Ultrathin silicon dioxide (SiO2) layers with excellent electrical characteristics can be formed using the nitric acid oxidation of Si (NAOS) method, i.e., by immersion of Si in nitric acid (HNO3) solutions. The SiO2 layer formed with 61 wt % HNO3 at its boiling temperature of 113 °C has a 1.3 nm thickness with a considerably high density leakage current. When the SiO2 layer is formed in 68 wt % HNO3 (i.e., azeotropic mixture with water), on the other hand, the leakage current density (e.g., 1.5 A/cm2 at the forward gate bias, VG, of 1 V) becomes as low as that of thermally grown SiO2 layers, in spite of the nearly identical SiO2 thickness of 1.4 nm. Due to the relatively low leakage current density of the NAOS oxide layer, capacitance–voltage (C–V) curves can be measured in spite of the ultrathin oxide thickness. However, a hump is present in the C–V curve, indicating the presence of high-density interface states. Fourier transformed infrared absorption measurements show that the atomic density of the SiO2 layers increases by 7% with an increase in the HNO3 concentration from 61 to 68 wt %. Measurements of valence band spectra clarify that this concentration increase causes the enhancement of the valence band discontinuity at the Si/SiO2 interface from 4.1 to 4.3 eV. When postmetallization annealing (PMA) treatment is performed at 400 °C in hydrogen on 〈aluminum (Al)/chemical SiO2/Si(100)〉 metal–oxide–semiconductor diodes, the leakage current density markedly increases, and this increase is attributed to a reaction between the Al electrode and the chemical SiO2 layer, resulting in a decrease in the SiO2 thickness. With PMA at 200 °C in hydrogen, on the other hand, the SiO2 thickness decreases only slightly to 1.3 nm. In this case, the leakage current density greatly decreases (e.g., 0.4 A/cm2 at VG=1 V and 5×10−3 A/cm2 at VG=−1 V), and consequently it becomes 1/3–1/10 of those for thermally grown SiO2 layers with the same thickness. The hump in the C–V curves disappears after PMA at 200 °C, indicating the elimination of interface states, and the interface state passivation is attributed to one of the reasons for the decrease in the leakage current density. Measurements of the valence band spectra show that another reason for the decrease in the leakage current density by PMA are an increase in the band discontinuity at the Si/SiO2 interface, and the elimination of SiO2 gap states.
Chemical oxidation of Si by use of azeotrope of nitric acid and water can form 1.4-nm-thick silicon dioxide layers with a leakage current density as low as those of thermally grown SiO2 layers. The capacitance–voltage (C–V) curves for these ultrathin chemical SiO2 layers have been measured due to the low leakage current density. The leakage current density is further decreased to ∼1/5 (cf. 0.4 A/cm2 at the forward gate bias of 1 V) by post-metallization annealing at 200 °C in hydrogen. Photoelectron spectroscopy and C–V measurements show that this decrease results from (i) increase in the energy discontinuity at the Si/SiO2 interface, and (ii) elimination of Si/SiO2 interface states and SiO2 gap states.
Observation of both longitudinal optical and transverse optical phonons of ∼1.3 nm ultrathin silicon dioxide (SiO2) layers formed by immersion in nitric acid shows that the SiO2 density increases by 16% after postoxidation annealing (POA) at 900 °C. For the SiO2 layers without POA, postmetalization annealing (PMA) greatly decreases the SiO2 thickness from 1.3 to 0.2 nm, the effect of which is attributable to the reaction of aluminum with SiO2 to form a metallic mixture of aluminum oxide and Si. For SiO2 layers with POA, PMA decreases the SiO2 thickness to a lesser extent (from 1.4 to 0.9 nm), because of the suppression of aluminum diffusion into SiO2 due to its dense structure. PMA is found to decrease the interface state density but increase the leakage current density.
Crown-ether cyanide treatment, which includes the immersion of Si in KCN solutions containing 18-crown-6 molecules, is found to greatly decrease the leakage current density of Si-based metal–oxide–semiconductor (MOS) diodes. The decrease by one order of magnitude for the single crystalline Si-based MOS diodes is attributable to the elimination of Si/SiO2 interface states by reaction with cyanide ions and formation of Si–CN bonds. The reduction in the leakage current density by two orders of magnitude is caused for polycrystalline Si-based MOS diodes, and this decrease is attributed to the passivation of trap states in poly-Si as well as the interface states.
Several lanthanoid oxide thin films such as those of PrO x , Sm 2 O 3 , Tb 4 O 7 , Er 2 O 3 and Yb 2 O 3 have been prepared on Si(100) wafers by the pulsed laser deposition method (PLD). PrO x film shows thin SiO 2 -equivalent oxide thickness (EOT) and low leakage current simultaneously. On the other hand, SmO x thin film does not show good properties. It is revealed by XPS spectra of the PrO x film that the deposition in O 2 ambient of 0.2 Torr produces an interfacial SiO 2 or silicate layer. The sample deposited in a high vacuum at RT has only an ultra-thin interfacial layer, but hysteresis in the C-V characteristic and leakage current are large. Other techniques have been carried out to reduce the energy of ablated particles in order to prevent the growth of an interfacial layer. In the deposition method using a shadow mask, very flat thin films were obtained. However, the deposition rate was very low, and growth of the interfacial layer could not be prevented. By enlarging the distance between substrate and target, the smallest EOT with the PrO x film in our study has been obtained by the reduction of the energy of ablated particles.
We have fabricated high-performance ultraviolet (UV) detectors with high-quality undoped and B-doped homoepitaxial diamond layers which were sequentially grown on a high-pressure/high-temperature-synthesized (HPHT) type-Ib (100) substrate by means of a high-power microwave-plasma chemical vapor deposition method. The detector performance measured had large quantum efficiencies due to an effective built-in current amplification function, fast temporal responses, and high UV/visible sensing ratios although the HPHT substrate used had considerable amounts of various defects inducing visible light absorptions and slow detector responses. The usefulness of the bilayer detector structure employed is discussed.
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