The prehistory of solar cells
Bell Labs’ solar PV panel, presented in 1954, came not out of nowhere. The silicon solar cell had its roots in less complex devices that could produce electricity from either light or heat.
In 1821, Thomas Seebeck found that an electrical current will flow in a circuit made from two dissimilar metals, with the junctions at different temperatures. This “thermoelectric effect” formed the basis for the “thermoelectric generator” — which converts heat (for example,
from a wood stove) directly into electricity. In 1839, Antoine Becquerel discovered that light could also convert into electricity, and during the 1870s, several scientists proved this effect in solids, most notably in selenium. This “photoelectric effect” formed the basis for the “photoelectric generator” — which we now call a “photovoltaic” generator or solar PV cell. In 1883, Charles Fritts constructed the first photovoltaic module ever made, using selenium on a thin layer of gold.
Throughout this period – and until the 1950s – the practical uses of thermoelectric and photoelectric devices were limited. Inventors built many experimental thermoelectric generators, usually powered by a gas flame, but their efficiency did not exceed 1%. Likewise, Charles Fritts’ solar panel, and the selenium solar cells made afterward, obtained just 1-2% efficiency in converting sunlight into electricity. (...)
A forgotten pioneer of solar power
(….) If Philip Pesavento’s historical account and hypotheses are correct, George Cove set out to build a thermoelectric generator but accidentally made a photovoltaic generator – a PV solar cell. Although this happened in the early 1900s, Cove obtained a comparable power output and efficiency to the Bell Labs scientists in 1954. His design also showed much higher performance than the selenium solar cells built between the 1880s and the 1940s.
16 Philip Pesavento:
“It would be quite exciting to prove that relatively high-efficiency solar cells were invented 40 years before the development of silicon cells. More importantly, if it turns out there was a solar photovoltaic cell and panel system before World War I, it might also have some advantages concerning the cheapness of raw materials, low embodied energy to convert the ores into metallic materials, the efficiency of the final PV cells, and ease of fabrication.”
In other words, if Philip Pesavento’s historical account and hypotheses are correct, it may be possible to build low-tech solar panels.
George Cove’s solar electric generator
George Cove presented his first “solar electric generator” in 1905 in the Metropole Building in Halifax, Nova Scotia, Canada. Apart from an image, there are no data about this panel.
17 However, its power output and efficiency were remarkable enough for US investors to send an expert to Halifax. Based on this expert’s examination of the machine, they then brought Cove to the US (Sommerville, Mass.) to continue the development of his device.
Cove presented his second solar electric generator there in 1909. This 1.5m2 panel could produce 45 watts of power and was 2.75% efficient in converting solar energy into electricity. By mid-1909, Cove had moved to New York City, where he presented his third prototype, a solar array consisting of four solar panels of 60 watt-peak each, which charged a total of five lead-acid batteries. The total surface area was 4.5 m2, the maximum power output was 240 watts, and efficiency rose to 5% – similar to the first solar panel presented by Bell Labs.
Although George Cove is absent from most historical accounts of solar power, his solar electric generator impressed some popular tech media of the day. For example, in 1909, Technical World Magazine wrote that “such a machine is cheap and indestructible as a kitchen range. Even in its present and somewhat crude and experimental state, given two days of sun, it will store sufficient electrical energy to light an ordinary house for a week. The inventor has proved this now for months in his establishment”.
Plugs set in asphalt
How did George Cove manage to build a solar panel that was 40 years ahead of its time? According to Philip Pesavento, who has a background in semiconductor engineering, Cove intended to build a better thermoelectric generator (TEG). He exposed his generator to the heat from a wood stove and direct solar energy — Edward Weston had made the first experimental solar thermoelectric generator (or STEG) in 1888. Cove’s intentions are also clear from how he described his device:
“The frame contains a number of panes of violet glass, behind which are set, through an asphalt compound backing, many little metal plugs. One end of the plugs is always exposed by sunlight, while the other end is cool and sheltered.”
Creating the largest possible temperature difference is key to thermoelectric power production, so Cove’s design makes sense. The problem is that when he measured the power output of his generator, it did not respond to heat like a thermo-electric generator was supposed to do. Initially, Cove observes that his invention uses both heat and light to produce electricity when exposed to solar energy:
“The principal part of my invention is the peculiar composition of the metallic plugs which are acted upon by the sun in such a way that the current is generated not only by heat rays but the violet rays as well”.
However, after further experiments with both the wood stove and solar energy, Cove states:
“When the machine is exposed to various sources of artificial heat it gives no electricity whatsoever. Other than the heat rays of the sun (short-wave infrared), perhaps the violet or ultraviolet rays are active in setting up the electrical current”.
The primary cell of Cove’s solar PV panel was a three-inch-long plug or rod of metallic composition, an alloy of several common metals. The 1.5 m2 panel had 976 rods, while the 4.5 m2 array had 4 x 1804 plugs. However, keeping the rods cool on one side and hot on another – separated by an asphalt layer – did not matter. What mattered is that Cove had unknowingly built a metal-semiconductor contact.
The semiconductor bandgap
George Cove did not understand how his solar generator worked, and neither did anyone else at the time. It was only with Einstein’s work on the photoelectric effect (in 1905) and later work in quantum mechanics (1930s and beyond) that the concept of a
semiconductor bandgap was realized. Electrons orbit the nucleus of an atom in different “states”, which form regions that are called “bands”. These bands keep their electrons firmly in place. In between these bands are “bandgaps” – states in which no electron can be.George Cove did not understand how his solar generator worked, and neither did anyone else at the time.
Conductors have no bandgaps, and so electrons flow through them. That is why a copper wire conducts electricity, for example. In insulators (like wood, glass, plastics, or ceramics), there is a very wide bandgap, which blocks the flow of electricity. Finally, in semiconductors, there’s a relatively narrow bandgap. That allows them to either act as an insulator or a conductor. Semiconductors can become conductors when they absorb a “photon” (an elementary particle of light) with an energy potential equal to or greater than the bandgap of the semiconductor material.
20
The understanding of semiconductors led to the birth of the modern solar PV cell in the 1950s. It also improved the performance of thermoelectric generators – be it for different reasons. Thermoelectric generators do not take advantage of the semiconductor bandgap. However, semiconductors have higher thermo-voltages and lower thermal conductivities than metal and metal alloys with no bandgap, making thermoelectric generators more efficient.
The Schottky Junction
For a photovoltaic effect to exist, there must be some inhomogeneity in the system. In the 1950s, Bell Labs scientists managed to do this with the so-called p-n junction, which forms a boundary between a positively charged and a negatively charged semiconductor. P-type semiconductors have electron vacancies called “holes” (which attract electrons), while N-type semiconductors have extra electrons. At the junction between both is an electric potential.
However, it’s also possible to create a PV cell from a so-called Schottky junction, which connects a semiconductor with a metal. In this case, the metal functions as the n-type semiconductor. Philip Pesavento:
“My hypothesis is that George Cove stumbled upon a Schottky contact photovoltaic cell, decades before it was described by Walter Schottky.
21 There is the possibility of both photovoltaic (predominantly) and thermoelectric responses from these devices. The plug was an alloy of zinc and antimony – which we now know is a semiconductor. It was alternately capped by German silver (a nickel, copper, and zinc alloy) and copper on opposite ends. This formed an ohmic contact and Schottky contact, respectively. This is a photovoltaic device.”
Accidental discovery
According to Philip Pesavento, George Cove probably started with “German silver” as the negative material on both ends of the plugs, and an antimony-zinc alloy (ZnSb) as the positive material. These were the best available thermoelectric materials at the time:
“He probably ran out of German silver and substituted copper to finish making up a bunch of plugs since the difference in thermoelectric voltage between using copper and German silver was small. Then, during testing, Cove noted that these plugs (with a German silver cap at one end and a copper cap at the other end) gave a much greater voltage: 100s of mV’s versus the usual 10s of mV for a thermoelectric generator.”
What happened? By using copper, Cove had unknowingly built a Schottky junction. That converted his thermoelectric generator into a “thermophotovoltaic generator.” Such a device works the same as a photovoltaic solar cell but on a different wavelength. The solar spectrum covers a range of approximately 0.5 to 2.9 electron-Volts (eV), from infrared to ultraviolet. A semiconductor with a bandgap between 1 and 1.7 eV efficiently converts visible light into electricity (a photovoltaic generator) — while a semiconductor with a bandgap between 0.4 and 0.7 eV efficiently converts short-wave infrared solar energy into electricity (a thermophotovoltaic generator).
Above: This drawing from
Cove’s 1906 patent shows the zinc-antimony alloy “b”; the german silver (ohmic) end cap “c”; and the copper or tin (Schottky) end cap “f”. All these are press-fit because soldering the connections lowered the efficiency.
We now know that ZnSb – the negative material in Cove’s plugs – is a semiconductor with a bandgap of 0.5 eV. That largely explains why the inventor initially observed that his solar generator converted both heat and light into electricity. A thermophotovoltaic generator matches not only the infrared tail of the solar spectrum — it also matches the direct spectrum of a burning flame or a red hot emitting surface which is heated by burning wood or natural gas. It also converts the lower portion of the visible spectrum into electricity, be it very inefficiently.
According to Philip Pesavento, Cove then managed to refine the composition of the alloy close to Zn4Sb3 – a zinc-antimony alloy with proportions of 4 parts zinc to 6 parts antimony. That, we now know, is also a semiconductor. However, it has a bandgap of 1.2 eV – very close to the bandgap of silicon (1.1 eV). Consequently, it turned his thermophotovoltaic generator into a photovoltaic generator:
“In his enthusiasm, Cove probably made up a larger number of plugs and somehow got the proportions “wrong” on one batch. He then measured an even larger voltage. Finally, he made a careful study of zinc-antimony alloys and found that the 40-42% range zinc alloy gave the highest voltage (compared to 35% zinc in ZnSb). Having – accidentally – discovered Zn4Sb3, the higher bandgap of this semiconductor meant that it no longer worked when it was exposed to the heat from a wood stove. However, it worked even better when it was exposed to solar energy – because it was now converting far more of the visible spectrum of sunlight efficiently into electricity.”
Using colored glass filters, George Cove determined that most of the response was from the violet end of the spectrum and only a little from the so-called heat rays. His earlier PV plugs had responded equally well to heat rays and violet rays, while the older thermoelectric generators (German silver at both sides) did not respond to the violet rays at all.
Bring back the Schottky solar cell?
Schottky junction solar cells have commanded only a small amount of attention from researchers and corporations – few solar cell designs use metals in the active region, other than for contacts.
22 Nevertheless, Philip Pesavento believes that it would be worthwhile to attempt to fabricate some Schottky solar cells according to Cove’s design:
“If it could be demonstrated that Zn4Sb3 (bandgap 1.2 eV) can be used in a photovoltaic cell, there is a good chance that such a solar cell design will be sustainable. It would be a good candidate for a quick EROI and have an acceptably long operational life with a surplus energy output over several decades. It’s astounding that everyone seems to have missed this material and its application to photovoltaic cells and that no development has been done – even after researchers briefly recognized it as being a possible option in the early to mid-1980s. It fits in the category of a premature discovery which should mean it could be developed very quickly in this day and age.”
Apart from solar PV, Philip Pesavento sees potential in thermophotovoltaics for a wood stove, solar thermal, or dual junction tandem applications, using ZnSb instead of Zn4Sb3. Furthermore, if the plug-type solar cells prove to be effective, he believes that they would allow line concentrator solar collectors – such as parabolic troughs or non-imagining CPC concentrators – to be built at greatly reduced costs.
What happened to George Cove?
If Cove’s solar panel was so revolutionary, why is it forgotten? On this question, Philip Pesavento’s research material reads like a crime novel. Cove’s attempt to produce and market his solar energy device failed in mysterious ways.
The inventor became involved with a stock manipulator – Elmer Burlingame – who in 1909 and 1910 issued stock from businesses that were not his, including Cove’s start-up the Sun Electric Generator Company. In October 1909, Cove was allegedly kidnapped, and his life was threatened if he did not cease the development of his solar invention. However, the police dismissed Cove’s kidnapping as a hoax. In 1911, both Cove and Burlingame were arrested for stock fraud and spent a year in jail. Although Cove worked on other inventions after that, none of those were related to solar energy.
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In October 1909, Cove was allegedly kidnapped, and his life was threatened if he did not cease the development of his solar invention.
Was George Cove a charlatan? Was he the victim of one? Or was his reputation destroyed because the solar electric generator threatened other companies’ interests? (…)
Source:
George Cove, a forgotten solar power pioneer, may have built a highly efficient photovoltaic panel 40 years before Bell Labs engineers invented silicon cells. If proven to work, his design could lead to less complex and more sustainable solar panels.
solar.lowtechmagazine.com
