US2816850A - Semiconductive translator - Google Patents

Semiconductive translator Download PDF

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Publication number
US2816850A
US2816850A US401419A US40141953A US2816850A US 2816850 A US2816850 A US 2816850A US 401419 A US401419 A US 401419A US 40141953 A US40141953 A US 40141953A US 2816850 A US2816850 A US 2816850A
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US
United States
Prior art keywords
type
coating
semiconductive
conductivity
germanium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US401419A
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English (en)
Inventor
Horace E Haring
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AT&T Corp
Original Assignee
Bell Telephone Laboratories Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE534505D priority Critical patent/BE534505A/xx
Priority to NLAANVRAGE8002515,A priority patent/NL189769C/xx
Application filed by Bell Telephone Laboratories Inc filed Critical Bell Telephone Laboratories Inc
Priority to US401419A priority patent/US2816850A/en
Priority to CH328878D priority patent/CH328878A/de
Priority to FR1110900D priority patent/FR1110900A/fr
Priority to GB34061/54A priority patent/GB760563A/en
Application granted granted Critical
Publication of US2816850A publication Critical patent/US2816850A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3157—Partial encapsulation or coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/958—Passivation layer

Definitions

  • This invention involves the use on semiconductive devices of particular coatings containing ions of appropriate charge so as to render and maintain the semiconductive Surface in the desired condition as to conductivity type.
  • the unwanted leakage paths are formed either by the electrons associated with adsorbed positive ions or by the positive holes associated With adsorbed negative ions.
  • the term bridges has been applied to describe the nature of the conductivity.
  • hydrogen ions are electrolytically discharged on the surface of germanium as a result of the reaction between germanium and water. It appears that the discharged hydrogen is present as positively charged hydrogen ions (H+) and their associated conductivity electrons. Considering the effeet of this increase in the surface concentration of positive ionsL and conductivity electrons in relation to the type of germanium involved indicates the nature of objectionable leakage paths.
  • P-type germanium which is P-type because it contains a slight fice excess of negative ions, such an increase generally more' than neutralizes the slight excess of negative ions which make it P-type thereby establishing an N-type layer on P-type germanium.
  • Such a layer will constitute an extra conducting path or bridge.
  • This invention involves a surface treatment of the semiconductive material which comprises the application of a surface coating containing an agent capable of transferring ions of the appropriate charge to the semiconductor surface thereby to control the surface potential and the surface conductivity type, and thus avoid the formation of eXtra-conducting paths regardless of the moisture content of the ambient atmosphere.
  • improved semiconductor devices are attained by applying to the clean external surfaces of the assembled devices a coating of an inhibiting primer.
  • a suitable material for coating junction transistors of the N-P-N type may comprise a mixture of red lead (Pb304) and a vehicle composed of polyethylene and polybutene.
  • Pb304 red lead
  • ⁇ zine chromate or strontium chromate may be substituted for read lead with equally satisfactory results.
  • Other oxidants may also be used. In certain applications it may be found advantageous to apply the coating only to the intermediate or base zone.
  • a remarkable feature of the structure 'attained by the practice of this invention is the permanence of the surface stabilization.
  • Devices provided with the inhibitive coatings of this invention remain permanently free from bridges regardless of the moisture content of the ambient atmosphere.
  • the invention involves the continuous inhibition of .the hydrogen-forming reaction andthe complete: removal offhydrogen adsorbed during the cleaning process, by providingaV surface coating of a material which will furnish oxygenfor adsorptionon the germaniumi surface.
  • the surface is thereby converted from an unstable N-type to a'stable P-type as a resultof the replacement of hydrogen ions (H+). by oxygen ions (O- Inv this way, the: effectiveenergy level of the surface is fixed so that the surface conductivity type is thesameas that of the adjacentfbulkvmaterial regardless of the moisturecontent of the ambient atmosphere. Under such circumstances the formation of the objectionable bridge or leakage path is impossible.
  • Fig. l showsin section one embodiment of this invention
  • Fig. 2 is another section of the embodiment of Fig. 1; and.
  • Fig. 3 shows in section ⁇ another embodiment of this invention.
  • a lilamentary semiconductive!deviceofV the junction type such as is disclosed'in the aforementioned patent to Shockley.
  • the device comprises .a layer or.zone11" of P-type material, such as germanium or silicon, interposed between two layers or zones 12 ⁇ an ⁇ d ⁇ 13fof ⁇ 'N-type material ofthesame composition as that 'of .theP-type zone, separated respectively by barriers 14 and'lS.' Connections are made to each layer by electrodesterm'ed emitter (E), collector (C), and base. (B).
  • E electrodesterm'ed emitter
  • C collector
  • B base.
  • the Aentire'b'ody is encased in' al coating ⁇ 16' composed and appliedas hereinafter set forth: Fig. Z'isasection taken along the kline 2-2 of Fig.: l throughthe'base region to showA the adherence offthe'oxidant coating '16 to' the entire periphery ofthelarnent.
  • Fig. 3 is a longitudinal section of a-Semiconductive device identical to thatV of Fig.' l -towhichthe'coating of this invention is appliedfonly overthebase'region'and a portion of the adjacent ⁇ N-'type regions -12 and'1-13'and includingfthe barriers 14-fand 15.1
  • Such'a technique requires less coatingmaterial .and.1leaves the-lam'entends:freeioff coating for possible fabrication steps..
  • the inhibiting agent' shouldbe non-conductive.: Where a vehicleis used. the agentshould not reactwithvfthevvehicle so as to deteriorate the iilr'n. In the presence of moisture, the water solubility ofthe agent should be sufficient top rovidc a uniform and continuous'oxidizingenviron- 4ment at. theinterface between thesemicondctorland" the coating.
  • Stable surfaces of the desired potential and conductivity type can be established and maintained by inhibiting agents such as red lead regardless of the moisture content of the ambient atmosphere. It is desirable even where the semiconductive material is conned within an atmosphere of a high degree of dryness to provide an environment of a definite character in order to firmly tix the surface in the desired condition and thus stabilize device characteristics.
  • the abovementioned oxidizing agents namely red lead (Pb304), zinc chromate (ZnCrO4), and strontium chromate (SrCrO4) are generally employed in the form of powdered pigments.
  • red lead Pb304
  • zinc chromate ZnCrO4
  • strontium chromate SrCrO4
  • gel-type, hot-melt coatings of the class composed of lowl molecular weight polyethylene and poly'butene mixtures may be used with the pigment type inhibitors heretofore mentioned. Mixture is readily accomplished by adding the polyethylene to the polybutene at a temperature of the order of 160 C. with thorough stirring.
  • the epoxide resins and other well-known paint vehicles may be employed.
  • satisfactory oxidizing coatings containing pigmeut ltype oxidants, such as red lead may comprise about 25. percent by volume with the vehicle making up the balance of the finished coating.
  • the percentage range of the oxidant may vary to the extent of fifteen or twenty above and below the above-determined figure.
  • suitable coating material involves conventional practices for the grinding or powdering of pigment type oxidants which may then be mixed with a vehicle of the polyethylene-polybutene type by stirring at a temperature somewhat above the melting point, or by mixing on a paint mill at a temperature either above or below the melting point.
  • the coating may then be applied to the device in any of a number of conventional ways such as dipping, brushing, or spraying at a temperature above the melting point.
  • elevated temperatures of the order of to 160 C. aredesirableto insure the proper fluidity for convenient mixing,l application, surface wetting, adhesion and coverage.
  • the oxidant may be dispersed. throughout the vehicle with the aid of a suitable solvent such as toluene and then applied at room temperature to the surface to be coated.
  • a suitable solvent such as toluene
  • Any of the conventional. methods of application may be employed;
  • Amonggthe'paints which appear to be suitable for the purposeof this invention is one with a polymeric vehicle known asepoxide resin.
  • This vehicle readily obtainable.commercially, is a product of the condensationv reaction between bisphenol A and epichlorhydrin. It may be prepared for mixing with the oxidizing pigment by thinning with toluene.
  • a curingagent such as triethylamine or diethylene triamiiie may be added to cross link the polymer ⁇ and thushardenthe film. Baking at 50 to 60 C. for
  • the'semiconductive material should present a proper surface before coating.
  • the'material may be subjected to any of the chemicalor electrolytic etchingtechniques known to the art followed by rinsing in high purity water and thorough drying.
  • an N-P-N junctiontype transistor of germanium as disclosed in the aforementioned patent to Shockley was coated as described below.
  • the coating mixture comprised one part by volume of commercial grade 97 percent red lead to three parts by volume of a mixture consisting of 7.5 percent by Weight of low molecular weight polyethylene and 92.5 percent by weight of polybutene. Adequate dispersion of the oxidant was accomplished by thorough mixing at a temperature in the range of 125 to 160 C.
  • the N-P-N junction device was then dipped in the coating mixture at a temperature of 112 C. Several seconds of immersion was sufcient to bring the device to the temperature of the coating compound and assure thorough wetting. It was then withdrawn, allowed to cool and subjected to initial measurements.
  • P-type germanium coated with an epoxide resin paint containing red lead was found to maintain a P-type surface regardless of the moisture content of the ambient atmosphere, thus demonstrating that this kind of coating also will stabilize the surface and protect semiconductor devices against moisture and its effects.
  • an oxidant such as red lead or a dichromate may be employed suspended or dissolved in dielectric oil.
  • a semiconductive body selected from the group consisting of germanium and silicon having two zones of N-type conductivity and an intermediate zone of P-type conductivity, and a surface coating on said zone of P-type conductivity comprising an oxidizing agent selected from the group consisting of red lead, zinc chromate, and strontium chromate, dispersed in a vehicle consisting of a mixture of 8 percent polyethylene and 92 percent polyisobutylene for producing a substantially continuous oxidizing environment at the interface between said layer and said body.
  • a semiconductive body selected from the group consisting of germanium and silicon having two zones of Ntype conductivity and an intermediate zone of P-type conductivity, and a surface coating on said zone of P-type conductivity comprising red lead dispersed in a mixture of 8 percent polyethylene and 92 percent polyisobutylene for producing a substantially continuous oxidizing environment at the interface between said layer and said body.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US401419A 1953-12-30 1953-12-30 Semiconductive translator Expired - Lifetime US2816850A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE534505D BE534505A (it) 1953-12-30
NLAANVRAGE8002515,A NL189769C (nl) 1953-12-30 Werkwijze voor het handhaven van badoplossingen voor het stroomloos afzetten van koper op substraatplaten in inrichtingen uit metaal.
US401419A US2816850A (en) 1953-12-30 1953-12-30 Semiconductive translator
CH328878D CH328878A (de) 1953-12-30 1954-07-27 Halbleiterkörper
FR1110900D FR1110900A (fr) 1953-12-30 1954-07-31 élément de transmission semi-conducteur
GB34061/54A GB760563A (en) 1953-12-30 1954-11-24 Semiconductor translating devices

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US401419A US2816850A (en) 1953-12-30 1953-12-30 Semiconductive translator

Publications (1)

Publication Number Publication Date
US2816850A true US2816850A (en) 1957-12-17

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Family Applications (1)

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US401419A Expired - Lifetime US2816850A (en) 1953-12-30 1953-12-30 Semiconductive translator

Country Status (6)

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US (1) US2816850A (it)
BE (1) BE534505A (it)
CH (1) CH328878A (it)
FR (1) FR1110900A (it)
GB (1) GB760563A (it)
NL (1) NL189769C (it)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918628A (en) * 1957-01-23 1959-12-22 Otmar M Stuetzer Semiconductor amplifier
US2989424A (en) * 1958-03-31 1961-06-20 Westinghouse Electric Corp Method of providing an oxide protective coating for semiconductors
US3089793A (en) * 1959-04-15 1963-05-14 Rca Corp Semiconductor devices and methods of making them
US3097308A (en) * 1959-03-09 1963-07-09 Rca Corp Semiconductor device with surface electrode producing electrostatic field and circuits therefor
US3104991A (en) * 1958-09-23 1963-09-24 Raytheon Co Method of preparing semiconductor material
US3110637A (en) * 1958-01-14 1963-11-12 Philips Corp Method of producing semi-conductive electrode systems
DE1163975B (de) * 1959-01-21 1964-02-27 Int Standard Electric Corp Verfahren zur Verbesserung der elektrischen Eigenschaften von Halbleiteranordnungen
US3145328A (en) * 1957-04-29 1964-08-18 Raytheon Co Methods of preventing channel formation on semiconductive bodies
US3146135A (en) * 1959-05-11 1964-08-25 Clevite Corp Four layer semiconductive device
US3154692A (en) * 1960-01-08 1964-10-27 Clevite Corp Voltage regulating semiconductor device
US3200310A (en) * 1959-09-22 1965-08-10 Carman Lab Inc Glass encapsulated semiconductor device
US3204160A (en) * 1961-04-12 1965-08-31 Fairchild Camera Instr Co Surface-potential controlled semiconductor device
US3226614A (en) * 1962-08-23 1965-12-28 Motorola Inc High voltage semiconductor device
US3293010A (en) * 1964-01-02 1966-12-20 Motorola Inc Passivated alloy diode
US3297500A (en) * 1963-02-15 1967-01-10 Int Standard Electric Corp Method of passivating semiconductor devices
US3340445A (en) * 1962-01-19 1967-09-05 Rca Corp Semiconductor devices having modifier-containing surface oxide layer
US4818727A (en) * 1987-06-23 1989-04-04 Sgs-Thomson Microelectronics Inc. Method of improving the corrosion resistance of aluminum contacts on semiconductors
US5119167A (en) * 1987-06-23 1992-06-02 Sga-Thomson Microelectronics, Inc. Method of improving the corrosion resistance of aluminum contacts on semiconductors

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3372472A (en) * 1962-05-22 1968-03-12 Carrier Corp Method for forming a thermoelectric module
DE1278017B (de) * 1964-05-06 1968-09-19 Siemens Ag Von einer Vergussmasse umhuelltes oder mittels dieser gegen die Umgebung angedichtetes elektrisches Bauelement, insbesondere Halbleiter-Gleichrichter

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2349622A (en) * 1941-12-18 1944-05-23 Gen Electric Manufacture of rectifiers of the blocking layer type
US2391706A (en) * 1940-10-10 1945-12-25 Battelle Memorial Institute Method of forming blocking layers on selenium coated plates
US2438110A (en) * 1943-07-28 1948-03-23 Bell Telephone Labor Inc Electrical translating materials and devices and method of making them
US2444255A (en) * 1944-11-10 1948-06-29 Gen Electric Fabrication of rectifier cells
US2569892A (en) * 1941-11-05 1951-10-02 Hazeltine Research Inc Crystal contacts of which one element is mainly silicon
US2615587A (en) * 1949-06-24 1952-10-28 Trailmobile Inc Conveyer system for vehicles
US2655626A (en) * 1949-07-11 1953-10-13 Fansteel Metallurgical Corp Selenium rectifier
US2722490A (en) * 1950-07-24 1955-11-01 Bell Telephone Labor Inc Germanium elements and methods of preparing same
US2743430A (en) * 1952-03-01 1956-04-24 Rca Corp Information storage devices
US2748325A (en) * 1953-04-16 1956-05-29 Rca Corp Semi-conductor devices and methods for treating same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2391706A (en) * 1940-10-10 1945-12-25 Battelle Memorial Institute Method of forming blocking layers on selenium coated plates
US2569892A (en) * 1941-11-05 1951-10-02 Hazeltine Research Inc Crystal contacts of which one element is mainly silicon
US2349622A (en) * 1941-12-18 1944-05-23 Gen Electric Manufacture of rectifiers of the blocking layer type
US2438110A (en) * 1943-07-28 1948-03-23 Bell Telephone Labor Inc Electrical translating materials and devices and method of making them
US2444255A (en) * 1944-11-10 1948-06-29 Gen Electric Fabrication of rectifier cells
US2615587A (en) * 1949-06-24 1952-10-28 Trailmobile Inc Conveyer system for vehicles
US2655626A (en) * 1949-07-11 1953-10-13 Fansteel Metallurgical Corp Selenium rectifier
US2722490A (en) * 1950-07-24 1955-11-01 Bell Telephone Labor Inc Germanium elements and methods of preparing same
US2743430A (en) * 1952-03-01 1956-04-24 Rca Corp Information storage devices
US2748325A (en) * 1953-04-16 1956-05-29 Rca Corp Semi-conductor devices and methods for treating same

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918628A (en) * 1957-01-23 1959-12-22 Otmar M Stuetzer Semiconductor amplifier
US3145328A (en) * 1957-04-29 1964-08-18 Raytheon Co Methods of preventing channel formation on semiconductive bodies
US3110637A (en) * 1958-01-14 1963-11-12 Philips Corp Method of producing semi-conductive electrode systems
US2989424A (en) * 1958-03-31 1961-06-20 Westinghouse Electric Corp Method of providing an oxide protective coating for semiconductors
US3104991A (en) * 1958-09-23 1963-09-24 Raytheon Co Method of preparing semiconductor material
DE1163975B (de) * 1959-01-21 1964-02-27 Int Standard Electric Corp Verfahren zur Verbesserung der elektrischen Eigenschaften von Halbleiteranordnungen
DE1163975C2 (de) * 1959-01-21 1964-08-27 Int Standard Electric Corp Verfahren zur Verbesserung der elektrischen Eigenschaften von Halbleiteranordnungen
US3097308A (en) * 1959-03-09 1963-07-09 Rca Corp Semiconductor device with surface electrode producing electrostatic field and circuits therefor
US3089793A (en) * 1959-04-15 1963-05-14 Rca Corp Semiconductor devices and methods of making them
US3146135A (en) * 1959-05-11 1964-08-25 Clevite Corp Four layer semiconductive device
US3200310A (en) * 1959-09-22 1965-08-10 Carman Lab Inc Glass encapsulated semiconductor device
US3154692A (en) * 1960-01-08 1964-10-27 Clevite Corp Voltage regulating semiconductor device
US3204160A (en) * 1961-04-12 1965-08-31 Fairchild Camera Instr Co Surface-potential controlled semiconductor device
US3340445A (en) * 1962-01-19 1967-09-05 Rca Corp Semiconductor devices having modifier-containing surface oxide layer
US3226614A (en) * 1962-08-23 1965-12-28 Motorola Inc High voltage semiconductor device
US3226612A (en) * 1962-08-23 1965-12-28 Motorola Inc Semiconductor device and method
US3226611A (en) * 1962-08-23 1965-12-28 Motorola Inc Semiconductor device
US3226613A (en) * 1962-08-23 1965-12-28 Motorola Inc High voltage semiconductor device
US3297500A (en) * 1963-02-15 1967-01-10 Int Standard Electric Corp Method of passivating semiconductor devices
US3293010A (en) * 1964-01-02 1966-12-20 Motorola Inc Passivated alloy diode
US4818727A (en) * 1987-06-23 1989-04-04 Sgs-Thomson Microelectronics Inc. Method of improving the corrosion resistance of aluminum contacts on semiconductors
US5119167A (en) * 1987-06-23 1992-06-02 Sga-Thomson Microelectronics, Inc. Method of improving the corrosion resistance of aluminum contacts on semiconductors

Also Published As

Publication number Publication date
CH328878A (de) 1958-03-31
BE534505A (it)
NL189769C (nl)
FR1110900A (fr) 1956-02-17
GB760563A (en) 1956-10-31

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