The effects of As doping, at concentrations CAs⩽4.8×1018 cm-3, on the growth kinetics of Si(001):As layers deposited at temperatures Ts=575–900 °C by gas-source molecular-beam epitaxy from Si2H6 and AsH3 have been investigated. With constant AsH3 and Si2H6 fluxes, film deposition rates RSi increase while CAs decreases with increasing Ts. All incorporated As resides at substitutional electrically active sites for CAs up to 3.8×1018 cm-3 (Ts=800 °C), the highest value yet reported for Si(001):As growth from hydride source gases. Immediately following film growth or partial-monolayer As adsorption on clean Si(001), the samples were quenched to 300 °C and exposed to atomic deuterium (D) until saturation coverage. In situ D2 temperature-programmed desorption (TPD) spectra from both as-deposited Si(001):As and As-adsorbed Si(001) layers are composed of β1 and β2 peaks, due to D2 desorption from Si monodeuteride and dideuteride surface phases, together with a new peak β3 which we attribute to desorption from Si–- As mixed dimers. Analyses of the TPD spectra show that, because of the lone-pair electrons associated with each As surface atom, the total dangling-bond coverage, and hence RSi, decreases with increasing incoming flux JAsH3 at constant Ts. From measurements of the steady-state As surface coverage θAs vs CAs and Ts, we obtain an As surface segregation enthalpy ΔHs=-0.92 eV. Dissociative AsH3 adsorption on Si(001) was found to follow second-order kinetics with a relatively Ts-independent reactive sticking probability of 0.3. Associative As2 desorption is also second order with a rate constant kd,As2=1×1013 exp(-3.0 eV/kTs). From the combined set of results, we develop a predictive model with no fitting parameters for CAs vs JAsH3, JSi2H6, and Ts. © 2000 American Institute of Physics.