Described in this review are our electron-microscopic, energy dispersion, and optical (IR absorption and low-temperature (4.5 K) photoluminescence) investigations of layered InSe and GaSe crystals intercalated using the considered below methods with various concentrations of hydrogen or hydrogen-containing molecules (HCM) of water, toluene, and alcohol. It has been shown that these crystals are efficiently intercalated-deintercalated (IC-DIC) not only with hydrogen but also with HCM. It has been ascertained that the layered crystals kept for a long term in natural conditions contain molecules of water and carbon dioxide gas in the subsurface area, where their concentration increases with time. It has been shown that the concentration of molecules intercalated into the crystal decreases when deepening inside its bulk both along crystal layers and the normal to them. Also adduced were empirical equations relating concentration distribution of molecules intercalated into the crystal with the duration of IC-DIC processes. Ascertained are the optimal dimensions allowing to efficiently perform IC-DIC of the whole crystal bulk. It has been shown that the IC-DIC process in time has the look of a hysteresis loop-fast initial growth of the HCM concentration with the following slowdown when intercalating and fast drop with the following retardation when deintercalating under permanent evacuation of the chamber with the crystal. The availability of two types of conductivity in n-InSe and p-GaSe crystals causes some features in the emission spectra of the crystals intercalated with hydrogen or HCM. In the case of n-InSe crystals, the availability of HCM results, in the whole, in predominant emission of free excitons, and in the opposite case of p-GaSe crystals, the recombination of carriers via deep centers becomes predominant.

Features of photoluminescence (PL) and photoconductivity (PC) spectra, taken at 4.2 to 60 K, of GaSe crystals of stoichiometric composition and grown with an excess and with a lack of Ga atoms are analyzed. It is shown that the presence of excessive Se atoms in the matrix of GaSe crystals results in the formation of centres where triplet excitons are bound. Excessive Ga atoms formed in a crystal both, in the process of its growth and under the effect of laser irradiation give rise to regions with another polytype composition (γ‐modification). The presence of such (γ‐polytype) regions is shown to produce packing defects whre localization of excited electron states (n > 1) occurs. An effect of PC signal increase with increasing exposure dose is found, which is attributed to the formation of acceptor centres.