电子级磷酸的结晶精制技术发展现状与研究进展

doi:10.11949/0438-1157.20241138

化工学报 ›› 2025, Vol. 76 ›› Issue (2): 438-453.DOI: 10.11949/0438-1157.20241138

电子级磷酸的结晶精制技术发展现状与研究进展

董举¹(), 余留洋¹, 贾晟哲¹, 史连军²^,³, 王诗瀚²^,³, 胡国涛²^,³, 汤伟伟¹(), 王静康¹, 龚俊波¹()

^1.天津大学化工学院，化学工程联合国家重点实验室，天津 300072
^2.中低品位磷矿及其共伴生资源高效利用国家重点实验室，贵州贵阳 550016
^3.瓮福（集团）有限责任公司，贵州贵阳 550000

收稿日期:2024-10-15 修回日期:2024-11-14 出版日期:2025-02-25 发布日期:2025-03-10
通讯作者: 汤伟伟,龚俊波
作者简介:董举（2002—），男，硕士研究生，dongju@tju.edu.cn
基金资助:
中低品位磷矿及其共伴生资源高效利用国家重点实验室开放课题基金项目(2015DQ820763)

Current status and research progress of crystallization technology of electronic grade phosphoric acid

Ju DONG¹(), Liuyang YU¹, Shengzhe JIA¹, Lianjun SHI²^,³, Shihan WANG²^,³, Guotao HU²^,³, Weiwei TANG¹(), Jingkang WANG¹, Junbo GONG¹()

^1.State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
^2.State Key Laboratory of Efficient Utilization for Low Grade Phosphate Rock and Its Associated Resources, Guiyang 550016, Guizhou, China
^3.Wengfu (Group) Co. , Ltd. , Guiyang 550000, Guizhou, China

Received:2024-10-15 Revised:2024-11-14 Online:2025-02-25 Published:2025-03-10
Contact: Weiwei TANG, Junbo GONG

摘要/Abstract

摘要：

电子级磷酸作为电子工业常用的一种超高纯试剂，广泛应用于大屏幕液晶显示器和超大规模集成电路等微电子工业中的湿法蚀刻和清洗。随着电子元器件加工精度的迭代更新，对电子级磷酸中杂质含量与微粒的要求也在日益提高。综述了电子级磷酸深度净化的常用方法，重点阐述了结晶精制技术在电子级磷酸深度净化中的优势和应用进展，总结了结晶法在磷酸深度净化过程中的杂质包藏与迁移机制，并概述了结晶纯化的过程强化手段。最后，对电子级磷酸结晶精制技术的发展作出了前景展望。

关键词: 电子级磷酸, 电子材料, 结晶, 纯化, 过程强化

Abstract:

As an ultra-high purity reagent commonly used in electronics industry, electronic grade phosphoric acid is widely used in wet etching and cleaning in microelectronics industry such as large-screen liquid crystal display and huge scale integration circuit. With the iterative update of the processing precision of electronic components, the requirements for impurity content and particles in electronic grade phosphoric acid are also increasing. In this paper, the common methods for the deep purification of electronic grade phosphoric acid are reviewed, the advantages and application progress of crystallization refining technology in the deep purification of electronic grade phosphoric acid are emphasized, the mechanism of impurity accumulation and migration in the process of crystallization purification is summarized, and the strengthening means of crystallization purification process is outlined. Finally, the prospect of the development of crystallization refining technology of electronic grade phosphoric acid is presented.

Key words: electronic grade phosphoric acid, electronic material, crystallization, purification, process intensification

中图分类号:

TQ 026.5

董举, 余留洋, 贾晟哲, 史连军, 王诗瀚, 胡国涛, 汤伟伟, 王静康, 龚俊波. 电子级磷酸的结晶精制技术发展现状与研究进展[J]. 化工学报, 2025, 76(2): 438-453.

Ju DONG, Liuyang YU, Shengzhe JIA, Lianjun SHI, Shihan WANG, Guotao HU, Weiwei TANG, Jingkang WANG, Junbo GONG. Current status and research progress of crystallization technology of electronic grade phosphoric acid[J]. CIESC Journal, 2025, 76(2): 438-453.

图/表 22

图1 一种湿法磷酸工艺流程[7]

Fig.1 A kind of wet phosphoric acid process flow[7]

图2 Si3N4与SiO2膜的蚀刻速率(a)与Si3N4对SiO2的刻蚀选择性(b)随NH4HF2在含有质量分数0.15% Si(OH)4的H3PO4溶液中浓度的变化；Si3N4与SiO2膜的蚀刻速率(c)与Si3N4对SiO2的刻蚀选择性(d)随Si(OH)4在含有质量分数0.30% NH4HF2的H3PO4溶液中浓度的变化[11](1 Å =0.1 nm)

Fig.2 Etch rates of Si3N4 and SiO2 films (a) and etch selectivity of Si3N4 to SiO2 (b) with the addition of NH4HF2 in the presence of 0.15%(mass) of Si(OH)4 in H3PO4; Etch rates of Si3N4 and SiO2 films (c) and etch selectivity of Si3N4 to SiO2 (d) with the concentration of Si(OH)4 in the presence of 0.30%(mass) of NH4HF2 in H3PO4[11]

表1 《电子级磷酸》质量标准（GB/T 28159—2011）

Table1 Quality standard for Electronic Grade Phosphoric Acid （GB/T 28159—2011）

项目	指标
项目	E1	E2
磷酸（H₃PO₄）质量分数（85%）/(%)	85~87	85~87
易氧化物（以H₃PO₄计）质量分数/%	≤0.005	≤0.001
硝酸盐（ $N O_{3}^{-}$ ）质量分数/(mg/kg)	≤5	≤0.5
硫酸盐（ $S O_{4}^{2 -}$ ）质量分数/(mg/kg)	≤10	≤5
氯化物（Cl^-）质量分数/(mg/kg)	≤1	≤0.5
铝（Al）/(μg/kg)	≤200	≤50
硼（B）/(μg/kg)	—	≤50
锑（Sb）/(μg/kg)	≤3000	≤300
砷（As）/(μg/kg)	≤100	≤20
钡（Ba）/(μg/kg)	≤100	≤20
镉（Cd）/(μg/kg)	≤100	≤20
钙（Ca）/(μg/kg)	≤1000	≤50
铬（Cr）/(μg/kg)	≤100	≤20
钴（Co）/(μg/kg)	≤100	≤20
铜（Cu）/(μg/kg)	≤50	≤20
镓（Ga）/(μg/kg)	≤100	≤10
金（Au）/(μg/kg)	≤100	≤10
铁（Fe）/(μg/kg)	≤300	≤50
铅（Pb）/(μg/kg)	≤100	≤20
锂（Li）/(μg/kg)	≤100	≤10
镁（Mg）/(μg/kg)	≤100	≤20
锰（Mn）/(μg/kg)	≤100	≤20
镍（Ni）/(μg/kg)	≤100	≤20
钾（K）/(μg/kg)	≤100	≤20
银（Ag）/(μg/kg)	≤100	≤20
钠（Na）/(μg/kg)	≤500	≤50
锡（Sn）/(μg/kg)	—	≤10
锶（Sr）/(μg/kg)	≤100	≤20
钛（Ti）/(μg/kg)	≤100	≤50
锌（Zn）/(μg/kg)	≤100	≤50

表1 《电子级磷酸》质量标准（GB/T 28159—2011）

Table1 Quality standard for Electronic Grade Phosphoric Acid （GB/T 28159—2011）

项目	指标
项目	E1	E2
磷酸（H₃PO₄）质量分数（85%）/(%)	85~87	85~87
易氧化物（以H₃PO₄计）质量分数/%	≤0.005	≤0.001
硝酸盐（ $N O_{3}^{-}$ ）质量分数/(mg/kg)	≤5	≤0.5
硫酸盐（ $S O_{4}^{2 -}$ ）质量分数/(mg/kg)	≤10	≤5
氯化物（Cl^-）质量分数/(mg/kg)	≤1	≤0.5
铝（Al）/(μg/kg)	≤200	≤50
硼（B）/(μg/kg)	—	≤50
锑（Sb）/(μg/kg)	≤3000	≤300
砷（As）/(μg/kg)	≤100	≤20
钡（Ba）/(μg/kg)	≤100	≤20
镉（Cd）/(μg/kg)	≤100	≤20
钙（Ca）/(μg/kg)	≤1000	≤50
铬（Cr）/(μg/kg)	≤100	≤20
钴（Co）/(μg/kg)	≤100	≤20
铜（Cu）/(μg/kg)	≤50	≤20
镓（Ga）/(μg/kg)	≤100	≤10
金（Au）/(μg/kg)	≤100	≤10
铁（Fe）/(μg/kg)	≤300	≤50
铅（Pb）/(μg/kg)	≤100	≤20
锂（Li）/(μg/kg)	≤100	≤10
镁（Mg）/(μg/kg)	≤100	≤20
锰（Mn）/(μg/kg)	≤100	≤20
镍（Ni）/(μg/kg)	≤100	≤20
钾（K）/(μg/kg)	≤100	≤20
银（Ag）/(μg/kg)	≤100	≤20
钠（Na）/(μg/kg)	≤500	≤50
锡（Sn）/(μg/kg)	—	≤10
锶（Sr）/(μg/kg)	≤100	≤20
钛（Ti）/(μg/kg)	≤100	≤50
锌（Zn）/(μg/kg)	≤100	≤50

表2 SEMI对于湿电子化学品的纯度要求［20］

Table 2 The purity of wet electronic chemicals in Semiconductor Equipment Materials International［20］

级别	单项金属杂质	控制微粒粒径	颗粒数	IC集成度
Grade1	≤100 ppb	≥1 μm	≤25/ml	64 K
Grade2	≤10 ppb	≥0.5 μm	≤25/ml	4 M
Grade3	≤1 ppb	≥0.5 μm	≤5/ml	256 M
Grade4	≤0.1 ppb	≥0.2 μm		16 G
Grade5	≤0.01 ppb

图3 [Me2NH2]V3O7的结构示意图[28]

Fig.3 Structure diagram of [Me2NH2]V3O7[28]

图4 溶剂萃取法纯化磷酸流程示意图[31]

Fig.4 Schematic diagram of purification process of phosphoric acid by solvent extraction[31]

表3 水溶液中不同比例Na+、Al3+、Mg2+、F-混合后的沉淀情况与去除效果［32］

Table 3 Precipitation situations and removal efficiencies of Al3+， Mg2+ and F- for the Na x Al y Mg z F w in aqueous solution［32］

Molar ratio	Al³⁺ removal efficiency/%	Mg²⁺ removal efficiency/%	F^- removal efficiency/%	Phenomenon
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 1∶1∶1∶1	0	0	0	no precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 2∶1∶1∶2	0	0	0	no precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 3∶1∶1∶3	0	0	0	no precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 4∶1∶1∶4	48.9	44.5	38.4	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 5∶1∶1∶5	65.4	55.4	58.1	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 6∶1∶1∶6	99.4	83.8	88.7	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 7∶1∶1∶6	98.1	83.4	88.2	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 5∶1∶1∶6	99.6	80.1	82.6	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 5∶1∶1∶7	99.5	96.7	84.5	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 5∶1.5∶1∶6	96.98	93.68	95.17	precipitation
Na⁺∶Al³⁺∶Mg²⁺∶F^-= 6∶1.5∶1∶7	96.94	93.55	85.23	precipitation

图5 用于磷酸净化的逐层纳滤膜[24]

Fig.5 Layer-by-layer nanofiltration membranes for phosphoric acid purification[24]

图6 结晶法生产电子级磷酸工艺流程示意图[25]

Fig.6 The process flow for producing electronic grade phosphoric acid by crystallization[25]

图7 H3PO4-H2O体系相图[37]

Fig.7 Phase diagram of H3PO4-H2O system[37]

图8 液膜结晶（FFMC）与静态熔融结晶（SMC）示意图[40]

Fig.8 Diagram of FFMC and SMC[40]

图9 悬浮熔融结晶程序示意图[35]

Fig.9 Schematic diagram of suspension melting crystallization procedure[35]

表4 层熔融结晶技术与悬浮熔融结晶技术的比较［50］

Table 4 Comparison of layer melt crystallization technology and suspension melt crystallization technology［50］

项目	层熔融结晶	悬浮熔融结晶
熔融体温度	高于或低于关键组分熔点附近	低于关键组分熔点附近
结晶热转移	通过晶层	通过熔液
晶体生长速率	快，10^-7～10^-5 m/s	慢，10^-8~10^-7 m/s
晶体熔液相界面积	小，10~10² m²/m³	大，约10⁴ m²/m³
转动装置	无	有
传质速率	大	小
结垢现象	无	有
流体输送	易，均为液体	难，固液混合物
固液分离	易，液体单独排出	难
装置放大	容易	较难

图10 典型的溶质迁移和杂质迁移示意图[54]

Fig.10 Schematic diagram of typical solute and impurity migration[54]

图11 结晶过程中各种杂质掺入方法的示意图[62]

Fig.11 Schematic diagram of various impurity incorporation methods during crystallization[62]

图12 列管结晶生产电子级磷酸的装置结构示意图[42]1—结晶槽;2—喷淋器;3—红外灯管;4—立式列管;5—冷却介质出口;6—出酸口;7—出酸泵;8—循环泵;9—循环酸出口;10—调酸罐;11—产品出口;12—进料口;13—进水口;14—排气口;15—循环酸进口;16—进酸口;17—晶种投加口;18—冷却介质入口

Fig.12 Schematic diagram of a tube crystallization device for producing electronic grade phosphoric acid[42]1—crystallization tank; 2—spray thrower; 3—infrared lamp; 4—vertical tube; 5—cooling medium outlet; 6—acid outlet; 7—acid pump; 8—circulation pump; 9—recycle acid export; 10—acid tank; 11—product export; 12—feed port; 13—water inlet; 14—exhaust port; 15—circulating acid inlet; 16—acid inlet; 17—seed feeding port; 18—cooling medium inlet

图13 肥料磷酸提纯制电子级磷酸流程示意图[71]

Fig.13 Schematic diagram of purifying fertilizer phosphoric acid to produce electronic grade phosphoric acid[71]

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电子级磷酸的结晶精制技术发展现状与研究进展

Current status and research progress of crystallization technology of electronic grade phosphoric acid

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