Ma Junjie， Hong Ruoyu
College of Chemical Engineering， Fuzhou University， Fuzhou 350108， China
Abstract
Objective The preparation of titanium nitride （TiN） nanoparticles is a research focus in advanced nanomaterial synthesis and an effective approach 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 diffraction peaks. 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
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.
Received：2026-03-20， Revised： 2026-04-11，Online： 2026-06-08.
Funding：The research was supported by the National Natural Science Foundation of China (Grant No. 22278080) and the Strategic Emerging R&D Fund of Fujian Province (Grant No. 82918001).
DOI：10.13732/j.issn.1008-5548.2026.06.002
CLC No.：TQ134.1； TB4
Type Code：A
Serial No.：1008-5548（2026）06-0001-13
