乙二酸掺杂对KDP晶体光学和热学性质的影响

doi:10.16553/j.cnki.issn1000-985x.2025.0100

摘要/Abstract

摘要： 本文将不同浓度的乙二酸加入到磷酸二氢钾水溶液，通过“点籽晶”快速生长技术成功制备了乙二酸掺杂的KDP晶体。对于0%~2%（摩尔分数）掺杂浓度范围内得到的乙二酸掺杂KDP样品，粉末X射线衍射（PXRD）和傅里叶变换红外光谱（FT-IR）分析表明乙二酸分子已成功地掺入KDP晶体中，晶体结构没有显著影响，晶体样品保持了良好的结晶度。为了探究乙二酸掺杂对晶体光学和热学性能的影响，采用紫外可见近红外（UV-Vis-NIR）分光光度计和差示扫描量热仪（DSC）测量了样品的光学透过率和热学稳定性，结果表明当掺入低浓度的乙二酸后晶体的透过率有明显提高，当掺杂浓度为1%时光学透过率达到最优值，而掺杂过高浓度的乙二酸时光学透过率有所下降。DSC结果表明在一定的掺杂浓度范围内晶体的热稳定性有所提高。

关键词: 乙二酸; KDP晶体; 掺杂; 点籽晶; 光学透过率; 热稳定性

Abstract: Oxalic acid doped KDP crystals were successfully prepared by adding different concentrations of oxalic acid into potassium dihydrogen phosphate solution with "point seed" rapid growth technique. Powder X-ray diffraction （PXRD） and Fourier transform infrared spectroscopy （FT-IR） analysis of oxalic acid doped KDP samples in the range of 0%~2% （mole fraction） indicate that oxalic acid molecules have been successfully incorporated into KDP crystals， the crystal structure has no significant change， and the crystal samples maintain good crystallinity. In order to investigate the effect of oxalic acid doping on the optical and thermal properties of the crystal， the optical transmittance and thermal stability of the crystal were measured by UV-Vis-NIR spectrophotometer and differential scanning calorimeter （DSC）. The results show that the transmittance of the crystal is significantly improved when low concentration of oxalic acid is added. When the doping concentration is 1%， the optical transmittance reaches the optimal value， while when the doping concentration is too high， the optical transmittance decreases. DSC shows that the thermal stability of the crystals is improved in a certain doping concentration range.

Key words: oxalic acid; KDP crystal; doping; point seed; optical transmittance; thermal stability

中图分类号:

O734

周广刚, 文歆艾, 毛彩菊, 陈文轩, 王晓春, 陈松昊, 周湘雨, 张万松, 吴冲. 乙二酸掺杂对KDP晶体光学和热学性质的影响[J]. 人工晶体学报, 2025, 54(11): 1916-1922.

ZHOU Guanggang, WEN Xin’ai, MAO Caiju, CHEN Wenxuan, WANG Xiaochun, CHEN Songhao, ZHOU Xiangyu, ZHANG Wansong, WU Chong. Effect of Oxalic Acid Doping on Optical and Thermal Properties of KDP Crystals[J]. Journal of Synthetic Crystals, 2025, 54(11): 1916-1922.

图/表 6

图1 不同浓度乙二酸掺杂的KDP晶体

Fig.1 Different concentrations of oxalic acid doped KDP crystals

图2 不同浓度乙二酸掺杂的KDP晶体的PXRD图谱

Fig.2 PXRD patterns of KDP crystals doped with different concentrations of oxalic acid

图3 不同浓度乙二酸掺杂的KDP晶体的FT-IR光谱

Fig.3 FT-IR spectra of KDP crystals doped with different concentrations of oxalic acid

表1 不同浓度乙二酸掺杂的KDP晶体的振动频率

Table 1 Vibration frequency of KDP crystals doped with different concentrations of oxalic acid

Functional group assignment	IR vibration frequency/cm^-1
Functional group assignment	Pure KDP	1% oxalic acid	2% oxalic acid	3% oxalic acid
O—H symmetric stretching vibration	3 422.81	3 457.99	3 441.06	3 449.52
P＝O asymmetric stretching vibration	2 923.62	2 868.33	2 790.90	2 886.20
O＝P—OH asymmetric stretching vibration	2 348.69	2 417.86	2 426.33	2 444.20
C—H vibration	—	1 975.86	2 019.13	2 088.71
O＝P—OH stretching vibration	1 636.87	1 602.50	1 611.91	1 646.70
COO^- asymmetric stretching vibration	—	1 437.93	1 429.46	1 431.63
O＝P＝O asymmetric stretching vibration	1 300.65	1 359.87	1 351.41	1 386.20
O＝P＝O symmetric stretching vibration	1 108.04	1 082.44	1 112.31	1 000.31
HO—P—OH vibration	905.37	944.20	917.83	917.86
HO—P—OH bending	534.12	536.05	533.92	545.45

图4 不同浓度乙二酸掺杂的KDP晶体的透过光谱

Fig.4 Transmission curves of KDP crystals doped with different concentrations of oxalic acid

图5 不同浓度乙二酸掺杂的KDP晶体的DSC曲线

Fig.5 DSC curves of KDP crystals doped with different concentrations of oxalic acid

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