stylistic:tone
19th century

In 1839, Alexandre Edmond Becquerel discovered the related photovoltaic effect while studying the effect of light on electrolytic cells. Though not equivalent to the photoelectric effect, his work on photovoltaics was instrumental in showing a strong relationship between light and electronic properties of materials. In 1873, Willoughby Smith discovered photoconductivity in selenium while testing the metal for its high resistance properties in conjunction with his work involving submarine telegraph cables.

Johann Elster (1854–1920) and Hans Geitel (1855–1923), students in Heidelberg, investigated the effects produced by light on electrified bodies and developed the first practical photoelectric cells that could be used to measure the intensity of light. They arranged metals with respect to their power of discharging negative electricity: rubidium, potassium, alloy of potassium and sodium, sodium, lithium, magnesium, thallium and zinc; for copper, platinum, lead, iron, cadmium, carbon, and mercury the effects with ordinary light were too small to be measurable. The order of the metals for this effect was the same as in Volta's series for contact-electricity, the most electropositive metals giving the largest photo-electric effect.

In 1887, Heinrich Hertz observed the photoelectric effect and reported on the production and reception of electromagnetic waves. The receiver in his apparatus consisted of a coil with a spark gap, where a spark would be seen upon detection of electromagnetic waves. He placed the apparatus in a darkened box to see the spark better. However, he noticed that the maximum spark length was reduced when inside the box. A glass panel placed between the source of electromagnetic waves and the receiver absorbed ultraviolet radiation that assisted the electrons in jumping across the gap. When removed, the spark length would increase. He observed no decrease in spark length when he replaced the glass with quartz, as quartz does not absorb UV radiation.

The discoveries by Hertz led to a series of investigations by Wilhelm Hallwachs, Hoor, Augusto Righi and Aleksander Stoletov on the effect of light, and especially of ultraviolet light, on charged bodies. Hallwachs connected a zinc plate to an electroscope. He allowed ultraviolet light to fall on a freshly cleaned zinc plate and observed that the zinc plate became uncharged if initially negatively charged, positively charged if initially uncharged, and more positively charged if initially positively charged. From these observations he concluded that some negatively charged particles were emitted by the zinc plate when exposed to ultraviolet light.

With regard to the Hertz effect, the researchers from the start showed the complexity of the phenomenon of photoelectric fatigue—the progressive diminution of the effect observed upon fresh metallic surfaces. According to Hallwachs, ozone played an important part in the phenomenon, and the emission was influenced by oxidation, humidity, and the degree of polishing of the surface. It was at the time unclear whether fatigue is absent in a vacuum.

In the period from 1888 until 1891, a detailed analysis of the photoeffect was performed by Aleksandr Stoletov with results reported in six publications. Stoletov invented a new experimental setup which was more suitable for a quantitative analysis of the photoeffect. He discovered a direct proportionality between the intensity of light and the induced photoelectric current (the first law of photoeffect or Stoletov's law). He measured the dependence of the intensity of the photo electric current on the gas pressure, where he found the existence of an optimal gas pressure corresponding to a maximum photocurrent; this property was used for the creation of solar cells.

Many substances besides metals discharge negative electricity under the action of ultraviolet light. G. C. Schmidt and O. Knoblauch compiled a list of these substances.

In 1897, J. J. Thomson investigated ultraviolet light in Crookes tubes. Thomson deduced that the ejected particles, which he called corpuscles, were of the same nature as cathode rays. These particles later became known as the electrons. Thomson enclosed a metal plate (a cathode) in a vacuum tube, and exposed it to high-frequency radiation. It was thought that the oscillating electromagnetic fields caused the atoms' field to resonate and, after reaching a certain amplitude, caused subatomic corpuscles to be emitted, and current to be detected. The amount of this current varied with the intensity and color of the radiation. Larger radiation intensity or frequency would produce more current.

During the years 1886–1902, Wilhelm Hallwachs and Philipp Lenard investigated the phenomenon of photoelectric emission in detail. Lenard observed that a current flows through an evacuated glass tube enclosing two electrodes when ultraviolet radiation falls on one of them. As soon as ultraviolet radiation is stopped, the current also stops. This initiated the concept of photoelectric emission. The discovery of the ionization of gases by ultraviolet light was made by Philipp Lenard in 1900. As the effect was produced across several centimeters of air and yielded a greater number of positive ions than negative, it was natural to interpret the phenomenon, as J. J. Thomson did, as a Hertz effect upon the particles present in the gas.