1834, the French physicist peltier connected a bismuth wire to each end of the copper wire, and then connected the two bismuth wires to the positive and negative poles of the DC power supply respectively. After electrifying, he was surprised to find that one connector became hot and the other connector became cold. This phenomenon was later called peltier effect. The physical principle of peltier effect is that charge carriers move in a conductor to form a current. Because charge carriers are at different energy levels in different materials, when they move from high energy level to low energy level, they will release excess heat. On the other hand, it needs to absorb heat from the outside (that is, it is manifested as refrigeration).

Therefore, the effect of semiconductor refrigeration mainly depends on the energy level difference between the two materials in which carriers move, that is, the thermal potential difference. Pure metal has good electrical and thermal conductivity, but its refrigeration efficiency is extremely low (less than 1%). Semiconductor materials have extremely high thermoelectric potential and can be successfully used as small thermoelectric refrigerators. However, at that time, the thermoelectric effect was not applied in essence because of the poor thermoelectric performance of the metal materials used and the low energy conversion efficiency. Until 1950s, Academician Liu Fei of the Institute of Semiconductors of the Soviet Academy of Sciences did a lot of research on semiconductors and published the research results before 1945, which showed that bismuth telluride compound solid solution had good refrigeration effect. This is the earliest and most important thermoelectric semiconductor material, and it is still the main component of semiconductor materials in temperature difference refrigeration. After Yoffie theory was put into practice, many scholars studied it, and it was not widely used until the figure of merit of semiconductor refrigeration materials reached a considerable level in the 1960s. After 1980s, the performance of semiconductor thermoelectric refrigeration has been greatly improved, and the application field of thermoelectric refrigeration has been further developed.