In-context learning (ICL) with large language models (LLMs) has emerged as a powerful alternative to fine-tuning for Named Entity Recognition (NER), achieving strong performance with minimal annotation and no additional training. However, prior work has shown that despite their adaptability, LLMs still lag behind fully supervised models such as fine-tuned BERT in structured tasks like NER. While existing studies on ICL for NER have mainly explored few-shot settings, the potential of scaling to hundreds of demonstrations has not been thoroughly investigated. To address this gap, we conduct a comprehensive investigation of many-shot ICL for NER and further explore its effectiveness in annotating and refining data for low-resource NER tasks. Specifically, we evaluate various LLMs across multiple domains using hundreds of ICL examples and then assess the feasibility of using many-shot ICL as a data annotation framework. Our experiments demonstrate that: (1) scaling to hundreds of in-context examples enables LLMs to match or even surpass the performance of fully supervised BERT models; and (2) using about one hundred human-labeled examples as demonstrations, many-shot in-context annotation can generate high-quality labeled data, leading to approximately 10% absolute F1 improvement over existing state-of-the-art approaches when used to fine-tune BERT on low-resource NER.

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