Introduction

Abstract

Important dates and events in the history of semiconductors are chronologically listed, from the early days (Volta, Seebeck and Faraday) to the latest achievements like the blue and white LED. Many known and not so well known scientists are mentioned. Also a list of semiconductor related Nobel prizes and their winners is given.

The proper conduct of science lies in the pursuit of Nature’s puzzles, wherever they may lead.

J.M. Bishop [2]

The historic development of semiconductor physics and technology began in the second half of the 19th century. Interesting discussions of the history of the physics and chemistry of semiconductors can be found in [3–5]. The development of crystal growth is covered in [6]. The history of semiconductor industry can be followed in [7, 8]. In [9] 141 pioneering papers on semiconductor devices are compiled. In 1947, the commercial realization of the transistor was the impetus to a fast-paced development that created the electronics and photonics industries. Products founded on the basis of semiconductor devices such as computers (CPUs, memories), optical-storage media (lasers for CD, DVD), communication infrastructure (lasers and photodetectors for optical-fiber technology, high frequency electronics for mobile communication), displays (thin film transistors, LEDs), projection (laser diodes) and general lighting (LEDs) are commonplace. Thus, fundamental research on semiconductors and semiconductor physics and its offspring in the form of devices has contributed largely to the development of modern civilization and culture.

1.1 Timetable and Key Achievements

In this section important milestones in semiconductor physics and technology are listed.

1782

A. Volta—coins the phrase ‘semicoibente’ (semi-insulating) which was translated then into English as ‘semiconducting’ [10].

1821

T.J. Seebeck—discovery of thermopower (electrical phenomena upon temperature difference) in metals and PbS, FeS$_2$, CuFeS$_2$ [11, 12].

1833

M. Faraday—discovery of the temperature dependence of the conductivity of Ag$_2$S (sulphuret of silver, negative dR/dT) [13].

1839

A.E. Becquerel¹—photoelectric effect (production of a photocurrent when electrodes covered by copper or silver halides salts (in an electrolyte) were illuminated by solar light) [14–17].

1834

J. Peltier—discovery of the Peltier effect (cooling by current) [18].

1873

W. Smith—discovery of photoconductivity in selenium [19, 20]. Early work on photoconductivity in Se is reviewed in [21, 22].

1874

F. Braun²—discovery of rectification in metal–sulfide semiconductor contacts [24], e.g. for CuFeS$_2$ and PbS. The current through a metal–semiconductor contact is nonlinear (as compared to that through a metal, Fig. 1.1), i.e. a deviation from Ohm’s law. Braun’s structure is similar to a MSM diode.

Fig. 1.1

Experimental data from [24]

Current through a silver–CuFeS$_2$–silver structure as a function of the current through the metal only, 1874. Data points are for different applied voltages.

1876

W.G. Adams and R.E. Day—discovery of the photovoltaic effect in selenium [25].

W. Siemens—large response from selenium photoconductor [26], made by winding two thin platinum wires to the surface of a sheet of mica, and then covering the surface with a thin film of molten selenium. Resistance ratio between dark and illuminated by sunlight was larger than ten [26] and measured to 14.8 in [27].

1879

E.H. Hall—measurement of the transverse potential difference in a thin gold leaf on glass [28, 29]. Experiments were continued by his mentor H.A. Rowland [30]. A detailed account of the discovery of the Hall efect is given in [31, 32].

1883

Ch. Fritts—first solar cell, based on an gold/selenium rectifier [27]. The efficiency was below 1%.

1901

J.C. Bose—point contact detector for electromagnetic waves based on galena (PbS) [33]. At the time, the term semiconductor was not introduced yet and Bose speaks about ‘substances of a certain class (...) presenting a decreasing resistance to the passage of the electric current with an increasing impressed electromotive force’.

1906

G.W. Pickard—rectifier based on point contact (cat’s whisker) diode on silicon [34–36]. Erroneously, the rectifying effect was attributed to a thermal effect, however, the drawing of the ‘thermo-junction’ (TJ in Fig. 1.2) developed into the circuit symbol for a diode (cmp. Fig. 21.63a).

Fig. 1.2

Adapted from [34]

Circuit diagram for a radio receiver with a point-contact diode (TJ).

1907

H.J. Round—discovery of electroluminescence investigating yellow and blue light emission from SiC [37].

K. Bädeker—preparation of metal (e.g. Cd, Cu) oxides and sulfides and also CuI from metal layers using a vapor phase transport method [38]³. CuI is reported transparent ($\sim 200$ nm thick films) with a specific resistivity of $\rho =4.5\times 10^{-2}$ $\Omega$ cm, the first transparent conductor.⁴ Also CdO (films of thickness 100–200 nm) is reported to be highly conductive, $\rho =1.2\times 10^{-3}$ $\Omega$ cm, and orange-yellow in color, the first reported TCO (transparent conductive oxide).

1909

K. Bädeker—discovery of doping. Controlled variation of the conductivity of CuI by dipping into iodine solutions (e.g. in chloroform) of different concentrations [41].

1910

W.H. Eccles—negative differential resistance of contacts with galena (PbS), construction of crystal oscillators⁵ [45].

1911

The term ‘Halbleiter’ (semiconductor) is introduced for the first time by J. Weiss [46] and J. Königsberger and J. Weiss [47]. Königsberger preferred the term ‘Variabler Leiter’ (variable conductor).

1912

M. von Laue—X-ray diffraction of bulk crystals including ZnS (Fig. 1.3) [48, 49].

Fig. 1.3

Adapted from [48]

Laue images of ’regular’ (cubic) ZnS along three major crystallographic directions, directly visualizing their 4-, 3- and 2-fold symmetry.

1925

J.E. Lilienfeld⁶—proposal of the metal-semiconductor field-effect transistor (MESFET) [53], with suggested copper sulfide thin film channel and aluminum gate.⁷ (Fig. 1.4). Lilienfeld was also awarded patents for a depletion mode MOSFET [55] with proposed copper sulfide, copper oxide or lead oxide channel and current amplification with nppn- and pnnp-transistors [56]. Due to the lack of other publications of Lilienfeld on transistors, it is under discussion whether Lilienfeld just patented ideas or also build working devices with mounting evidence for the latter [51, 54, 57].

Fig. 1.4

From [53]

Sketch of a field-effect transistor, 1926.

1927

A. Schleede, H. Buggisch—synthesis of pure, stoichiometric PbS, influence of sulphur excess and impurities [58].

A. Schleede, E. Körner—activation of luminescence of ZnS [59, 60].

1928

F. Bloch—quantum mechanics of electrons in a crystal lattice, ‘Bloch functions’ [61].

O.V. Losev—description of the light emitting diode⁸ (SiC) [65]; light emission was observed in forward direction and close to breakdown (Fig. 1.5a). Also current modulation of LED light output was reported (Fig. 1.5b) [65].

Fig. 1.5

Adapted from [65]

a I–V characteristic of SiC/steel wire light emitting diode. The dotted curve is the flipped curve for negative voltage (3rd quadrant). b Recording of current modulated (at 500 Hz) LED on moving photographic plate.

1929

R. Peierls—explanation of positive (anomalous) Hall effect with unoccupied electron states [66, 67].

1930

R. Peierls—first calculation of a band structure and band gap⁹ (Fig. 1.6) [69].

Fig. 1.6

Adapted from [69]

First band structure calculation from Peierls ($\xi =k \, a$).

1931

W. Heisenberg—theory of hole (‘Löcher’) states [70].

R. de L. Kronig and W.G. Penney—properties of periodic potentials in solids [71].

A.H. Wilson¹⁰—development of band-structure theory [74, 75].

1933

C. Wagner—excess (‘Elektronenüberschuss-Leitung’, n-type) and defect (‘Elektronen-Defektleitung’, p-type) conduction [76–79]. Anion deficiency in ZnO causes conducting behavior [80].

1934

C. Zener—Zener tunneling [81].

1936

J. Frenkel—description of excitons [82].

1938

B. Davydov—theoretical prediction of rectification at pn-junction [83] and in Cu$_2$O [84].

W. Schottky—theory of the boundary layer in metal–semiconductor contacts [85], being the basis for Schottky contacts and field-effect transistors.

N.F. Mott—metal–semiconductor rectifier theory [86, 87].

R. Hilsch and R.W. Pohl—three-electrode crystal (KBr) [88].

1940

R.S. Ohl—Silicon-based photoeffect (solar cell, Fig. 1.7) [89] from a pn-junction formed within a slab of polycrystalline Si fabricated with directed solidification due to different distribution coefficients of p- and n-dopants (boron and phosphorus, cmp. Fig. 4.6b) (J. Scaff and H. Theurer) [90, 91].

Fig. 1.7

Adapted from [89]

a Optical image of directionally solidified silicon. The lower part contains predominantly boron, the upper part contains predominantly phosphorous. First the growth is porous and subsequently columnar. Adapted from [90]. b Spectral response of silicon pn-junction photoelement, 1940. The inset depicts schematically a Si slab with built-in pn-junction formed during directed solidification as shown in panel (a). The arrow denotes the direction of solidification (cmp. Fig. 4.6).

1941

R.S. Ohl—Silicon rectifier with point contact [92, 93] (Fig. 1.8), building on work from G.W. Pickard (1906) and using metallurgically refined and intentionally doped silicon (J. Scaff and H. Theurer) [90].

Fig. 1.8

Adapted from [92]

Characteristics of a silicon rectifier, 1941.

1942

K. Clusius, E. Holz and H. Welker—rectification in germanium [94].

1945

H. Welker—patents for JFET and MESFET [95].

1947

W. Shockley, J. Bardeen and W. Brattain fabricate the first transistor in the AT&T Bell Laboratories, Holmdel, NJ in an effort to improve hearing aids [96].¹¹ Strictly speaking the structure was a point-contact transistor. A 50-$\upmu$m wide slit was cut with a razor blade into gold foil over a plastic (insulating) triangle and pressed with a spring on n-type germanium (Fig. 1.9a) [97]. The surface region of the germanium is p-type due to surface states and represents an inversion layer. The two gold contacts form emitter and collector, the large-area back contact of the germanium the base contact [98]. For the first time, amplification was observed [99]. Later models use two close point contacts made from wires with their tips cut into wedge shape (Fig. 1.9b) [98].¹² More details about the history and development of the semiconductor transistor can be found in [100], written on the occasion of the 50th anniversary of its invention.

Fig. 1.9

Adapted from [98]

a The first transistor, 1947 (length of side of wedge: 32 mm). b Cutaway model of a 1948 point contact transistor (‘Type A’) based on n-type bulk Ge ($n=5 \times 10^{14}$ cm$^{-3}$) and common base circuit diagram. The surface region ($\sim 100$ nm depth) of the Ge is p-type due to surface states and represents an inversion layer. The two wires are made from phosphor bronze.

1948

W. Shockley—invention of the bipolar (junction) transistor [101].

1952

H. Welker—fabrication of III–V compound semiconductors¹³ [104–107].

W. Shockley—description of today’s version of the (J)FET [108].

1953

G.C. Dacey and I.M. Ross—first realization of a JFET [109].

D.M. Chapin, C.S. Fuller and G.L. Pearson—invention of the silicon solar cell at Bell Laboratories [110]. A single 2 cm$^2$ photovoltaic cell from Si, Si:As with an ultrathin layer of Si:B, with about 6% efficiency generated 5 mW of electrical power.¹⁴ Previously existing solar cells based on selenium had very low efficiency ($<0.5$%).

1958

J.S. Kilby made the first integrated circuit at Texas Instruments. The simple 1.3 MHz RC-oscillator consisted of one transistor, three resistors and a capacitor on a $11\times 1.7$ mm$^2$ Ge platelet (Fig. 1.10a). J.S. Kilby filed in 1959 for a US patent for miniaturized electronic circuits [111]. At practically the same time R.N. Noyce from Fairchild Semiconductors, the predecessor of INTEL, invented the integrated circuit on silicon using planar technology [112]. A detailed and (very) critical view on the invention of the integrated circuit can be found in [113].

Fig. 1.10

a The first integrated circuit, 1958 (germanium, $11\times 1.7$ mm$^2$). b The first planar integrated circuit, 1959 (silicon, diameter: 1.5 mm)

Figure 1.10b shows a flip-flop with four bipolar transistors and five resistors. Initially, the invention of the integrated circuit¹⁵ met scepticism because of concerns regarding yield and the achievable quality of the transistors and the other components (such as resistors and capacitors).

1959

J. Hoerni¹⁶ and R. Noyce—first realization of a planar transistor (in silicon) (Fig. 1.11) [115–119].

Fig. 1.11

(a) Optical image of planar pnp silicon transistor (2N1613 [120]), 1959. The contacts are Al surfaces (not bonded). (b) Housing of such transistor cut open

1960

D. Kahng and M.M. Atalla—first realization of a MOSFET [121, 122].

1962

The first semiconductor laser on GaAs basis at 77 K at GE [123, 124] (Fig. 1.12) and at IBM [125] and MIT [126].

First visible laser diode [127].¹⁷

Fig. 1.12

Adapted from [124]

Schematics of GaAs-based laser diode. The active layer is highlighted in red.

1963

Proposal of a double heterostructure laser (DH laser) by Zh.I. Alferov [130, 131] and H. Kroemer [132, 133].

J.B. Gunn—discovery of the Gunn effect, the spontaneous microwave oscillations in GaAs and InP at sufficiently large applied electric field (due to negative differential resistance) [134].

1966

C.A. Mead—proposal of the MESFET (‘Schottky Barrier Gate FET’) [135].

1967

Zh.I. Alferov—report of the first DH laser on the basis of Ga(As,P) at 77 K [136, 137].

W.W. Hooper and W.I. Lehrer—first realization of a MESFET [138].

1968

DH laser on the basis of GaAs/(Al,Ga)As at room temperature, independently developed by Zh.I. Alferov [139] and I. Hayashi [140].

GaP:N LEDs with yellow-green emission (550 nm) and 0.3% efficiency [141].

1968

SiC blue LED with efficiency of 0.005% [142].

1970

W.S. Boyle and G.E. Smith—invention of the charge coupled device (CCD) [143, 144].

1971

R.F. Kazarinov and R.A. Suris—proposal of the quantum cascade laser [145].

1975

R.S. Pengelly and J.A. Turner—first monolithic microwave integrated circuit (MMIC) (Fig. 1.13) [146]

Fig. 1.13

Adapted from [146]

Equivalent circuit and optical image of first monolithic microwave integrated circuit (exhibiting gain ($4.5\pm 0.9$ dB) in the frequency range 7.0–11.7 GHz).

1992

S. Nakamura—growth of high-quality group-III–nitride thin films [147], blue nitride heterostructure LED with efficiency exceeding 10% (1995) [148] (Fig. 1.14a). Later the white LED was built by combining a blue LED with yellow phosphors (Fig. 1.14b, c).

Fig. 1.14

a Blue LED (standard housing). 50 W, 4000 lm, b warm white and c cold white LED ($45\times 45$ mm$^2$)

1994

J. Faist and F. Capasso—quantum cascade laser [149].

N. Kirstaedter, N.N. Ledentsov, Zh.I. Alferov and D. Bimberg—quantum dot laser [150].

2004

H. Hosono and T. Kamiya—thin film transistor (TFT) from amorphous oxide semiconductor [151].

1.2 Nobel Prize Winners

Several Nobel Prizes¹⁸ have been awarded for discoveries and inventions in the field of semiconductor physics (Fig. 1.15).

1909

Karl Ferdinand Braun

‘in recognition of his contributions to the development of wireless telegraphy’

1914

Max von Laue ‘for his discovery of the diffraction of X-rays by crystals’

1915

Sir William Henry Bragg

William Lawrence Bragg

‘for their services in the analysis of crystal structure by means of X-rays’

1946

Percy Williams Bridgman

‘for the invention of an apparatus to produce extremely high pressures, and for the discoveries he made therewith in the field of high pressure physics’

1953

William Bradford Shockley

John Bardeen

Walter Houser Brattain

‘for their researches on semiconductors and their discovery of the transistor effect’

1973

Leo Esaki

‘for his experimental discoveries regarding tunneling phenomena in semiconductors’

Fig. 1.15

Winners of Nobel Prize in Physics and year of award with great importance for semiconductor physics

1985

Klaus von Klitzing

‘for the discovery of the quantized Hall effect’

1998

Robert B. Laughlin

Horst L. Störmer

Daniel C. Tsui

‘for their discovery of a new form of quantum fluid with fractionally charged excitations’

2000

Zhores I. Alferov

Herbert Kroemer

‘for developing semiconductor heterostructures used in high-speed and optoelectronics’

Jack St. Clair Kilby

‘for his part in the invention of the integrated circuit’

2009

Willard S. Boyle

George E. Smith

‘for the invention of an imaging semiconductor circuit—the CCD sensor’

2010

Andre Geim

Konstantin Novoselov

‘for groundbreaking experiments regarding the two-dimensional material graphene’

2014

Isamu Akasaki

Hiroshi Amano

Shuji Nakamura

‘for the invention of efficient blue light-emitting diodes which has enabled bright and energy-saving white light sources’

Table 1.1 Physical properties of various (bulk) semiconductors at room temperature. ‘S’ denotes the crystal structure (d: diamond, w: wurtzite, zb: zincblende, ch: chalcopyrite, rs: rocksalt)

1.3 General Information

In Fig. 1.16, the periodic table of elements is shown.

In Table 1.1 the physical properties of various semiconductors are summarized. Data on semiconductors can be found in [152–166].

Fig. 1.16

From [167]

Periodic table of elements.