Gd-doped HfO 2 films were deposited on p-type silicon substrates in a reducing atmosphere. Photoemission measurements indicate the ntype character of Gd-doped HfO 2 due to overcompensation with oxygen vacancies. The Gd 4 f photoexcitation peak at 5.5 eV below the valence band max imum is identified using both resonant photoemission and first-principles calculations of the f hole. The rectifying (diode-like) properties of Gd-doped HfO 2 to silicon heterojunctions are demonstrated.PACS 68.55.Ln; 29.40.Wk; 81.05.Je ________________________________________ While HfO 2 has attracted considerable attention as a high-κ dielectric oxide [1][2][3][4], the gadolinium doping of a number of wide band gap semiconductors [5][6][7][8][9] suggests that Gd doping of HfO 2 may also lead to a dilute magnetic semiconduc tor [10,11]. Moreover, semiconducting Gd-doped HfO 2 may provide a promising new class of materials for neutron detec tion technologies.A gadolinium-based semiconductor diode might be better for neutron detection because of the large thermal neutron absorption cross section of gadolinium (on average ~ 46,000barns). The 157 Gd(n,γ)→ 158 Gd and 155 Gd(n,γ)→ 156 Gd reactions lead to the emission of low-energy gamma rays and conversion electrons, most of which are emit ted at energies below 220 eV [12][13][14][15]. The appeal of using 157 Gd is due to its large thermal neutron cross section of 240 000 barns [16,17]. Although sensitive to gamma radia tion, the big advantage of gadolinium over boron is not only the high neutron capture cross section but also that this cross section extends to higher neutron energies (200 meV)thanis the case for boron. While all-boron-carbide neutron detectors have been demonstrated [18][19][20], and their potential detection efficiency is much higher than that of many semiconductor materials (likely well above 50% for 10 B-enriched devices), the drawback to all boron-based devices is the need for a mod erator to reduce the neutron kinetic energies to 25-30 meV. Fissile radiation sources like 235 U or 239 Pu produce 1-2MeV neutrons, so the moderator must be significant.Since neutron capture by gadolinium leads to production of a conversion electron, the pulse height will be smaller than in the case of neutron capture by boron (10 4 charges versus 10 6 per neutron capture). Accordingly, it is advantageous to see if a Gd-doped HfO 2 diode can be fabricated that can be impedance matched and compatible with a high gain, low noise amplifier. A heterojunction diode with silicon would serve this purpose. Although Gd is expected to be a p-type dopant in HfO 2 , we attempted to fabricate a heterojunction diode of n-type Gd-doped HfO 2 with silicon by overcompen sating the Gd acceptor states by donor states introduced by oxygen vacancies, as such a device would likely have a larger depletion region and therefore larger detection volume.The Gd-doped (3 at. %) HfO 2 films were deposited on single crystal silicon (100) p-type substrates using pulsed laser deposition (PLD) at a growth rate of a...