New semiconductor technologies for advanced applications are more prone to defects and imperfections related, among several different causes, to the manufacturing process, aging and cross-talks. These phenomena negatively affect the circuit’s timing and can be effectively modeled by means of the path delay fault (PDF) model. While path delay testing is currently supported by commercial Automatic Test Pattern Generation tools for scan designs, functional testing covering PDFs is not widely adopted, mainly because of the high cost for test generation. On the other side, functional test is already widely adopted for in-field test of stuck-at faults, which is often performed resorting to the execution of suitable test programs (Self Test Libraries, or STLs). This approach is attractive, since it can be performed at-speed with limited time constraints and high flexibility, making it a suitable in-field test solutions. Previous work assessed the feasibility and validity of functional approaches based on test programs targeting PDFs. In this work, we present the first systematic method for the development of very high fault coverage test programs for PDFs, which largely outperform test programs written for other fault models. Moreover, the proposed method allows the identification of functionally untestable faults. The effectiveness of the proposed approach was proven on an open-source RISC-V processor core, where 100% coverage of the functionally testable longest paths was achieved, compared with an initial coverage of 0.52% achieved with test programs targeting stuck-at faults. Results demonstrate that shorter paths are also effectively covered.