 6N, which meets the manufacturing needs of advanced process integrated circuits and provides a reference for the low-cost production of ultra-high-purity deuterium gas.

Key words: electrolysis, preparation, catalysis, adsorption, purification, separation

摘要：

电子级氘气在集成电路制造的高温退火工艺中起到关键作用，高端制程工艺要求其纯度高达6N。提出了完整的6N氘气电解制备与纯化技术路线，包括：（1）设计出高效FeNi@ClBC OER催化剂，性能显著优于商用催化剂，提高了催化效率并降低整体能耗；（2）提出了电解阳极端氧气气提脱除重水中氮气等杂质的工艺流程，重水杂质的减少降低了氘气纯化的难度；（3）提出了深度脱氧、脱水工艺流程，筛选出最佳脱氧催化剂和脱水吸附分子筛并对工艺参数进行了优化，实现产品中杂质氧和水含量（体积分数）分别低于1×10^-8和1.65×10^-7的目标。实验得到的超高纯氘气产品指标达到了6N，满足先进制程集成电路制造需求，为低成本生产超高纯氘气提供了参考。

关键词: 电解, 制备, 催化, 吸附, 纯化, 分离

CLC Number:

TQ 028.8

Xiangjun MENG, Yingxi HUA, Changjin ZHANG, Chi ZHANG, Linrui YANG, Ruoxi YANG, Jianyi LIU, Chunjian XU. Preparation and purification of 6N electronic-grade deuterium gas[J]. CIESC Journal, 2024, 75(1): 377-390.

孟祥军, 花莹曦, 张长金, 张弛, 杨林睿, 杨若昔, 刘鉴漪, 许春建. 6N电子级氘气的制备与纯化技术研究[J]. 化工学报, 2024, 75(1): 377-390.

Figures/Tables 23

References 32

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技术指标	要求
化学纯度/%（体积分数）	99.9999
丰度/%	99.8
O₂（体积分数）	0.2×10^-6
N₂（体积分数）	0.2×10^-6
CO₂（体积分数）	0.1×10^-6
CO（体积分数）	0.1×10^-6
总碳氢化合物（体积分数）	0.2×10^-6
水分（体积分数）	0.2×10^-6

技术指标	要求
化学纯度/%（体积分数）	99.9999
丰度/%	99.8
O₂（体积分数）	0.2×10^-6
N₂（体积分数）	0.2×10^-6
CO₂（体积分数）	0.1×10^-6
CO（体积分数）	0.1×10^-6
总碳氢化合物（体积分数）	0.2×10^-6
水分（体积分数）	0.2×10^-6

技术指标	先进制程集成电路用6N电子级氘气技术指标	电解产生粗品氘气
化学纯度/%（体积分数）	99.9999	99.69
丰度/%	99.8	99.1
O₂（体积分数）	0.2×10^-6	3000
N₂（体积分数）	0.2×10^-6	4.6×10^-6
CO₂（体积分数）	0.1×10^-6	3.2×10^-6
CO（体积分数）	0.1×10^-6	2.9×10^-6
总碳氢化合物（体积分数）	0.2×10^-6	2.7×10^-6
水分（体积分数）	0.2×10^-6	16900×10^-6

技术指标	先进制程集成电路用6N电子级氘气技术指标	电解产生粗品氘气
化学纯度/%（体积分数）	99.9999	99.69
丰度/%	99.8	99.1
O₂（体积分数）	0.2×10^-6	3000
N₂（体积分数）	0.2×10^-6	4.6×10^-6
CO₂（体积分数）	0.1×10^-6	3.2×10^-6
CO（体积分数）	0.1×10^-6	2.9×10^-6
总碳氢化合物（体积分数）	0.2×10^-6	2.7×10^-6
水分（体积分数）	0.2×10^-6	16900×10^-6

原料N₂含量（体积分数）×10⁶	产品N₂含量（体积分数）×10⁶
原料N₂含量（体积分数）×10⁶	60%	65%	70%	75%	80%	90%
200	78.88	71.21	61.30	51.40	41.49	21.67
100	39.44	35.60	30.65	25.70	20.74	10.84
50	19.72	17.80	15.33	12.85	10.37	5.42
20	7.89	7.12	6.13	5.14	4.15	2.17
5	1.97	1.78	1.53	1.28	1.037	0.54