A History of Perovskite Solar Cells

The following is an excerpt “Milestones in the History of Perovskite Solar Cells” from BCC Research Report “Perovskite Solar Cells: Materials, Fabrication, and Global Markets” by Margareth Gagliardi.

The origin of perovskite solar cells can be traced back to 1839, when a German scientist, Gustav Rose, during a trip to Russia, discovered a new calcium titanate-based mineral in the Ural Mountains, which was named “perovskite,” in honor of the Russian mineralogist Lev von Perovski.

As summarized in the next table, approximately half a century later, H.L. Wells et al. at Sheffield Scientific School – a pre-World War I unit of Yale University – prepared the first synthetic halide perovskite based on cesium and lead, although its perovskite structure was determined only during the 1950s by C.K. Møller at the Royal Veterinary and Agricultural College in Copenhagen, Denmark. Møller also observed photoconductivity in this material.

Meanwhile, researchers at Philips (Eindhoven, the Netherlands) and Western Electric (New York, N.Y.) introduced oxide perovskites for use in condensers and electromechanical transducers. Starting in the 1950s, research and development related to oxide perovskites flourished, leading to the introduction of these materials in the fabrication of various products, such as fuel cells, glass-ceramic articles, catalysts, gas sensors, heating elements, lasers and superconducting devices, in addition to increasingly popular multilayer capacitors.

In 1978, D. Weber at the University of Stuttgart in Germany developed the first organic-inorganic halide perovskite, in which methylammonium ions replaced the cesium cations in the original halide compound synthesized by Wells et al. in 1892.

However, an additional 16 years would pass before the optoelectronic properties of halide perovskites were exploited for commercial applications. In 1994, researchers at IBM T.J. Watson Research Center (Yorktown Heights, N.Y.) developed light-emitting devices based on luminescent organic-inorganic halide perovskites, and in 1996 Boeing North America (Seal Beach, Calif.) created nonlinear optical crystals based on cesium-germanium halide salts.

In 1999, M. Chikao et al. at the National Institute of Advanced Industrial Science & Technology (Tokyo, Japan) reported the fabrication of an optical absorption layer for a solar cell using a rare-earth-based perovskite compound.

The new millennium began with a sharp increase in research activity related to perovskite solar cells, leading to the introduction of new material formulations and fabrication methods, and the first steps in their commercialization.

Period	Inventor[s]/Organization	Description
1839	Gustav Rose (Berlin, Germany)	During an expedition in Russia, he discovered the mineral based on CaTiO3 in the Ural Mountains. The mineral was named “perovskite” after the Russian mineralogist Lev Aleksevich von Perovski.
1892	H.L. Wells, G.F. Campbell, P.T. Walden and A.P. Wheeler/ Sheffield Scientific School (New Haven, Conn.)	Prepared compounds based on cesium, lead and halides from aqueous solutions.
1947	Philips (Eindhoven, the Netherlands)	Introduced barium titanate for production of condensers.
1955	Western Electric (New York, N.Y.)	Reported the use of ferroelectric crystalline oxides with perovskite structure for fabrication of electromechanical transducers.
1957	C.K. Møller/ Chemical Laboratory at the Royal Veterinary and Agricultural College (Copenhagen, Denmark)	Evaluated the microstructure of the compounds produced by H.L. Wells and his collaborators and found that they had a perovskite structure.
1957	Siemens (Munich, Germany)	Developed barium titanate-based resistors
1959	Clevite (Cleveland, Ohio)	Introduced perovskite materials in the fabrication of piezoelectric resonators for electromechanical filters.
1962	A.E. Ringwood/ Australian National University (Canberra, Australia)	Proposed that the Earth’s lower mantle is made primarily of MgSiO3 perovskite.
1964	Compagni e Generale d’Electricité (Paris, France)	Developed perovskite-based solid electrolytes for fuel cells.
1971	Corning Glass Works (Corning, N.Y.)	Reported the use of perovskite oxides in frits for glass-ceramic articles.
1971	Exxon Research Engineering (Linden, N.J.)	Developed perovskite-based cathode catalysts for electrochemical cells used to convert alcohols into ketones.
1975	Hitachi (Tokyo, Japan)	Manufactured the first gas sensors based on oxide perovskites.
1978	D. Weber/University of Stuttgart (Stuttgart, Germany)	Developed the first organic-inorganic halide perovskites.
1979	NGK Insulators (Nagoya, Japan)	Introduced a honeycomb structural body based on barium titanate for use as a heating element
1981	GTE Laboratories (Waltham, Mass.)	Introduced lasers based on perovskite crystals.
1988	Ferranti Plc (Oldham, U.K.)	Developed a superconducting composition with a perovskite structure.
1988	Sharp (Osaka, Japan)	Developed a thermoelectric material with a perovskite structure composed of a rare earth element and a transition metal.
1994	D.B. Mitzi et al./ IBM (Yorktown Heights, N.Y.)	Developed luminescent organic-inorganic halide perovskites for light-emitting devices.
1996	Boeing North America (Seal Beach, Calif.)	Introduced cesium-germanium halide salts with perovskite structure as nonlinear optical crystals for optoelectronics.
1999	Murase Chikao et al./National Institute of Advanced Industrial Science & Technology (Tokyo, Japan)	Created an optical absorption layer for a solar cell using a rare earth oxide having a perovskite crystal structure.
2000 and beyond		New processes for fabrication of solar cells based on perovskite materials were developed leading to an increase of activities in this field, the creation of the first devices, and the first