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Refer this http://shivanandarao.wordpress.com/2012/09/20/applying-psu-patch-in-a-dataguard-physical-standby-environment/
The link refers for applying PSU patch but the process is same for the upgrade method as well.
I hope you would be doing an out-of-place upgrade.
Make sure you apply the pre-requisite patches to your primary and standby database.
You need to follow the same step of what you do on primary, the only main thing that you need to keep in mind, is to not to run any upgrade scripts (catupgrd.sql or catbundle.sql) on the standby database. These scripts need to be run on the primary database with the MRP being active on the standby database. The archives generated on the primary database would be shipped and applied to the standby database. So, make sure that you do not run the upgrade scripts on the standby database.
Follow these simple steps
Disable log shipping from the Primary
Install 126.96.36.199 on Standby
Startup Standby in recovery mode (do NOT run any Upgrade SQL at the standby)
Install 188.8.131.52 on Primary
Run Upgrade SQL on Primary or use DBUA
Copy the Primary password file to the Standby and rename it in the new Oracle home.
Re-enable log shipping
Monitor the redo apply from Primary to Standby --- this will also upgrade the Standby data dictionary.
Also remember to check your listener.ora and tnsnames and make sure they are in the correct Oracle home after the upgrade
For additional information :
See Oracle support article : How do you apply a Patchset,PSU or CPU in a Data Guard Physical Standby configuration [ID 278641.1]
So what I do is wait until the primary upgrade is complete, then start the Standby in the new home with the new copy of the password file.
Make sure you have an spfile in the new oracle home on the standby server too. A copy works fine.
Generally you will get several logs in a short amount of time to complete the standby upgrade.
Note the listener and tsnames move to the new oracle home. Restart listener on Standby.
If any of this does not make sense let me know. Did 3 of these last Saturday and its very fresh in my head.
Edited by: mseberg on Dec 6, 2012 8:16 AM
Here are my notes on upgrading from [url http://www.ora00600.com/articles/10g-to-11g-database-upgrade.html]10g to 11g, a few paragraphs down the page are the step by step instructions which include the parts for data guard. Although it's from 10g to 11g, the process will be the same. You need to consider how to rollback if it fails. We used snap technology at the SAN level but you could replace that with Oracle flashback. Just test it thoroughly first because I had some issues when attempting to use it initially.
The steps in that guide are much exact notes so I know they work but you should most definitely still read the upgrade guide and appropriate docs, too.