An obvious answer would be tar, but I can't find any analytical evidence for this. I have even found some weak evidence* against this. It seems that it's not even one particular substance.
Haemosiderin is sometimes implicated, but acculumation of this compound is seen equally in smokers and non-smokers.**
*Joyce K. Newman PhD , A. E. Vatter PhD & O. K. Reiss PhD (1967) Chemical and Electron Microscopic Studies of the Black Pigment of the Human Lung, Archives of Environmental Health: An International Journal, 15:4, 420-429, DOI: 10.1080/00039896.1967.10664943
** Craig, P. J., Wells, A. U., Doffman, S., Rassl, D., Colby, T. V., Hansell, D. M., ... & Nicholson, A. G. (2004). Desquamative interstitial pneumonia, respiratory bronchiolitis and their relationship to smoking. Histopathology, 45(3), 275-282, DOI: 10.1111/j.1365-2559.2004.01921.x