- Are ALL segfaults undefined behavior?
This question is trickier than it might seem, because "undefined behavior" is a description of either a C source program, or the result of running a C program in the "abstract machine" that describes behavior of C programs in general; but "segmentation fault" is a possible behavior of a particular operating system, often with help from particular CPU features.
The C Standard doesn't say anything at all about segmentation faults. The one nearly relevant thing it does say is that if a program execution does not have undefined behavior, then a real implementation's execution of the program will have the same observable behavior as the abstract machine's execution. And "observable behavior" is defined to include just accesses to volatile objects, data written into files, and input and output of interactive devices.
If we can assume that a "segmentation fault" always prevents further actions by a program, then any segmentation fault without the presence of undefined behavior could only happen after all of the observable behavior has completed as expected. (But note that valid optimizations can sometimes cause things to happen in a different order from the obvious one.)
So a situation where a program causes a segmentation fault (for the OS) although there is no undefined behavior (according to the C Standard) doesn't make much sense for a real compiler and OS, but we can't rule it out completely.
But also, all that is assuming perfect computers. If RAM is bad, an intended address value might end up changed. There are even very infrequent but measurable events where cosmic rays can change a bit within otherwise good RAM. Soft errors like those could cause a segmentation fault (on a system where "segmentation fault" is a thing), for practically any perfectly written C program, with no undefined behavior possible on any implementation or input.
- If no, is there any way to ensure a segfault?
That depends on the context, and what you mean by "ensure".
Can you write a C program that will always cause a segfault? No, because some computers might not even have such a concept.
Can you write a C program that always causes a segfault if it is possible on a computer? No, because some compilers might do things to avoid the actual problem in some cases. And since the program's behavior is undefined, not causing a segfault is just as valid a result as causing a segfault. In particular, one real obstacle you might run into, doing even simple things like deliberately dereferencing a null pointer value, is that compiler optimizations sometimes assume that the inputs and logic will always turn out so that undefined behavior will not happen, since it's okay to not do what the program says for inputs that do lead to undefined behavior.
Knowing details about how one specific OS, and possibly the CPU, handle memory and sometimes generate segmentation faults, can you write assembly instructions that will always cause a segfault? Certainly, if the segfault handling is of any value at all. Can you write a C program that will trigger a segfault in roughly the same manner? Most probably.