Novel and more conventional boron carbides were combined with n-type silicon to make heterojunction diodes, with neutron capture signal at zero applied bias. The boron carbides were based on the cross linking of closo-1,2-dicarbadodecaborane (ortho-carborane; 1,2-B10C2H12), and cross linking based on the combination of closo-1,2-dicarbadodecaborane (ortho-carborane; 1,2- B10C2H12) and pyridine. In the latter devices, pyridine concentration was varied; samples with a closo-1,2-dicarbadodecaborane (ortho-carborane; 1,2- B10C2H12) to pyridine ratio of 1:1 (BC:Py1) and 1:3 (BC:Py3). The result is a nonvolatile robust p-type semiconductor of boron carbide (B10C2Hx):(C5NHx)y. The I(V) curves for the resulting heterojunction diodes exhibit strong rectification where the normalized reverse bias leakage currents are largely unperturbed with increasing pyridine inclusion. The devices are largely gamma insensitive and yet neutron voltaic properties of these boron carbides is demonstrated. The neutron capture generated pulses from these heterojunction diodes were obtained at zero bias voltage although without the characteristic signatures of complete charge collection from boron neutron capture generated electron-hole pair production. These results, nonetheless, suggest that modifications to boron carbide may result in better neutron voltaic materials with linking groups chosen from family of aromatic compounds that stretch between borazine (B3N3H6) and benzene that point the way to a whole family of future studies that may ultimately lead to boron carbides better suited to low power and low flux neutron detection.