I am looking to develop a system in which i need to assign every user a unique pin code for security. The user will only enter this pin code as a means of identifying himself. T
There's a difference between guessing the PIN of a target user, and that of any valid user. From your use case, it seems that the PIN is used to gain access to certain resource, and it is that resource that attackers may be after, not particular identities of users. If that's indeed the case, you will need to make valid PIN numbers sufficiently sparse among all possible numbers of the same number digits.
As mentioned in some answers, you need to make your PIN sufficiently random, regardless if you want to generate it from an algorithm. The randomness is usually measured by the entropy of the PIN.
Now, let's say your PIN is of entropy N, and there are 2^M users in your system (M < N), the probability that a random guess will yield a valid PIN is 2^{M-N}. (Sorry for the latex notations, I hope it's intuitive enough). Then from there you can determine if that probability is low enough given N and M, or compute the required N from the desired probability and M.
There are various ways to generate the PINs so that you won't have to remember every PIN you generated. But you will need a very long PIN to make it secure. This is probably not what you want.