It depends on favorable season of growth and flowering for herbs. Mostly it depend on parts in which you are interested. Although their is various method depends on maturity at which they have maximum phytochemical content. Please find some method.
For plant collection for phytochemical anaylsis you have to decide
1. ... the plant part you want to collect:
2. ...if you want to work on the fresh material; then you have to work it up immediately; or you may collect it into ethanol (70% or more).
3. ...if you want to stabilize the material e.g. by drying to work on it later; in this case drying at a dry place in the shadow is recommended. However, you will not have the original native stage after that because decompositon of the material already occurs (cell disruption, enzyme activity).
4. You can also collect the material in liquid nitrogen; in this case, you will have mostly the fresh situation stabilized; in this case you should take care that until extraction the material is never thawing.
In any case it is the aim to inactivate the enzymes in the material, in particular glycosidases, oxidases, hydrolases etc thereby stabilizing the plant natural compounds in it.