随着社会发展，多个领域对现场质谱分析的需求使得质谱系统的小型化成为发展趋势。微流控芯片离子源同时集成前处理与离子化功能的能力，使其有潜力与现场质谱仪联用直接分析液相复杂样品，受到了学界广泛关注。但是对于现场质谱分析的需求，传统的软光刻 PDMS 模制工艺一定程度上限制了微流控芯片从实验室走向实际应用，立体光固化增材制造技术有潜力打破这一限制，提高微流控芯片离子源的实际应用能力。 本研究基于立体光固化技术快速原型制造、复杂三维结构制造、自动化整体制造等优势，结合现场质谱分析需求，开发了多种全三维微流控芯片离子源。通过全三维流道结构设计在立体三维空间内改进流场分布，提高芯片集成度，实现了稳定高效的芯片离子化模式，拓展微流控芯片离子源的应用范围，具体研究内容如下。 首先，本研究设计了全三维微流控芯片的 CAD 结构模型，并使用全三维流道结构进行气流场仿真研究。基于仿真结果进行了 3D 结构设计改进以及双液路三维集成设计，开发了流体聚焦芯片、自吸喷雾芯片以及双液路芯片用于质谱分析。 其次，开发了基于立体光固化技术的全三维芯片制造流程，此流程能够以通用参数进行自动化批量生产本研究设计的全三维芯片，可重复性良好。在此基础上加工全三维微流控芯片离子源进行质谱联用测试，本研究开发的全三维芯片均可以实现无需高电压的高速气流喷雾离子化模式, 长时间稳定性测试的 RSD 均小于 4 %。流体聚焦芯片适用样品流量范围广，能够高效稳定地离子化流量可控的液相样品。自吸喷雾芯片以及两种双液路芯片都可以实现负压进样的单路或双路自吸喷雾离子化模式，进样流量稳定，且双路独立喷雾具有提高灵敏度，改善离子抑制以及液液萃取直接分析复杂样品的能力。 最后，使用本研究开发的全三维芯片进行实际应用研究。芯片的高速气流喷雾离子化模式可以同时生成正负离子，同时立体光固化使得芯片在易用性与鲁棒性上有了显著改善，整体芯片离子源系统实现小型便携化，操作简单灵活，可快速进行高通量分析。通过双路内标萃取定量分析以及联用小型质谱仪直接分析复杂液相样品，证明了全三维微流控芯片离子源面向现场质谱分析的实际应用能力。

With the increasing demand for onsite mass spectrometry (MS) analysis in various fields, miniaturization of MS systems has become a development trend. Microfluidic chip ionization sources, with the ability to integrate pretreatment and ionization functions, have attracted widespread attention. However, the traditional soft lithography PDMS molding process has limited their practical onsite application. Stereo lithography Appearance (SLA) additive manufacturing has the potential to enhance the practical on-site MS application of microfluidic chip ionization sources. This research mainly developed a variety of 3D microfluidic chip ionization sources coupling with MS, which is on the background of on-site MS, and based on the SLA advantages as rapid prototyping, complex 3D structure fabrication, and automated overall manufacturing. Through the design of the 3D flow channel structure, the 3D flow field distribution and the microfluidic chip integration are improved. All the 3D structure designs of these microfluidic chips are expected to achieve a stable and efficient chip ionization mode, and expand the application scope of microfluidic chip ionization sources. The main contents of this thesis are as follows. Firstly, this research designed the CAD structure model of the 3D microfluidic chips, and the airflow field simulation study was conducted using the 3D flow channel structure. Based on the simulation results, the 3D structural design improvement and the 3D integrated design of the dual liquid path were carried out, and the Sonic flow focusing spray chip, the Self-aspiration sonic spray chip, and the dual-channel spray chips were developed for MS. Secondly, based on the SLA, this research developed a complete set of the 3D microfluidic chip manufacturing process, which can automatically mass-produce the 3D microfluidic chips designed in this research with common parameters and has great repeatability. On this basis, the 3D microfluidic chip ionization sources were fabricated for MS. The 3D chips developed in this research can work as a sonic-spary ionization source without high voltage under the action of high speed airflow, and the RSD of the long-term stability test is less than 4%. The Sonic flow focusing spray chip is suitable for a wide range of sample flow rates, and can efficiently and stably ionize liquid phase samples with controllable flow rates. The Self-aspiration sonic spray chip and the dual-channel spray chips are available for stable single or dual self-aspiration sonic spray ionization (SASI). The dual-channel SASI mode can improve sensitivity, alleviate the ion suppression effect and implement liquid-liquid extraction of untreated compounds in complex matrices without sample pretreatments, further expand the application range of the 3D microfluidic chip ionization source. Finally, the 3D microfluidic chips developed in this research were used for MS practical application research. The 3D chips can generate positive and negative ions simultaneously by sonic-spary ionization, and SLA makes the 3D chip significantly better in terms of ease of use and robustness, and the overall chip system is small and portable, simple and flexible in operation, allowing rapid high-throughput analysis. The practical application capability of the SLA 3D microfluidic chip ionization source for on-site MS was demonstrated through quantitative analysis by dual SASI internal calibration and direct analysis of complex liquid phase samples coupling with mini MS.