马骏杰， 洪若瑜
福州大学 化工学院，福建 福州 350108
引用格式：
马骏杰， 洪若瑜. 等离子体法TiCl4-NH3体系制备TiN纳米颗粒［J］. 中国粉体技术， 2026， 32（6）： 1-13.
Get citation:Ma Junjie， Hong Ruoyu. Plasma preparation of TiN nanoparticles using a TiCl4-NH3 system［J］. China Powder Science and Technology， 2026， 32（6）： 1-13.
DOI：10.13732/j.issn.1008-5548.2026.06.002
收稿日期： 2026-03-20， 修回日期： 2026-04-11，上线日期： 2026-06-08。
基金项目：国家自然科学基金项目，编号：22278080；福建省战略性新兴产业研发基金项目，编号：82918001。
第一作者： 马骏杰（2001—），男，硕士生，研究方向为粉体材料的制备及应用。E-mail： 15666377801@163.com。
通信作者： 洪若瑜（1966—），男，嘉熙学者特聘教授，博士，博士生导师，研究方向为材料的制备与应用。E-mail： rhong@fzu.edu.cn。
摘要： 【目的】开发连续、 快速、高质量的TiN纳米颗粒制备工艺，解决传统非等离子体制备方法工艺流程繁琐、反应温度高、难以连续生产等问题。【方法】 搭建等离子体增强化学气相沉积反应装置，以TiCl4为钛源，NH3为氮源，N2为载气，在常压下合成TiN纳米颗粒，系统探究氮钛物质的量比、等离子体功率对产物化学组成与形貌特征的影响，并通过X射线衍射、X射线光电子能谱等手段表征产物性能。【结果】粗产物中副产物NH4Cl可通过高温煅烧完全去除；氮钛物质的量比大于或等于2时可制备出TiN晶体颗粒，随NH3比例增大，产物氧化现象被抑制，NH4Cl含量提升，并可以有效抑制颗粒团聚，粒径分布更均匀；同时提升等离子体功率可增强产物结晶性，但功率过低会导致结晶性差，晶粒细小，功率过高时颗粒粒径分布不均。【结论】 确定等离子体法制备TiN纳米颗粒的适宜条件，该方法简单高效、可连续生产，制备的产物纯度与结晶性符合生产要求，可为TiN纳米颗粒的规模化制备提供有效途径。
关键词： 氮化钛； 等离子体法； 纳米颗粒
Abstract
Objective The preparation of titanium nitride （TiN） nanoparticles is aresearch focus in advanced nanomaterial synthesis and an effective aproach to enhancing preparation efficiency and product quality. Compared with traditional non-plasma methods， plasma method features a simple process， low reaction activation energy， and continuous production， yielding high-purity， well-crystallized TiN nanoparticles. However， the main difficulty lies in regulating crystallization， particle size distribution， and oxidation via reaction parameters， which can cause poor crystallinity， severe agglomeration， and high oxidation during preparation. Based on plasma-enhanced chemical vapor deposition （PECVD），the study investigates the effects of the ammonia-titanium tetrachloride molar ratio of NH3 to TiCl4 and plasma power on the composition， morphology， and crystallinity of TiN nanoparticles， providing guidance for large-scale， high-quality preparation.
Methods In this study， a TiCl4-NH3 PECVD system was firstbuilt， and a variable-parameter experimental scheme was designed to investigate key influencing factors of TiN preparation. TiN nanoparticles were then synthesized under different TiCl4-NH3 molar ratios to identify the optimal range. Then， the effects of different plasma powers on product properties were examined to select a suitable power. X‑ray diffraction （XRD）， X-ray photoelectron spectroscopy （XPS）， scanning electron microscope （SEM）， and transmission electron microscope （TEM） were adopted to characterize the physicochemical properties of the synthesized TiN. The preparation parameters were optimized， and the properties of productsobtained under optimized and non-optimized conditions were compared to develop an efficient and stable plasma preparation process for TiN nanoparticles.
Results and Discussion The crude TiN products from the TiCl4-NH3 plasma system contained an ammonium chloride （NH4Cl） by product， which was fully eliminated by annealing at 350 ℃ for 2 h under an Ar atmosphere， yielding pure crystalline TiN. The molar ratio of NH3 to TiCl4 was critical to product performance：a ratio of 1 yielded amorphous TiN， while ratios ≥2 formed crystalline TiN with distinct diffractionpeaks. Increasing the ratio suppressed oxidation （lower TiO2 impurity content）， elevated the NH4Cl content， inhibited particle agglomeration， and improved size uniformity.XPS results indicated that the Ti-N bond content increased from 8.5% to 14.4%. No chlorine （Cl） was detected in the final product， and energy dispersive spectroscopy （EDS） verified the occurrence of surface oxidation in TiN nanoparticles due to air exposure. Plasma power significantlyaffected TiN properties.At 1 000 W， poor crystallinity， small grains （<20 nm）， and severe agglomeration were observed due to insufficient precursor dissociation. Increasing power improved crystallinity and increased grain size， but at 7 000 W， excessive sintering occurred， forming large particles （above 300 nm） with an uneven size distribution. At 3 000~4 500 W， well-crystallized cubic TiN nanoparticles with clear lattice fringes （0.216 nm corresponding to the （200） plane） were obtained.
Conclusion This study successfully prepares TiN nanoparticles via a self-constructed atmospheric-pressure PECVD system with TiCl4 as the titanium source， NH3 as thenitrogen source， and N2 as the carrier gas. The optimal preparation conditions are determined as molar ratios of NH3 to TiCl4 of 6—8：1， plasma power of 3 000~4 500 W， and post-treatment by annealing at 350 ℃ for 2 h under an Ar atmosphere. The plasma method overcomes the drawbacks of traditional non-plasma processes， featuring simple operation， continuous production capacity， and the ability to produce TiN nanoparticles with high purity， good crystallinity， and uniform particle size distribution. This research provides a reliable and efficient technical approach for the large-scale industrial preparation of TiN nanomaterials， laying a foundation for their broader application in wear-resistant coatings， energy storage electrodes， and biomedical fields.
Keywords： titanium nitride； plasma method； nanoparticles'
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