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The capabilities of Baritt diodes in the millimeter wave range and the effects of the electron velocity versus field dependence in GaAs and InP are investigated. The influences of doping profile and material parameters are analysed by means of an exact large signal simulation. At millimeter frequencies, the Si Baritt r.f. power remains limited due to the small value of the negative resistance. This resistance is greatly improved by using GaAs or InP N+P N N+ structures; thus, better available power and efficiency can be expected. The InP material is found to be better than GaAs, because the r.f. levels can be higher and the diffusion phenomenon effect is smaller.