Applications and trends of nonequilibrium plasma chemistry with organic and organometallic compounds

The possibilities and limitations of available apparatus for nonequilibrium discharges are discussed. Especially for synthetic work there is a lack of suitable equipment. The unique possibilities which plasmas offer to chemistry are demonstrated by examples from the homogeneous gas phase, and from plasma liquid and plasma solid interactions. Various applications and major trends are being described. The most rapidly increasing field of plasma chemistry is presently the formation of thin films of metals, oxides, carbides, or nitrides by plasma enhanced CVD. The latest results, and especially the use of organometallic compounds and starting material, are being discussed.     

Deposition of copper oxide (Cu2O,CuO) thin films at high temperatures by plasma-enhanced CVD

Copper-oxide films are deposited by plasma-enhanced CVD using copper acetylacetonate as a precursor. The influence of various experimental parameters on deposition rate, film composition and resistivity have been studied. The substrate temperature and the bias are the parameters which affect these properties the most. An increase of the substrate temperature changes the phases of the deposit from Cu₂O-CuO over Cu₂O to Cu. At temperatures 500° C the deposition rates are high but the films consist mainly of metallic Cu. A negative bias enhances the deposition rate only slightly but has a strong effect on the film composition and can completely balance the oxygen deficiency. At a bias of –120 V the films consist of pure CuO even at temperatures 500° C.     

Ionen-Cyclotron-Resonanz-Messungen von Ion/Molekül-Reaktionen bei Chinonen

At a pressure of 10^?6 Torr the ion cyclotron resonance spectra of p-benzoquinone, methyl-p-benzoquinone, tetramethyl-p-benzoquinone and tetrafluoro-p-benzoquinone are identical to the normal mass spectra. Above 10^?5 Torr the spectra show a variety of signals for product ions. From double resonance measurements it was shown that all the product ions are formed by addition of the molecular ion or of a fragment ion to a neutral quinone molecule. In most cases the addition is accompanied by the elimination of carbon monoxide.     

Laser-induced CVD of rhodium

Stripes of rhodium metal were deposited by focusing an Ar⁺ laser (514.5 nm) onto glass and polyimide substrates in a heated vacuum cell that contained Rh(CO)₂acac vapor. Stripes were characterized by scanning profilometry, electrical resistivity, SEM and Auger measurements. Most stripes were 100–200 m wide and 1–3 m high. Very broad stripes (>500 m) were deposited when the Rh(CO)₂acac vapor pressure was greater than 1 Torr and when the laser power was more than 200 mW. Stripe resistivities were in general around 30 times that of the bulk material. Auger spectra show the presence of carbon in the stripes.     

Pressure effect on heterogeneous trifluoromethylation of fullerenes and its application

The first systematic study of heterogeneous fullerene trifluoromethylation using an innovative gradient-temperature gas-solid reactor revealed a significant effect of CF₃I pressure on the conversion of C₆₀ and C₇₀ into trifluoromethylated products and on the range of fullerene(CF₃)_n compositions that were obtained. The design of the reactor allowed us to lower the residence times of fullerene(CF₃)_n species in the hot zone which resulted in the significant differences in relative isomeric distributions as compared to the earlier methods. For the first time, gram quantities of trifluoromethylated fullerenes were prepared using the new reactor, and the selective synthesis of a single-isomer C₆₀(CF₃)₂ was developed. The relative reactivity of C₇₀ as a CF₃ radical scavenger was found to be much lower than that of C₆₀, especially at an early radical addition stage, which led to the cost-efficient synthesis of C₆₀(CF₃)₂ from a fullerene extract.