If you want such small structures, use electron beam lithography, if you have access to it. If not available, please try to get it done from IIT Bombay or IISc Bangalore.
The procedure for (cheap) silicon needles array is the pillar oxidation/etching. I remember making ~100nm diameter needles with 3.8um resolution mask on university stepper.
The process is:
1) DRIE pattern of silicon pillars
2) Oxidize to such depth what only thin central core remain non-oxidized
In collaboration with KTH (Sweden) and Leti (France), Debiotech (Switzerland) developed MEMS microneedles for pain-free and precise injection of drugs: