yes the word shiv appears in yajurved madhyandini samhita adhyaya 34 mantra 1 [and further upto 6]
Can u recognize the word shiv in sanskrit in the end:: shiv sankalpamastu.
Rishi Dayanand explains further:
“He is called Brahma – the Creator* of the Universe; Vishnu – All-pervading; Rudra – Punisher of the wicked, whom he causes to weep; Shiva – Blissful and Benefactor of all; Akshara – Immortal, Omnipresent; Swaraati – Self-effulgent; Kaalaagni – Cause of the dissolution** of the world and Regulator of time; Chandramaa – the true Source of Hapiness.” KAIVALYA UPNISHAD.
Shiva is One who is all Bliss and he Giver of happiness to all.
But the shiv ling or human bodied shiv does not exist in vedas.