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Copper was etched from a silicon surface using the chelator hexafluoroacetylacetone (hfacH) dissolved in supercritical carbon dioxide (scCO 2 ) at 40-60 °C and 100-250 atm. Copper was deposited on Si(100) using doped HF solutions in the form of 10-90 nm Cu islands, as shown by scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) indicated the islands were composed of Cu(I) 2 O due to air exposure before etching was attempted. Oxidation of the Cu(I) was performed using aqueous 30% H 2 O 2 or a UV-Cl 2 gas phase, forming shells of Cu(II)O or Cu(II)Cl 2 , respectively, surrounding cores of Cu(I) 2 O. SEM images showed that the Cu(II)O had a flake morphology. The Cu(II) shells were removed selectively to the Cu(I) 2 O cores by processing with pure scCO 2 and rapidly releasing the system pressure (300 atm/min). Mechanical failure of the Cu(II)O and Cu(II)Cl 2 when CO 2 in stress corrosion cracks quickly expanded delaminated these layers, leaving only Cu(I) 2 O on the surface. Etching of both Cu(II) and Cu(I) was achieved when oxidized samples were processed in scCO 2 containing approximately 120 ppm of hfacH for 2 min. Nucleophilic attack of Cu(II) centers by hfacH formed copper(bis-hexafluoroacetylacetonate), Cu(hfac) 2 and water, or the monohydrate Cu(hfac) 2 ‚H 2 O, which was soluble in scCO 2 . The Cu(hfac) 2 ‚H 2 O byproduct is proposed to oxidize Cu(I) 2 O to Cu(II), allowing attack and etching by hfacH.

An integrated reactor system was built for studying gas phase surface preparation chemistries. The system integrates HF/vapor and UV photochemistry modules with an ultrahigh vacuum deposition reactor and a surface analysis chamber (x-ray photoelectron spectroscopy and Auger) for in situ surface preparation, deposition, and analysis. Each vacuum chamber is mounted on a separate, isolated branch from a main sample transfer tube. The system was designed for samples with variable shapes and thickness, but less than 64mm (212in.) in diameter. This design allows for rapid transfer times between chambers (<5min) and for the simultaneous processing and storage of up to four samples. Use of standard sample transfer and vacuum hardware components minimized initial equipment costs and system maintenance. The capabilities of the clustered reactor apparatus and the importance of surface termination were demonstrated by (1) the removal of a mixed oxide and fluorocarbon residue on silicon, leaving the surface completely terminated with Cl atoms, (2) the removal of copper oxide and copper metal from silicon, (3) the deposition of Ti preferentially on a nonannealed, aqueous-cleaned SiO2 surface relative to an annealed surface, and (4) the use of complementary surface analysis techniques to chemically identify hydrogen-bonded silanol groups on a silicon surface after HF/vapor etching. Gas phase cleaning and surface termination utilized a combination of HF/vapor (100Torr, 27°C for 200s) and UV∕Cl2 (10SCCM Cl2, 90°C for 15min) steps. The results demonstrate that integrated processing provides a means to clean thin layers of organic, oxide, and metal contaminants from semiconductor surfaces and to control the terminating atom or chemical group.

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Using in situ X-ray photoelectron spectroscopy measurements after reaction, we show that hydrogen-terminated Si(100) perturbs the bonding of physisorbed NH3 enabling a photochemical decomposition pathway at wavelengths different from those characteristic of either the molecule in the gas phase or the semiconductor bandgap. UV illumination only of gas phase NH3 at partial pressures from 0.1 to 100 Torr produced a maximum at 10 Torr in the N surface coverage. This is in good agreement with a model of the radical production rate showing that at this pressure the gas density balances the flux of photons at the surface with energies sufficient to dissociate NH3. UV illumination of both the gas phase and the surface produced a monotonic increase in the N coverage with pressure as well as coverages that were 3-10 times higher than when only the gas phase was illuminated. The amine saturation coverage scaled with the UV fluence at 10 Torr and 75 °C, reaching 6.9 × 10(14) atoms/cm(2) (∼1 N atom per Si surface atom) at 19 mW/cm(2) and 12 × 10(14) atoms/cm(2) (∼1.8 N per Si) at 35 mW/cm(2). Monochromatic illumination showed that the wavelengths driving deposition were not correlated with the Si bandgap, but instead were roughly the same as gas phase photodissociation (λ < 220 nm). The primary driving force to replace the hydrogen termination with amine groups was direct photodissociation of NH3 molecules whose electronic structure was perturbed by interaction with the surface. Amine groups enhanced the surface reaction of water present as a contaminant in the source gas. These results show that molecules in weakly bound surface states can have a dramatic impact on the photochemistry.