By far, it's dawn and dusk that offer the best photo-ops. Take shots of the sunrise, sunset and the skies. The colour of the skies change very rapidly during these hours and make for brilliant photos. Take photos of your family members against the backdrop of a setting or rising sun.
Getting up early and exploring with your camera gives you the opportunity to shoot wildlife, as most animals and birds are out in the morning, but retire into shade as the sun warms up.