@Xiaochen Ni: Be aware that the Sky130 process does not have any devices that will tolerate 100V. That said, I used to play around with floating gate circuits on, I think, a 0.5um process (quite some years ago now) and assuming that required biasing the programming gate to somewhere between 50 and 100V. So assuming you know what you're doing and you're not exceeding dielectric breakdown then yes, you can get a high voltage through the Caravan pads at the top, because they are not connected to any ESD protection circuitry and so there are no connected devices to break down. Note that by doing so you inevitably create an antenna, so keep the connection to the pad as short as you can make it.