US2817798A - Semiconductors - Google Patents

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US2817798A
US2817798A US427098A US42709854A US2817798A US 2817798 A US2817798 A US 2817798A US 427098 A US427098 A US 427098A US 42709854 A US42709854 A US 42709854A US 2817798 A US2817798 A US 2817798A
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silicon
germanium
alloy
rectifying
electrode
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US427098A
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Dietrich A Jenny
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RCA Corp
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Priority to FR1123706D priority patent/FR1123706A/en
Priority to GB10698/55A priority patent/GB808973A/en
Priority to CH354168D priority patent/CH354168A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/185—Joining of semiconductor bodies for junction formation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D99/00—Subject matter not provided for in other groups of this subclass

Definitions

  • This invention relates to improved semiconductor materials and to improved rectifying and transistor devices made from these materials. More particularly, the invention relates to improved devices which utilize a germanium-silicon alloy.
  • germanium devices Many different semiconductor devices utilizing semiconductive germanium or silicon are known, but the operation of germanium devices is usually subject to relatively severe maximum temperature limitations. Silicon devices have certain electrical disadvantages when compared to those of germanium.
  • the maximum operating temperature of a typical device is determined primarily by the energy gap between the valence band and the conduction band of the semiconductive material of the device. When the temperature of the device is increased to a value at which thermal energy is sufficient to drive substantial numbers of electrons across the energy gap, the semiconductive characteristics of the material are adversely affected.
  • the energy gap of germanium is about 0.71 electron volt and many devices utilizing germanium become substantially inoperative above, temperatures as low as 40 C.
  • silicon has a higher energy gap and its operation as a semiconductor is not adversely affected by much wider normal temperature changes.
  • Silicon is a relatively more diflicult material to prepare in highly pure crystalline form and to fabricate into semiconductor devices such as transistors.
  • the semiconductive properties of silicon such as electron mobility, hole mobility and lifetime are considerably inferior to those of germanium.
  • alloys, of germanium and silicon permits the design and preparation of useful and practical semiconductor devices of prescribed intermediate temperature and electrical characteristics.
  • the use of such alloys avoids some of the less desirable characteristics of each of the component materials of the alloy.
  • Devices of such alloys thus provide much higher temperature stability normally only afforded by silicon and the greater lifetime and hole and electron mobility normally characteristic of germanium.
  • single crystal germanium-silicon alloy is suitable for making many different types of semiconductor devices.
  • the alloy may be prepared in polycrystalline form by melting together germanium and silicon. Utilizing a seed crystallite cut from a polycrystalline ingot, a single crystal may be grown from the melt by any of the conventional techniques such as the Czochralski process.
  • Another object of the instant invention is to provide semiconductor rectifying devices having improved electrical and operating temperature characteristics.
  • a further object of this invention is to provide improved semiconductor devices made from alloys of germanium and silicon.
  • Figure 1 is a schematic, partially cross-sectional, elevational view of one form of semiconductor device having rectifying properties and made in accordance with the present invention.
  • Figure 2 is a schematic, partially crosssectional, elevational view of another form of semiconductor device having rectifying properties and made in accordancewith the present invention.
  • Figure 3 is a schematic, partially cross-sectional, elevational view of another form of semiconductor device having point'contact rectifying electrodes and made in accordance with the present invention.
  • Figure 4 is a schematic, partially cross-sectional, elevational view of another. form of semiconductor device having alloy junction rectifying electrodes and made in accordance with the present invention.
  • the single crystal wafers for such devices are cut from a single crystal ingot prepared from a melt of germanium and silicon.
  • the single crystal ingot is prepared by taking a seed crystallite, for example, cut from a polycrystalline ingot, dipping this crystallite into the melt and slowly pulling it from the melt according to the Czochralski technique described in Crystal Growth by H. E. Buckley (Wiley, N. Y., 1951).
  • a method of making crystalline semiconducting silicon-germanium alloy having improved uniformity is described in a copending application of Everett R. Johnson, Serial No.
  • a germanium-silicon alloy suitable for making devices of the present invention is prepared by adding 1% or more of pure silicon powder to molten germanium which has previously been purified to provide a resistivity of over 1 ohm/cm.
  • the relative amounts of germanium and silicon in the alloy are not critical, but the upper temperature stability limit of the device is increased as the proportion of silicon is increased. From this alloy, as described above, a single crystalline ingot is prepared and Wafers are then cut from the ingot.
  • a specific embodiment of a device made in accordance with the present invention comprises a small area electrode type rectifying device wherein a wafer 3 of germanium-silicon alloy is afiixed to a conductive base electrode 4 by a layer of solder 5 to provide an ohmic base connection.
  • the electrode 6 is a rectifying electrode.
  • the surface of the alloy crystal in contact with the rectifying electrode 6 preferably is ground with A1 0 and etched according to the method hole and electron mobility as compared with devices .of
  • Figure 2 illustrates a conventional alloy junction rectifier type semiconductor device according to the invention.
  • This device is made from a. wafer 3" of'semiconductive germaniumsilicon,. alloy, ,for example, ofP-v type conductivity, which is dipped into an-etch solution consisting of:
  • rial such as antimony, capable of. imparting. N-type conductivity to semi-conducting germanium-.01: silicon, is al-. loyed to the upper surface 9 of. the germanium-silicon alloy wafer 3.
  • the pellet8 of antimony is, placed on the surface 9 of the etched wafer at room temperature and is heated for 5 to 10 minutes at 600 to700 C; to form a,
  • rectifying junction 10 After cooling to room. tempera? ture the alloy is etched in two stages without intermediate, washing to clean the area around and improve theelec trical characteristics of thejunction 10,.and to improve;
  • the first etch solution preferably con.-
  • An electrode lead 11 is affixed to the alloyed pellet.
  • the device of Figure 2 thus comprises a junction-type rectifier. Any other material, such as bismuth or vanadium, capableof imparting N-type conductivity to germanium or silicon, may be substituted for antimony.
  • the pellet 8 should be of aluminum, gallium, indium or;
  • Fig. 1 may be-modified' as in Fig. 3 to include an additional rectifying point contact electrode 12 to provide a transistor.
  • the electrode 14, soldered to the wafer 3 functions as a base electrode.
  • the device of Fig.2 may be modified, for example as shown in Fig. 4; to include an additional rectifying junction 13 and'an electrode lead 16 to provide a transistor device.
  • This device also includes a base electrode which may be'in the form of a nickel tab soldered to the wafer 3.
  • a semiconductor device including in combination a single crystal body of an alloy of germanium and at least 1% silicon having semiconductingproperties and at least one rectifyingelectrode connected thereto.
  • a device according to claim 1 in whichsaid rectifyingelectrodeis asmall area type electrode.
  • a semiconductor device comprising in combination a single crystal waferof germanium-silicon semiconducting-alloy ofone conductivity type and at least one P-N junction rectifying electrode.
  • a semiconductor device including in'cornbination a single crystal body of an alloy of germanium and at least 1% silicon having semiconducting properties and a plurality ofrectifying electrodes connected thereto.
  • a semiconductordevice of the alloy rectifying junction type comprising in combination a single crystalline wafer of germanium-silicon semiconducting alloy of one conductivity-type and a plurality of alloy junction type rectifying electrodes.
  • a semiconductor device including in combination a single crystal body of an alloy of germanium and at least 1% silicon having semiconducting properties and at least onelarge area rectifying electrode in contact therewith.
  • a semiconductor device including in combination a single crystal body of an alloy of germanium and at least 1% silicon having semiconducting properties and a plurality of large area rectifying electrodes in contact therewith.
  • a transistor device comprising a semiconductor body of single crystal alloy of germanium and silicon and emitter, collector, andbase electrodes connected thereto.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Description

Dec; 24, 1957 JENNY 2,817,798
SEMICONDUCTORS Filed May 3', 1954 F21. j 5 A;
IN V EN TOR.
' DIEIRIE'H H. JENNY SEMICONDUCTURS Dietrich A. Jenny, Princeton, N. J., assignor to Radio Corporation of America, a corporation of Delaware Application May 3, 1954, Serial No. 427,098
8 Claims. (Cl. 317-235) This invention relates to improved semiconductor materials and to improved rectifying and transistor devices made from these materials. More particularly, the invention relates to improved devices which utilize a germanium-silicon alloy.
Many different semiconductor devices utilizing semiconductive germanium or silicon are known, but the operation of germanium devices is usually subject to relatively severe maximum temperature limitations. Silicon devices have certain electrical disadvantages when compared to those of germanium. The maximum operating temperature of a typical device is determined primarily by the energy gap between the valence band and the conduction band of the semiconductive material of the device. When the temperature of the device is increased to a value at which thermal energy is sufficient to drive substantial numbers of electrons across the energy gap, the semiconductive characteristics of the material are adversely affected. For example, the energy gap of germanium is about 0.71 electron volt and many devices utilizing germanium become substantially inoperative above, temperatures as low as 40 C. On the other hand, silicon has a higher energy gap and its operation as a semiconductor is not adversely affected by much wider normal temperature changes. Silicon, however, is a relatively more diflicult material to prepare in highly pure crystalline form and to fabricate into semiconductor devices such as transistors. Moreover, the semiconductive properties of silicon, such as electron mobility, hole mobility and lifetime are considerably inferior to those of germanium.
In accordance with the present invention, it has been found that the use of alloys, of germanium and silicon permits the design and preparation of useful and practical semiconductor devices of prescribed intermediate temperature and electrical characteristics. The use of such alloys avoids some of the less desirable characteristics of each of the component materials of the alloy. Devices of such alloys thus provide much higher temperature stability normally only afforded by silicon and the greater lifetime and hole and electron mobility normally characteristic of germanium.
It is also known that semiconductor devices made of single crystals of material have certain advantages over devices made of polycrystalline material. Further, in accordance with the present invention, it has been found that single crystal germanium-silicon alloy is suitable for making many different types of semiconductor devices. The alloy may be prepared in polycrystalline form by melting together germanium and silicon. Utilizing a seed crystallite cut from a polycrystalline ingot, a single crystal may be grown from the melt by any of the conventional techniques such as the Czochralski process.
Accordingly, it is an object of the instant invention to provide improved semiconductor devices operable at relatively high temperatures.
Another object of the instant invention is to provide semiconductor rectifying devices having improved electrical and operating temperature characteristics.
it tat Patent 2,817,798 Patented Dec. 24,1957
A further object of this invention is to provide improved semiconductor devices made from alloys of germanium and silicon.
The invention will be described in greater detail in connection with the accompanying drawing in which:
Figure 1 is a schematic, partially cross-sectional, elevational view of one form of semiconductor device having rectifying properties and made in accordance with the present invention.
Figure 2 is a schematic, partially crosssectional, elevational view of another form of semiconductor device having rectifying properties and made in accordancewith the present invention."
Figure 3 is a schematic, partially cross-sectional, elevational view of another form of semiconductor device having point'contact rectifying electrodes and made in accordance with the present invention.
Figure 4 is a schematic, partially cross-sectional, elevational view of another. form of semiconductor device having alloy junction rectifying electrodes and made in accordance with the present invention.
Similar reference characters are applied to similar elements through-out the drawing.
Alloys of polycrystalline germanium and silicon of varying proportions have been prepared by Stohr and Klemrn, Zeitschrift fur Anorg. und Allgemeine Chem. 241, 205-424, June (1939). These alloys were not pre pared so as to be semiconductor materials. in accordance with the instant invention, however, single crystals of germanium-silicon alloy having semiconductor properties are prepared and utilized in the fabrication of rectifying and amplifying type semiconductor devices.
The single crystal wafers for such devices are cut from a single crystal ingot prepared from a melt of germanium and silicon. The single crystal ingot is prepared by taking a seed crystallite, for example, cut from a polycrystalline ingot, dipping this crystallite into the melt and slowly pulling it from the melt according to the Czochralski technique described in Crystal Growth by H. E. Buckley (Wiley, N. Y., 1951). A method of making crystalline semiconducting silicon-germanium alloy having improved uniformity is described in a copending application of Everett R. Johnson, Serial No. 427,357, filed concurrently with the present application, now abandoned, and a method of obtaining large crystalline ingots of uniform predetermined composition of germanium-silicon alloy is described in another copending application of Everett R. Johnson, Serial No. 427,067, also filed concurrently with this application, and now abandoned.
A germanium-silicon alloy suitable for making devices of the present invention, is prepared by adding 1% or more of pure silicon powder to molten germanium which has previously been purified to provide a resistivity of over 1 ohm/cm. The relative amounts of germanium and silicon in the alloy are not critical, but the upper temperature stability limit of the device is increased as the proportion of silicon is increased. From this alloy, as described above, a single crystalline ingot is prepared and Wafers are then cut from the ingot.
Referring now to Figure l, a specific embodiment of a device made in accordance with the present invention comprises a small area electrode type rectifying device wherein a wafer 3 of germanium-silicon alloy is afiixed to a conductive base electrode 4 by a layer of solder 5 to provide an ohmic base connection.
Another electrode 6, preferably in the form of a sharply pointed wire of Phosphor bronze, is supported in contact with another surface of the alloy body at a point remote from the base support electrode 4. The electrode 6 is a rectifying electrode. The surface of the alloy crystal in contact with the rectifying electrode 6 preferably is ground with A1 0 and etched according to the method hole and electron mobility as compared with devices .of
pure silicon, thus providing the preferredproperties of each component element.
Figure 2 illustrates a conventional alloy junction rectifier type semiconductor device according to the invention. This device is made from a. wafer 3" of'semiconductive germaniumsilicon,. alloy, ,for example, ofP-v type conductivity, which is dipped into an-etch solution consisting of:
Part 70%HNO s. 52% HZFZ H2O 1 The lower surface of the etched wafer is :soldered to a;con-, ductive base electrode 4 by a layer of solder. 5 to form an ohmic base connection. A small pellet 8 of a mate-.
rial such as antimony, capable of. imparting. N-type conductivity to semi-conducting germanium-.01: silicon, is al-. loyed to the upper surface 9 of. the germanium-silicon alloy wafer 3. The pellet8 of antimony is, placed on the surface 9 of the etched wafer at room temperature and is heated for 5 to 10 minutes at 600 to700 C; to form a,
rectifying junction 10. After cooling to room. tempera? ture the alloy is etched in two stages without intermediate, washing to clean the area around and improve theelec trical characteristics of thejunction 10,.and to improve;
the electrical characteristics of thegermanium-silicon alloy surface. The first etch solution. preferably con.-
An electrode lead 11 is affixed to the alloyed pellet. The device of Figure 2 thus comprises a junction-type rectifier. Any other material, such as bismuth or vanadium, capableof imparting N-type conductivity to germanium or silicon, may be substituted for antimony.
If the body of the wafer 3 is of N-type conductivity, the pellet 8 should be of aluminum, gallium, indium or;
boron, or other material capable of imparting P-type con-.-
ductivity to the semiconductor.
The specific embodiments described include only single rectifying elements providing diode operation. It should be understood that the device of Fig. 1 may be-modified' as in Fig. 3 to include an additional rectifying point contact electrode 12 to provide a transistor. In this transistor 5 device the electrode 14, soldered to the wafer 3, functions as a base electrode.
Similarly, the device of Fig.2 may be modified, for example as shown in Fig. 4; to include an additional rectifying junction 13 and'an electrode lead 16 to provide a transistor device. This device also includes a base electrode which may be'in the form of a nickel tab soldered to the wafer 3.
There have thus been described; improved semiconductive materials and diode and transistor devices utilizing:
15 an alloy of germanium and silicon.
What is claimed is:
l. A semiconductor device including in combination a single crystal body of an alloy of germanium and at least 1% silicon having semiconductingproperties and at least one rectifyingelectrode connected thereto.
2. A deviceaccording to claim 1 in whichsaid rectifyingelectrodeis asmall area type electrode.
3. A semiconductor device comprising in combination a single crystal waferof germanium-silicon semiconducting-alloy ofone conductivity type and at least one P-N junction rectifying electrode.
4; A semiconductor device including in'cornbination a single crystal body of an alloy of germanium and at least 1% silicon having semiconducting properties and a plurality ofrectifying electrodes connected thereto.
5. A semiconductordevice of the alloy rectifying junction type comprising in combination a single crystalline wafer of germanium-silicon semiconducting alloy of one conductivity-type and a plurality of alloy junction type rectifying electrodes.
6. A semiconductor device including in combination a single crystal body of an alloy of germanium and at least 1% silicon having semiconducting properties and at least onelarge area rectifying electrode in contact therewith.
7. A semiconductor device including in combination a single crystal body of an alloy of germanium and at least 1% silicon having semiconducting properties and a plurality of large area rectifying electrodes in contact therewith.
8. A transistor device comprising a semiconductor body of single crystal alloy of germanium and silicon and emitter, collector, andbase electrodes connected thereto.
References Cited in the file of this patent OTHER REFERENCES General and Physical Chem, Chem. Abstracts, vol. 33:
US427098A 1954-05-03 1954-05-03 Semiconductors Expired - Lifetime US2817798A (en)

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BE537841D BE537841A (en) 1954-05-03
US427098A US2817798A (en) 1954-05-03 1954-05-03 Semiconductors
FR1123706D FR1123706A (en) 1954-05-03 1955-03-11 Improvements in electrical semiconductors
GB10698/55A GB808973A (en) 1954-05-03 1955-04-13 Improvements in semiconductor devices and methods for their manufacture
CH354168D CH354168A (en) 1954-05-03 1955-05-02 A method of manufacturing an electrical semiconductor device and a semiconductor device manufactured by this method

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2919389A (en) * 1955-04-28 1959-12-29 Siemens Ag Semiconductor arrangement for voltage-dependent capacitances
US2945286A (en) * 1956-07-23 1960-07-19 Siemens And Halske Ag Berlin A Diffusion transistor and method of making it
US3005132A (en) * 1952-06-13 1961-10-17 Rca Corp Transistors
US3118094A (en) * 1958-09-02 1964-01-14 Texas Instruments Inc Diffused junction transistor
US3124493A (en) * 1959-01-26 1964-03-10 Method for making the same
US3235957A (en) * 1964-05-20 1966-02-22 Rca Corp Method of manufacturing a thermoelectric device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL266513A (en) * 1960-07-01
CN115975745A (en) * 2023-01-04 2023-04-18 四川晶科能源有限公司 Recipe and method of seed pickling

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB602140A (en) * 1944-07-20 1948-05-20 Western Electric Co Process for producing silicon and electrical translating elements made therefrom
US2538593A (en) * 1949-04-30 1951-01-16 Rca Corp Semiconductor amplifier construction
US2731704A (en) * 1952-12-27 1956-01-24 Raytheon Mfg Co Method of making transistors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB602140A (en) * 1944-07-20 1948-05-20 Western Electric Co Process for producing silicon and electrical translating elements made therefrom
US2538593A (en) * 1949-04-30 1951-01-16 Rca Corp Semiconductor amplifier construction
US2731704A (en) * 1952-12-27 1956-01-24 Raytheon Mfg Co Method of making transistors

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3005132A (en) * 1952-06-13 1961-10-17 Rca Corp Transistors
US2919389A (en) * 1955-04-28 1959-12-29 Siemens Ag Semiconductor arrangement for voltage-dependent capacitances
US2945286A (en) * 1956-07-23 1960-07-19 Siemens And Halske Ag Berlin A Diffusion transistor and method of making it
US3118094A (en) * 1958-09-02 1964-01-14 Texas Instruments Inc Diffused junction transistor
US3124493A (en) * 1959-01-26 1964-03-10 Method for making the same
US3235957A (en) * 1964-05-20 1966-02-22 Rca Corp Method of manufacturing a thermoelectric device

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Publication number Publication date
GB808973A (en) 1959-02-18
BE537841A (en) 1900-01-01
CH354168A (en) 1961-05-15
FR1123706A (en) 1956-09-26

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