Consider a simpler algorithm:
-  Pass 1: Build a map of counts of characters. You can use a simple intarray to store this mapping.
- Pass 2: For each index, if the count of the current character is 1, return the index.
- If pass 2 terminates without returning, then there are no unique characters, return -1.
This is simple, straightforward logic. The constant number of passes doesn't change the time complexity.
You could do it in a single pass too, but I would prefer to avoid the added complexity unless there is a compelling reason.
Example implementation of the above algorithm:
std::array<int, 26> counts {};
for (auto c : s) {
    counts[c - 'a']++;
}
for (std::size_t index = 0; index < s.size(); ++index) {
    auto c = static_cast<unsigned char>(s[index]);
    if (counts[c - 'a'] == 1) return index;
}
return -1;
 Note that the hack of using c - 'a' to map lowercase English letters to the range [0 .. 25] works with the ASCII character set, and may not be suitable for others. If that's a concern, you can use the approach of the other answer, or use a proper std::set.
 If there are more than INT_MAX repetitions of a character (as pointed out by @Toby), the count will overflow, and may even reach 1 again, producing incorrect result. If you need to add support for such input, then it will be better to consider a similar algorithm (alluded to by @greybeard):
- Pass 1: Build a set of characters seen, and another set of characters seen twice.
- Pass 2: For each index, if the character is not in the set of characters seen twice, return the index.
- If pass 2 terminates without returning, then there are no unique characters, return -1.
This uses an additional set (constant space), but has the advantage that it supports inputs of arbitrary length and repetitions.
Example implementation:
std::array<bool, 26> seen {}, repeated {};
for (auto c : s) {
    repeated[c - 'a'] = seen[c - 'a'];
    seen[c - 'a'] = true;
}
for (std::size_t index = 0; index < s.size(); ++index) {
    auto c = static_cast<unsigned char>(s[index]);
    if (!repeated[c - 'a']) return index;
}
return -1;
 
                