Here's a solution to the general case that doesn't involve needing to know the length of the array ahead of time, using collect, or using udfs. Unfortunately this only works for spark version 2.1 and above, because it requires the posexplode function.
Suppose you had the following DataFrame:
df = spark.createDataFrame(
    [
        [1, 'A, B, C, D'], 
        [2, 'E, F, G'], 
        [3, 'H, I'], 
        [4, 'J']
    ]
    , ["num", "letters"]
)
df.show()
#+---+----------+
#|num|   letters|
#+---+----------+
#|  1|A, B, C, D|
#|  2|   E, F, G|
#|  3|      H, I|
#|  4|         J|
#+---+----------+
Split the letters column and then use posexplode to explode the resultant array along with the position in the array. Next use pyspark.sql.functions.expr to grab the element at index pos in this array.
import pyspark.sql.functions as f
df.select(
        "num",
        f.split("letters", ", ").alias("letters"),
        f.posexplode(f.split("letters", ", ")).alias("pos", "val")
    )\
    .show()
#+---+------------+---+---+
#|num|     letters|pos|val|
#+---+------------+---+---+
#|  1|[A, B, C, D]|  0|  A|
#|  1|[A, B, C, D]|  1|  B|
#|  1|[A, B, C, D]|  2|  C|
#|  1|[A, B, C, D]|  3|  D|
#|  2|   [E, F, G]|  0|  E|
#|  2|   [E, F, G]|  1|  F|
#|  2|   [E, F, G]|  2|  G|
#|  3|      [H, I]|  0|  H|
#|  3|      [H, I]|  1|  I|
#|  4|         [J]|  0|  J|
#+---+------------+---+---+
Now we create two new columns from this result. First one is the name of our new column, which will be a concatenation of letter and the index in the array. The second column will be the value at the corresponding index in the array. We get the latter by exploiting the functionality of pyspark.sql.functions.expr which allows us use column values as parameters.
df.select(
        "num",
        f.split("letters", ", ").alias("letters"),
        f.posexplode(f.split("letters", ", ")).alias("pos", "val")
    )\
    .drop("val")\
    .select(
        "num",
        f.concat(f.lit("letter"),f.col("pos").cast("string")).alias("name"),
        f.expr("letters[pos]").alias("val")
    )\
    .show()
#+---+-------+---+
#|num|   name|val|
#+---+-------+---+
#|  1|letter0|  A|
#|  1|letter1|  B|
#|  1|letter2|  C|
#|  1|letter3|  D|
#|  2|letter0|  E|
#|  2|letter1|  F|
#|  2|letter2|  G|
#|  3|letter0|  H|
#|  3|letter1|  I|
#|  4|letter0|  J|
#+---+-------+---+
Now we can just groupBy the num and pivot the DataFrame. Putting that all together, we get:
df.select(
        "num",
        f.split("letters", ", ").alias("letters"),
        f.posexplode(f.split("letters", ", ")).alias("pos", "val")
    )\
    .drop("val")\
    .select(
        "num",
        f.concat(f.lit("letter"),f.col("pos").cast("string")).alias("name"),
        f.expr("letters[pos]").alias("val")
    )\
    .groupBy("num").pivot("name").agg(f.first("val"))\
    .show()
#+---+-------+-------+-------+-------+
#|num|letter0|letter1|letter2|letter3|
#+---+-------+-------+-------+-------+
#|  1|      A|      B|      C|      D|
#|  3|      H|      I|   null|   null|
#|  2|      E|      F|      G|   null|
#|  4|      J|   null|   null|   null|
#+---+-------+-------+-------+-------+