Thermionic diodes are thermionic-valve devices (also known as vacuum tubes, tubes, or valves), which are arrangements of electrodes surrounded by a vacuum within a glass envelope. Early examples were fairly similar in appearance to incandescent light bulbs.
In thermionic valve diodes, a current through the heater filament indirectly heats the cathode, another internal electrode treated with a mixture of barium and strontium oxides, which are oxides of alkaline earth metals; these substances are chosen because they have a small work function. (Some valves use direct heating, in which a tungsten filament acts as both heater and cathode.) The heat causes thermionic emission of electrons into the vacuum. In forward operation, a surrounding metal electrode called the anode is positively charged so that it electrostatically attracts the emitted electrons. However, electrons are not easily released from the unheated anode surface when the voltage polarity is reversed. Hence, any reverse flow is negligible.
For much of the 20th century, thermionic valve diodes were used in analog signal applications, and as rectifiers in many power supplies. Today, valve diodes are only used in niche applications such as rectifiers in electric guitar and high-end audio amplifiers as well as specialized high-voltage equipment.