It is narrated from Sayyiduna Ibn Umar (may Allah be pleased with them both) that the Messenger of Allah (peace and blessings be upon him) said: "'Al-shafaq' (twilight) means the redness; when the redness disappears, the prayer becomes obligatory."
Hadith Referenceالسنن الكبرى للبيهقي / كتاب الصلاة / 1744