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En-TYPE Y 28S P-TYPE Senducor July 9, 1957 H. WELKER 2,798,989 . SEMCONDUCTOR DEVICES AND METHODS OF THEIR MANUFACTURE. Filed March 10, 1952 m 2 Sheets-Sheet ELECTRODEScos sixSEMCONDUCTOR &isit" FIG 2 MEAL ELECTRODE AUGMENTED CONDUCTANCEEn-TYPE Y 28S P-TYPE SENDucor METAL ELECTRODE FIG.3 c.u M July 9, 1957 H. WELKER 2,798,989 SEMICONDUCTOR DEVICES AND METHODS OF THEIR MANUFACTURE Filed arch 10, 1952 2. Sheets-Sheet 2 32 FIG. 11. Z3 2,798,989 United States Patent Office Patented July 9, 1957 2 such, do not contribute to the electric conductivity. Closely related to these linkage conditions is the extreme 2,798,989 mobility, in such bodies, of electrons released photo SEMCONDUCTOR DEVICES AND METHODS OF electrically or coming from points of disturbance, this THER MANUFACTURE mobility reaching values of 3,000 cm./volt sec. in ger manium. Another value of great significance for the Heinrich Welker, Erlangen, Germany, assignor to Sie semiconductive qualities of these substances is the size mens-Schuckertwerke Aktiengesellschaft, Berlin-Sie of the energy band forbidden for the electrons. The mensstadt, Germany size of this band decreases progressively with the increas Application March 10, 1952, Serial No. 275,785 O ing atomic number of the elements. It amounts to 6 to 7 e. v. (electron volt) for diamond, 1.1 e. v. for silicon, Claims priority, application Germany March 10, 1951 0.7 e. v. for germanium, and 0.1 e. v. for gray tin. 15 Claims. (Cl. 317-237) The importance of the four substances for the physics and technology of semiconductors on the one hand, and My invention relates to semiconductors for electric 5 the various inherent difficulties on the other hand, such resistance devices, rectifiers, amplifiers, detectors, con as the infeasible synthetic production of diamond, the trol apparatus, photocells and other technological pur difficult production of pure crystals of silicon, the high poses, as well as to methods of producing such semicon cost of germanium and the instability of the diamond lat ductors, and is described hereinafter with reference to tice of gray tin, pose the problem of finding new sub the drawings in which Figs. 1 to 12 illustrate schemati stances which possess the important characteristic of a cally different respective embodiments of electric de saturated homopolar linkage of one center atom to the vices according to the invention. More particularly: four next neighbor atoms. For technological reasons, Figs. 1, 2 and 3 represent diagrammatically three re it is further desired to find a possibility of varying the spective semiconductor devices and include explanatory width of the electron-forbidden band in a more contin legends in accordance with the description given in the uous manner than offered by the series' C, Si, Ge, Sn. following; It is an object of the invention to solve these problems. Figs. 4, 5 and 6 show perspective views of a resistor, To this end, and in accordance with the invention, a a detector and a three-electrode device respectively; semiconductor for the purposes mentioned is provided by Fig. 7 shows a barrier-layer (dry-type) rectifier and employing a compound of an element AIII of the third Fig. 8 a three-electrode device with respective examples group of the periodic system with an element Bw of the of applicable electric circuits; - fifth group. These compounds are of the type AIBw, in Fig. 9 shows schematically a semiconductor crystal which AIII is an element of the second subgroup in group. with a p-n junction, and Fig. 10 a different semiconductor III, and Bv is an element of the second subgroup in group crystal likewise with a p-n junction; . V of the periodic system. The second subgroup in Group Fig. 11 shows a semiconductor crystal with two p-n 35 III comprises the elements: boron (B), aluminum (al), junctions; and gallium (Ga), indium (In) and thallium (Tl). The Fig. 12 illustrates schematically a semiconductor crys second subgroup in group V comprises the elements: tal with a p-n junction, comprising a Zone of augmented nitrogen (N), phosphorus (P), arsenic (As), antimony p-type conductance and a zone of augmented n-type con (Sb) and bismuth (Bi). Compounds produced of any ductance. 40 two elements of the respective two subgroups are semi During the recent past, the elements in the second conductive, but such compounds of the high-atomic subgroup of the fourth group of the periodic system (C, elements T1 and Bi have not been available or have been Si, Ge, Sn) have gained prominence as semiconductors found much less suitable than those of the remaining for rectifiers, crystal detectors and crystal amplifiers, as four elements of each subgroup. For that reason, the well as for photoelectric, thermoelectric and other ap 45 term AIIIBv is hereinafter used to denote only compounds plications. Carbon, which is a semiconductor only, in of an element selected from boron, aluminum, gallium, its diamond modification, has so far been of merely indium with an element selected from nitrogen, phos scientific interest due to the high price of diamonds and phorus, arsenic and antimony. Semiconductors of this the impossibility of producing them synthetically. Sili type greatly reduce or avoid the abovementioned diffi con has been useful in crystal detectors for electromag 50 culties and, as regards their properties, may be looked netic waves, although the production of its crystals in upon as representing, so to say, replicas or good substitutes pure condition still encounters extreme difficulties so that of the four above-mentioned tetravalent semiconductive the theoretical upper limit of its electric resistance is far elements. Examples of such AIIIBv compounds are the from being attained, Germanium can be produced with following: a purity virtually up to the theoretical upper limit of 55 Substitutes for Si: AIP, GaN its electrical resistance. For that reason, germanium, Substitutes for Ge: GaAs, AlSb, InP in spite of its high cost, has largely superseded silicon Substitute for gray Sn: InSb for detectors and has afforded the possibility of pro ducing controllable crystal devices for industrial appli The substitution is especially complete as regards the cations. Tin, here of interest only in its gray, diamond lattice spacing. Thus the spacing of: latticed modification, has so far been of scientific inter est only, since gray tin is stable only at inconveniently Si-Sis2.35 A., and of AIP=2.36 A. low temperatures and cannot readily be produced in large Ge-Ge=2.43 A., and of GaAs=2.435 A. crystals. - Sn-Sn=2.79 A., and of InSb=2.79 A. The four mentioned elements have the common char 65 The invention also offers the possibility of producing acteristic of a diamond lattice, exhibiting the essential par semiconductive compounds which correspond to extant ticularity that any atom within the crystal lattice is ad or theoretical combinations of the four elements of the jacent to four other atoms which occupy the corners of fourth group. For example: a regular tetrahedron with the first atom on its center. The atoms are linked together by a polarized, saturable 70 Substitutes for Si-C: BP, AlN valence force acting between immediately adjacent atoms. Substitutes for Si-Ge (nonexistent): AlAs, GaP Each such bond is occuplied by two electrons which, as Substitutes for Ge-Sn (nonexistent): GaSb, InAs 2,798,989 3 4. Referring now to Fig. 1, it will be understood that, According to another feature of the invention, indium as a rule, a semiconductor according to the invention, antimonide (InSb) is preferably chosen from among when used as a component of an electrical device, is the antimonides. This compound has a stable cubic joined with two electrodes of metal or other conductive lattice of the zinc-blende type, and therefore represents a material. While in Fig. 1, the electrodes are flat and form good substitute for the unstable gray tin. Indium anti with the AIII Bv semiconductor, a sandwich structure as monide is employed especially when electrically a rela customary for dry rectifiers such as the one shown in Fig. tively high intrinsic conductance (mingled electron-hole 7 and described below, the electrodes as well as the semi conductance) is required from the pure compound. conductor crystal may be given other shapes, such as Aluminum antimonide, according to another feature those apparent from Figs. 4 to 6 and 8, depending upon 10 of the invention is employed as a substitute for ger the particular design or purpose. Regardless of the shape manium. This compound, in its pure monocrystalline and combination in which the semiconductive compounds condition, has an intrinsic conductance smaller than that AIIrBv are used, these compounds offer distinct advan of germanium. Since the compound does not involve the tages over the known semiconductor crystals as will appear slightest problems as regards raw material, it is superior from the following. to germanium mainly in economical respects. The crystal lattices of the compounds AIIIBv differ from those of the corresponding elements of the fourth Gallium antimonide is employed according to the in group. As mentioned, in the fourth-group elements the vention if a semiconductive body is required whose elec lattice points are occupied by tetravalent positive ions tric properties lie between those of InSb and Al Sb. bonded together by a homopolar valence force. In the With the antimonides, a certain technological super compounds AIII. By, the lattice points are occupied by 20 iority of the bodies of the type AIII Bv over bodies of the the third-group elements as trivalent ions and by the fifth type AII. BVI is in evidence. While the solidification or group elements as pentavalent ions, while the remaining phase diagrams for the AIBVI compounds are unknown (3--5-) eight electrons form the linking bond between because of the greatly varying BVI contents due to evap neighboring atoms, each bond being occupied by two oration, these diagrams can be determined for the anti electrons.
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