History of Semiconductors

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Invited paper

History of Semiconductors
Lidia Łukasiak and Andrzej Jakubowski

Abstract—The history of semiconductors is presented begin- (whisker) [3]. Although Braun’s discovery was not imme-
ning with the first documented observation of a
diately appreciated, later it played a significant role in the
semiconductor effect (Faraday), through the development of development of the radio and detection of microwave ra-
the first devices (point-contact rectifiers and transistors, early diation in WWII radar systems [4] (in 1909 Braun shared
field-effect tran- sistors) and the theory of semiconductors up a Nobel Prize in physics with Marconi). In 1874 rectifica-
to the contem- porary devices (SOI and multigate devices). tion was observed by Arthur Schuster in a circuit made of
copper wires bound by screws [4]. Schuster noticed that
Keywords—band theory, laser, Moore’s law, semiconductor, the effect appeared only after the circuit was not used for
transistor. some time. As soon as he cleaned the ends of the wires
(that is removed copper oxide), the rectification was gone.
In this way he discovered copper oxide as a new semicon-
1. Introduction ductor [5]. In 1929 Walter Schottky experimentally con-
firmed the presence of a barrier in a metal-semiconductor
There is no doubt that semiconductors changed the world junction [5].
beyond anything that could have been imagined before
them. Although people have probably always needed to 2.2. Photoconductivity and Photovoltaics
communicate and process data, it is thanks to the semicon-
ductors that these two important tasks have become easy In 1839 Alexander Edmund Becquerel (the father of a great
and take up infinitely less time than, e.g., at the time of scientist Henri Becquerel) discovered the photovoltaic ef-
vacuum tubes. fect at a junction between a semiconductor and an elec-
The history of semiconductors is long and complicated. trolyte [6]. The photoconductivity in solids was discovered
Obviously, one cannot expect it to fit one short paper. by Willoughby Smith in 1873 during his work on subma-
Given this limitation the authors concentrated on the facts rine cable testing that required reliable resistors with high
they considered the most important and this choice is never resistance [7]. Smith experimented with selenium resistors
fully impartial. Therefore, we apologize in advance to all and observed that light caused a dramatic decrease of their
those Readers who will find that some vital moments of resistance. Adams and Day were the first to discover the
the semiconductor history are missing in this paper. photovoltaic effect in a solid material (1876). They noticed
The rest of this paper is organized in four sections devoted that the presence of light could change the direction of the
to early history of semiconductors, theory of their opera- current flowing through the selenium connected to a bat-
tion, the actual devices and a short summary. tery [8]. The first working solar cell was constructed by
Charles Fritts in 1883. It consisted of a metal plate and a
thin layer of selenium covered with a very thin layer of
2. Early History of Semiconductors gold [8]. The efficiency of this cell was below 1% [9].

According to G. Busch [1] the term “semiconducting” was


used for the first time by Alessandro Volta in 1782. The 3. Theory
first documented observation of a semiconductor effect is
that of Michael Faraday (1833), who noticed that the resis- In 1878 Edwin Herbert Hall discovered that charge carri-
tance of silver sulfide decreased with temperature, which ers in solids are deflected in magnetic field (Hall effect).
was different than the dependence observed in metals [2]. This phenomenon was later used to study the properties
An extensive quantitative analysis of the temperature de- of semiconductors [10]. Shortly after the discovery of the
pendence of the electrical conductivity of Ag2S and Cu2S electron by J. J. Thomson several scientists proposed theo-
was published in 1851 by Johann Hittorf [1]. ries of electron-based conduction in metals. The theory of
For some years to come the history of semiconductors fo- Eduard Riecke (1899) is particularly interesting, because
cused around two important properties, i.e., rectification of he assumed the presence of both negative and positive
metal-semiconductor junction and sensitivity of semicon- charge carriers with different concentrations and mobilities
ductors to light and is briefly described in Subsections 2.1 [1]. Around 1908 Karl Baedeker observed the dependence
and 2.2. of the conductivity of copper iodide on the stoichiometry
(io- dine content). He also measured the Hall effect in this
ma- terial, which indicated carriers with positive charge
2.1. Rectification [1]. In 1914 Johan Koenigsberger divided solid-state
In 1874 Karl Ferdinand Braun observed conduction and materials into three groups with respected to their
rectification in metal sulfides probed with a metal point conductivity: metals,

1
Lidia Łukasiak and Andrzej Jakubowski

insulators and “variable conductors” [1]. In 1928 were caused by bad quality of the semiconductor. There-
Ferdinand Bloch developed the theory of electrons in fore he melted the silicon in quartz tubes and then let it
lattices [10]. In 1930 Bernhard Gudden reported that the cool down. The obtained material was still polycrystalline
observed proper- ties of semiconductors were due but the electrical tests demonstrated that the properties
exclusively to the presence of impurities and that were much more uniform. Ohl identified the impurities that
chemically pure semiconductor did not exist [1]. cre- ated the p-n junction that he accidentally obtained
during his technological experiments. He held four patents
on sil- icon detectors and p-n junction [13].

4.3. Bipolar Transistor

In 1945 William Shockley put forward a concept of a semi-


conductor amplifier operating by means of the field-effect
principle. The idea was that the application of a transverse
electric field would change the conductance of a semi-
conductor layer. Unfortunately this effect was not ob-
served experimentally. John Bardeen thought that this was
due to surface states screening the bulk of the material
Fig. 1. Alan Wilson’s theory of bands in solids. from the field (Fig. 2). His surface-theory was published
in 1947 [14].
In 1930 Rudolf Peierls presented the concept of forbid-
den gaps that was applied to realistic solids by Brillouin the
same year. Also in 1930 Kronig and Penney developed a
simple, analytical model of periodic potential. In 1931
Alan Wilson developed the band theory of solids based
on the idea of empty and filled energy bands (Fig. 1).
Wilson also confirmed that the conductivity of
semiconduc- tors was due to impurities [10]. In the same
year Heisen- berg developed the concept of hole (which
was implicit in the works of Rudolf Peierls [10]). In 1938
Walter Schot- tky and Neville F. Mott (Nobel Prize in
1977) indepen- dently developed models of the potential
barrier and cur- rent flow through a metal-semiconductor
junction. A year later Schottky improved his model Fig. 2. The idea of surface states.
including the presence of space charge. In 1938 Boris
Davydov presented a the- ory of a copper-oxide rectifier
including the presence of a p-n junction in the oxide, While working on the field-effect devices, in December
excess carriers and recom- bination. He also understood the 1947 John Bardeen and Walter Brattain built a germanium
importance of surface states [11]. In 1942 Hans Bethe point-contact transistor (Fig. 3) and demonstrated that this
developed the theory of thermionic emission (Nobel Prize device exhibited a power gain. There was, however, an
in 1967). uncertainty concerning the mechanism responsible for the
transistor action [13]. Bardeen and Brattain were convinced
that surface-related phenomena had the dominant role in
the operation of the new device while Shockley favoured
4. Devices bulk conduction of minority carriers. About one month
later he developed a theory of a p-n junction and a junction
4.1. Point-Contact Rectifiers tran- sistor [15]. Shockley, Bardeen and Brattain received
the Nobel Prize in physics in 1956 (John Bardeen received
In 1904 J. C. Bose obtained a patent for PbS point-contact an- other one in 1972 for his theory of superconductivity).
rectifiers [12]. G. Pickard was the first to show that sili- In February 1948 John Shive demonstrated a correctly
con point-contact rectifiers were useful in detection of ra- oper- ating point-contact transistor with the emitter and
dio waves (patent in 1906) [10]. The selenium and copper collector placed on the opposite sides of a very thin slice of
oxide rectifiers were developed, respectively, in 1925 by ger- manium (0.01 cm). This configuration indicated that
E. Presser and 1926 by L. O. Grondahl [10]. The sele- the conduction was indeed taking place in the bulk, not
nium rectifiers were heavily used in the WWII in military along the surface (the distance between the emitter and
communications and radar equipment [10]. collec- tor along the surface would be much longer) [15].
It was only then that Shockley presented his theory of
transistor operation to the coworkers [15], [16].
4.2. The p-n Junction It is worth remembering that the crucial properties of
semiconductors at the time were “structure sensitive”
During his work on the detection of radio waves Russel
Ohl realized that the problems with cat’s whisker detectors
(as Bardeen put it in [14]), that is they were strongly de- in 1960. In the same year Jean Hoerni proposed the pla-
pendent on the purity of the sample. The semiconduc- nar transistor (both base and emitter regions diffused). The
tor material with which Bardeen and Brattain worked was oxide that served as a mask was not removed and acted as
prepared using a technique developed by Gordon K. Teal a passivating layer [15].
and John B. Little based on the Czochralski method. The Further improvement of speed was proposed by Herbert
crystal was then purified using the zone refining method Kroemer. A built-in electric field could be introduced into
proposed by William G. Pfann [11]. the base by means of graded doping. Another way of in-

troducing the electric field in the base he thought of was


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5
tion op- eration speed without The transistor was much
problowering the breakdown more reliable, worked
lemsvoltage too much John faster and generated less
[17].Early thought of a collector heat when compared to the
consisting of two layers, vacuum tubes [18]. Thus it
i.e., high-resistivity one on was anticipated that large
4.4. top of a highly doped one.
systems could be built
A transistor with epitaxial using these devices. The
layer added was reported distance between them
had, however, to be as
short as possible to
minimize delays caused by
interconnects. In 1958
Jack Kilby demonstrated
the first integrated circuit
where several devices
were fab- ricated in one
silicon substrate and
connected by means of
wire bonding. Kilby
realized that this would be
a dis- advantage therefore
in his patent he proposed
formation of interconnects
by means of deposition of
aluminum on a layer of
SiO2 covering the
semiconductor material
[15]. This has been
achieved independently by
Moreover, a lot of Robert Noyce in 1959. In
semiconductor material 2000 Jack Kilby received
was wasted. In 1952 a Noble Prize in physics
alloyed junction transistor for his achievements.
was re- ported (two pellets
of indium were alloyed on
the opposite sides of a slice 4.5. Tunnel Diode
of silicon). Its production
was simpler and less Leo Esaki studied heavily
material-consuming and doped junctions to find out
could be automated at least how high the base of a
partially. The obtained bipolar transistor could be
Fig. 3. The first point-contact doped before the injection
base width was around 10
transistor [16]. at the emitter junction
m, which let the device
operate up to a few MHz became inadequate. He
Point-contact transistors only. The first diffused Ge was aware that in very
were the first to be transistor (diffusion was narrow junctions tunneling
produced, but they were used to form the base could take place. He
extremely unstable and the region, while the emitter obtained the first Ge
electrical charac- teristics was alloyed) with a charac- tunneling diode in 1957
were hard to control. The teristic “mesa” shape was and a silicon one in 1958.
first grown junction reported in 1954. The base Esaki’s presentation at the
transistors were width was 1 m and the International Conference
manufactured in 1952. cut-off frequency 500 of Solid State Physics in
They were much better MHz. It was gener- ally Electrons and
when compared to their understood that for most Telecommunications in
point-contact predecessor, applications silicon 1958 was highly
but the production was transistors would be better appreciated by Shockley
much more difficult. As a than germanium ones due
result of a complicated [19]. Unfortunately,
to lower reverse currents. Shockley exhibited a com-
doping procedure the The first commercially
grown crystal con- sisted plete lack of interest when
available silicon devices Robert Noyce came to him
of three regions forming (grown junction) were
an n-p-n structure. It had to present his idea of a
manufactured in 1954 by tunnel diode two years
to be cut into individual Gordon Teal. The first
devices and contacts had earlier. As a re- sult Noyce
diffused Si transistor moved to other projects
to be made. The process appeared in 1955. To
was difficult and could not [20]. The tunnel diode was
reduce the resistivity of the extremely resistant to the
be auto- mated easily. collector that limited the
6
environmental conditions
due to the fact that
4.6. Metal-Oxide-
conduction was not based
on minority carri- ers or Semiconductor
thermal effects. Field-Effect
Moreover, its switching Transistor
times were much shorter (MOSFET)
than those of the
transistor. Leo Esaki re- In 1930 and 1933 Julius
ceived a Nobel Prize in Lilienfeld obtained Fig. 4. A cross section of a metal-oxide-semiconductor transistor.
physics in 1973 for his patents for de- vices
work on tunneling and resembling today’s
superlattices [21], [22]. MESFET and MOSFET, Early MOSFETs had [35]). Short-channel effects
respec- aluminum gate. are con- siderably reduced
tively. In 1934 Oskar Heil Development of a poly-Si when gate oxide is thin. As
It is estimated that gate gate [28] led to a self- a result of decreased
applied for a patent for his leakage current increases
theoretical work on aligned device, where the thickness, gate leakage
approxi- mately 30 times gate itself constitutes the current obviously grows,
capacitive control in field- every technology
effect tran- sistors [3]. mask for source and drain increasing power
generation, as opposed to diffu- sion. In this way consumption of the entire
The first bipolar transistors 3–5 times increase of
were quite unreliable be- parasitic gate-to-source and chip, which is an
channel leakage current gate-to-drain capacitances undesirable effect for
cause semiconductor [36]. Apart from leakage
surface was not properly associated with gate battery-powered mobile
current, the reduction of overlap could be con- systems.
passivated. A group gate-oxide thickness
directed by M. M. Atalla trolled. Since polysilicon
increases the had relatively high
worked on this problem susceptibility of the
and found out that a layer resistance, gates made of
device to boron penetra- silicides of refractory
of silicon dioxide could be tion from the poly-Si gate
the answer [23]. During metals were proposed (e.g.,
into the channel. A [29], [30]).
the course of this work a number of different high-
new con- cept of a field- Reduction of the size of the
k materials are extensively device led to the so-called
effect transistor was investigated.
developed and the actual short-channel effects
device manufactured [24]. (SCE) including threshold
Unfortunately, the device Fig. 5. A cross section of a
could not match the SOI MOSFET.
performance of bipolar
transistors at the time and
was largely forgotten [15].
Several years before Bell
Laboratories demonstrated
an MOS transistor Paul
Weimer and Torkel
Wallmark of RCA did
work on such devices.
Weimer made transistors
of cadmium sulfide and
cadmium selenide [11]. In
1963 Steven Hofstein and
Fredric Heiman published voltage roll-off and drain-
a paper on a silicon induced barrier lowering.
MOSFET [25] (Fig. 4). In The ways to cope with this
the same year the first problem include a
CMOS circuit was reduction of the depth of
proposed by Frank source and drain [31]
combined with efforts to
Wanlass [26]. In 1970 avoid increased resistance
Willard Boyle and George (e.g., lightly doped drain
Smith presented the [32], ele- vated
concept of charge-coupled source/drain (S/D) [33] or
devices (CCD) – a possibly Schottky bar- rier
semiconductor equivalent S/D [34]). Threshold
of magnetic bubbles [27]. voltage and punchthrough
Both scientists received a are controlled by means of
Nobel Prize in physics in the appropriate doping
2009 for their work on profile of the channel that
CCD. makes it possible to
maintain relatively good
surface mobility (e.g.,

7
Significant progress in year. Many things we are
semiconductor lasers is taking for granted (such
associated, among other, as, e.g., computers,
with the use of quantum Internet and mobile
wells and new ma- terials, phones) would not be
especially gallium nitride. possible without silicon
microelectronics.
Electronic circuits are also
5. S present in cars, home
appliances, machinery, etc.
Fig. 6. Mutigate transistors:
(a) double gate; (b) FinFET;
u Optoelectronic devices are
(c) sur- rounding gate. m equally important in
An interesting extension of emitted by a semicon- everyday life, e.g., fiber-
the classical bulk ductor appeared in 1907 in
m optic communications for
MOSFET is silicon-on- a note by H. J. Round. ar data transfer, data storage
insulator (SOI) – see Fig. Funda- mental work in this (CD and DVD recorders),
5 [37]. The advantage of area was conducted, among y digital cameras, etc.
SOI is the ease of other, by Since the beginning of
electrical isolation of a Silicon may be considered semiconductor electronics
device from the rest of the as the information carrier the num- ber of transistors
integrated circuit, which of our times. In the history in an integrated circuit has
increases packing density. of information there were been increasing
Moreover, the area of two revolutions exponentially with time.
source and drain junctions (approximately 500 years This trend had been first
is significantly reduced, apart). The first was that noticed by Gordon Moore
thus decreasing parasitic of Johan Gutenberg who [43] and is called Moore’s
capaci- tances. Finally, the made information law. This law is illustrated
depletion width is limited available to many, the in Fig. 7, where the
by the Si body thickness, other is the invention of number of transistors in
therefore it is widely the transistor. Currently successive Intel processors
believed that SOI helps the global amount of is plotted as a function of
reduce short channel information doubles every time (data after [44]).
effects unless source-to- Losev. A very interesting description of the development
drain coupling through
channel and BOX cannot o
be neglected. The f
properties of SOI devices
are improved with the re- l
duction of body thickness. i
It is believed that fully g
depleted ultra-thin-body h
SOI (FD UTB SOI) is one t
of the best scal- ing -
solutions. Due to excellent e
gate control of the channel m
these devices may be i
undoped or very lightly t
doped. In this way t
mobility is not degraded i
and threshold voltage is
n
less dependent on the
fluctuations of doping g
concentra- tion [38].
Another advantage of SOI d
is that it facilitates i
development of new o
device concepts [39] (Fig. d
6), but this is another e
story. s

m
4.7. Semiconductor a
Lasers y

Semiconductors are b
widely used for emission e
and detection of radiation.
The first report on light f
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devices and became Fig. 7. Number of [2] F. Laeri, F. Schüth, U.
Simon, and M. Wark, [4] J. Orton, Semiconductors
familiar with p-i-n and p- transistors in successive
Host-Guest-Sys- tems Based and the Information
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[44] Hardware components, e , Teaching of the Institute of
Intel processor history, t
http://www.interfacebus.co Microelectronics and
m/intel-processor-types- o h r Optoelec- tronics. Her
release-date.html f e e research interests include
s modeling and char-
M P p acterization of
i h e semiconductor devices and
c . c microprocessor systems.
r D t e-mail:
o . i
e v [email protected]
l a e Institute of
e n l Microelectronics and
c d y Optoelectronics Warsaw
t . University of
r D Technology
o . S Koszykowa st 75
n S i 00-662 Warsaw, Poland
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h Institute of
e Microelectronics and
Optoelectronics
H Warsaw University of
e Technology
a Koszykowa st 75
d 00-662 Warsaw, Poland
of the Division of
Microelectronics and
Nanoelectronics Devices
of IMiO. He was the
Director of the Institute
of Electron Technology
(ITE) in the years 1989–
1992 and Director of
IMiO from 2004 till
2008. Between 1990 and
1991 he was the
Chairman of the
Committee of Applied
Research and a member
of the Prime Minister’s
Commit- tee of Science
and Technical Progress.
He was the Vice-
chairman of the
Committee of Electronics
and Telecom-
munications of Polish
Academy of Sciences
between 1989 and 2007.
He was also the
Chairman of the
Microelec- tronics
Section of this Committee
from 1988 till 2003. He
was the editor-in-chief of
“Electron Technology”
be- tween 1990 and 1994.
He is the author or co-
author of more than 600
publications (journal and
conference pa- pers,
monographs) and several
textbooks for students, as
well as popular-science
papers. He delivered
many invited lectures at
foreign universities and
international confer-
ences in Europe, United
States and Asia. He
supervised 23 Ph.D.
theses and more than 150
B.Sc., and M.Sc. the- ses.
He received 5 Awards of
the Minister of National
Education. The main
areas of his research are
modeling,
characterization and
fabrication of
semiconductor structures
(e.g., MOS, SOI MOS,
HBT, SiGe MOS).
e-mail:
[email protected].
pl

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