【摘要】 传统掺杂技术受限于热力学平衡与固溶度极限，难以同时满足现代半导体器件对高掺杂浓度、低温度及超浅结的需求。非平衡掺杂技术通过瞬时高能粒子、光子或电场等手段，在极短的时间尺度内打破热力学平衡约束引入杂质，其中以基于啁啾脉冲放大（CPA）技术的飞秒激光掺杂，展现出了突破平衡固溶度限制与实现超快非热激活的显著优势。本文综述了非平衡掺杂的主要技术，包括生长-同步型与后处理型两大类，重点介绍了基于CPA技术的飞秒激光掺杂以及其他超快激光掺杂技术的核心原理与应用进展；总结了非平衡掺杂技术在硅、宽禁带半导体及二维材料中的研究现状，涵盖电学性能提升、光学特性调控与器件兼容性优化等多个方面。最后，讨论了非平衡掺杂在掺杂稳定性、大面积均匀性及工艺集成等方面面临的挑战，并展望了其在未来半导体器件与产业升级中的应用潜力。更多还原

【Abstract】 Significance The continuous advancement of semiconductor technology relies on precise carrier control through doping. Traditional methods—thermal diffusion and ion implantation with furnace annealing—operate under thermodynamic equilibrium and solid solubility limits, now posing major bottlenecks. Scaling CMOS to sub-3 nm nodes requires ultra-shallow junctions（<10 nm） with doping concentrations exceeding 1×1021 cm^-3, while wide-bandgap（e.g., SiC, GaN） and 2D materials（e.g., MoS₂, WS₂） face distinct challenges: poor p-type activation in SiC, low dopant activation in GaN（<5%）, and thermal instability in 2D materials above 400 ℃. Meeting the simultaneous demands for high doping concentration, low thermal budget, and selective doping has led to the rise of non-equilibrium doping technologies, which utilize transient high-energy particles, photons, or electric fields to introduce and activate impurities on sub-equilibrium timescales, enabling supersaturated doping and low-temperature processing.Progress Non-equilibrium doping techniques can be broadly categorized into two groups: growth-synchronous and post-growth approaches.Growth-synchronous methods incorporate doping during deposition. Molecular beam epitaxy（MBE） achieves monolayer precision（Fig. 1）; low-temperature MBE suppresses diffusion for abrupt doping in Ge, Si, and III-V compounds. Delta doping, a hallmark of MBE, confines dopants to atomic layers, forming high-density 2D electron gases in β-Ga₂O₃ and GaAs nanowires. Metal-organic chemical capor deposition（MOCVD）（Fig. 4）, though near-equilibrium, attains non-equilibrium doping via rapid precursor switching, enabling high p-type AlGaN and Si-doped AlN for high-voltage devices. Pulsed laser deposition（PLD）（Fig. 5）, an inherently non-equilibrium process, utilizes laser plasma quenching to form metastable phases and supersaturated doped oxides（e.g., Sm-doped CeO2）, thereby enhancing heterojunctions and solar cell performance. Unbalanced magnetron sputtering（UMS）（Fig. 6） improves ion bombardment, yielding conductive Al∶ZnO and flexible In₂O₃@SiO₂ films.Post-growth techniques modify existing materials. Ion implantation remains versatile, with precise depth and dose control; rapid thermal annealing（RTA） enables dopant activation and defect recovery, exemplified by high-performance Er/O-doped Si photodiodes. Pulsed laser annealing（PLA） and pulsed laser melting（PLM） promote liquid-phase regrowth and supersaturation of deep-level dopants（Ag, Ti, S, Se, Te）, forming intermediate bands for sub-bandgap absorption, while Ar hyperdoping in Si and Ge enhances infrared detection（Fig. 8）. Plasma treatments provide low-damage alternatives: nitrogen plasma converts WS2 and MoS2 from n-to p-type via substitutional doping, enabling high-speed p-i-n photodiodes in WSe2.Laser doping marks a paradigm shift—achieving supersaturation and activation in one step. Femtosecond laser doping, based on chirped pulse amplification（CPA）, induces ultrafast melting and recrystallization, trapping dopants（S, Se, Te, Ag, Ti） from gaseous or thin-film sources at concentrations orders of magnitude above the solubility limit（Fig. 10）. It simultaneously creates micro/nanostructures forming black silicon（b-Si） with broadband absorption. b-Si photodetectors exhibit responsivities exceeding 100 A/W from UV to NIR. Advances include “flat” b-Si with low roughness, temporal pulse shaping for uniformity, and hybrid processing combining femtosecond and nanosecond laser steps or substrate heating to improve crystallinity. The technique extends to wide-bandgap systems, including F-hyperdoped ZnO and B-doped SiC nanowire junctions（Fig. 15）. Picosecond laser doping offers a balance between non-equilibrium and thermal effects, achieving higher crystallinity for certain dopants, such as Se in Si. Nanosecond laser annealing, though mainly thermal, is effective for recrystallization and dopant activation, enabling superconducting Si∶B and SiGe∶B layers. Ultrafast laser plasma doping（ULPD）, a recent advance, uses laser-generated plasma plumes to inject dopants(e.g., Er³⁺ in SiO₂) at low temperatures, achieving extreme doping for active photonic waveguides. A comparative summary of these methods is provided in Table 1.Conclusions and Prospects Non-equilibrium doping technologies have demonstrated their capability to surpass equilibrium limits, enabling new material states and device functionalities. To advance from laboratory exploration to industrial deployment, several challenges must be addressed:（1） ensuring uniformity and reproducibility over large wafers;（2） enhancing dopant activation while minimizing defects;（3） establishing quantitative models for ultrafast non-equilibrium kinetics; and（4） integrating these processes with CMOS-compatible platforms.Future research should emphasize:（1） Hybrid Process Optimization, combining complementary techniques（e. g., ion implantation with ultrafast laser annealing） to optimize profiles and activation;（2） Cross-Scale Mechanistic Studies, leveraging in-situ characterization and multiscale modeling to clarify defect dynamics and activation mechanisms;（3） Exploration in Emerging Materials, applying non-equilibrium doping to Ga₂O₃, AlN, diamond, 2D materials, and oxide heterostructures for power, UV, and quantum devices;（4） Low-Dimensional Doping, exploiting confinement and interface effects for new functionalities; and（5） Scalability and Integration, developing high-throughput, controllable, and stable processes suitable for industrial fabrication.In summary, non-equilibrium doping is not an alternative but an essential evolution of semiconductor processing. As mechanistic insights deepen and process control improves, it will evolve from an exploratory technique to a key manufacturing cornerstone driving the next generation of electronics and photonics.更多还原