What you have there is good for reading array's, but not for writing them. Your code translates to:
Create words array with 1000 elements
For each index in the array
word = words(index)
word = "5"
Next index
At no point does it put the word back into the array. The code is missing:
...
words(index) = word
Next index
What you need to do is:
Dim words(999) As String
For index As Integer = 0 to words.Length - 1
words(index) = "5"
Next
Edit: In response to the comment below.
Once you've initialised the array, you can use a For/Each loop to read the elements.
For Each word As String in words
Console.WriteLine(word)
Next
This is the same as:
For index As Integer = 0 To words.Length - 1
Console.WriteLine(words(index))
Next
microsoft,visual, andbasic, asVB.NETautomatically means those things.Visual Studiois pretty much implied as well.