In the realm of automatic speech recognition (ASR), the quest for models that not only perform with high accuracy but also offer transparency in their decision-making processes is crucial. The potential of quality estimation (QE) metrics is introduced and evaluated as a novel tool to enhance explainable artificial intelligence (XAI) in ASR systems. Through experiments and analyses, the capabilities of the NoRefER (No Reference Error Rate) metric are explored in identifying word-level errors to aid post-editors in refining ASR hypotheses. The investigation also extends to the utility of NoRefER in the corpus-building process, demonstrating its effectiveness in augmenting datasets with insightful annotations. The diagnostic aspects of NoRefER are examined, revealing its ability to provide valuable insights into model behaviors and decision patterns. This has proven beneficial for prioritizing hypotheses in post-editing workflows and fine-tuning ASR models. The findings suggest that NoRefER is not merely a tool for error detection but also a comprehensive framework for enhancing ASR systems' transparency, efficiency, and effectiveness. To ensure the reproducibility of the results, all source codes of this study are made publicly available.