Try this
select empCode, [Date], [1] intime ,[2] break_out,[3] break_in,[4] outtime
from
(select empcode,convert(date,[DATE]) [date],convert(time,[time]) time ,ROW_NUMBER() over(partition by empcode,date order by empcode,date,time) Tin from emp
)data
pivot
(
max([time])
for Tin in ([1],[2],[3],[4])
)p