Let's Encrypt, since Certbot 2.0, issues ECC certificates by default. Some sending mail systems do not yet support those, but only RSA certificates.Therefore, to properly issue certificates for a Postfix mailserver, you would need two sets of certificate+key files:
smtpd_tls_chain_files = /etc/letsencrypt/live/mail.example.com-ecdsa/privkey.pem, /etc/letsencrypt/live/mail.example.com-ecdsa/fullchain.pem, /etc/letsencrypt/live/mail.example.com-rsa/privkey.pem, /etc/letsencrypt/live/mail.example.com-rsa/fullchain.pem
You can get them by commenting out key-type in /etc/letsencrypt/cli.ini and then issuing the certificates with the --key-type option in command line. That part is crucial, because the settings in cli.ini will override those in /etc/letsencrypt/renewal/*.conf, which will break things on the next automatic renewal. E.g.,
sudo certbot certonly \ --cert-name mail.example.com-ecdsa \ -d mail.example.com \ --key-type ecdsa sudo certbot certonly \ --cert-name mail.example.com-rsa \ -d mail.example.com \ --key-type rsa
A more elaborate answer: