Indexes can also be used to enforce uniqueness of a column's value, or the uniqueness of the combined values of more than one column.
CREATE UNIQUE INDEX name ON table (column [, ...]);
Currently, only B-tree indexes can be declared unique.
When an index is declared unique, multiple table rows with equal indexed values are not allowed. Null values are not considered equal. A multicolumn unique index will only reject cases where all indexed columns are equal in multiple rows.
PostgreSQL automatically creates a unique index when a unique constraint or primary key is defined for a table. The index covers the columns that make up the primary key or unique constraint (a multicolumn index, if appropriate), and is the mechanism that enforces the constraint.
Note: There's no need to manually create indexes on unique columns; doing so would just duplicate the automatically-created index.