US2983631A - Method for making diodes and products resulting therefrom - Google Patents

Method for making diodes and products resulting therefrom Download PDF

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Publication number
US2983631A
US2983631A US790280A US79028059A US2983631A US 2983631 A US2983631 A US 2983631A US 790280 A US790280 A US 790280A US 79028059 A US79028059 A US 79028059A US 2983631 A US2983631 A US 2983631A
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Prior art keywords
layer
semi
conductor
ribbon
ribbons
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Expired - Lifetime
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US790280A
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English (en)
Inventor
Hanlet Jacques Marie Noel
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Societe dElectronique et dAutomatisme SA
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Societe dElectronique et dAutomatisme SA
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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
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body (electrodes)
    • H01L23/485—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body (electrodes) consisting of layered constructions comprising conductive layers and insulating layers, e.g. planar contacts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/50—Substrate holders
    • C23C14/505—Substrate holders for rotation of the substrates
    • 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
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
    • 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
    • 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
    • Y10S438/942—Masking
    • Y10S438/944—Shadow

Definitions

  • the .presentinvention has for its object a process for making diodes and similar elements using the currentrectifying properties of semi-conductive crystals and par ticularly those of the semi-conductors of group IV of the classification ofjelements, such as germanium and silicon. .1- H a .Acfurther object. isj the production of such diodes which, though. made in a rapid and economical fashion, nevertheless offer intrinsically improved electrical performance when employed in circuits for currents of very highr-frequencies, such for example as commutation or switching circuits having great speed of operation.
  • -Still another object is the production of a diode structure comprising a semi-conductor obtained by the instant process, and. which includes a thin semi-conductive crystalline layer placed upon a polycrystalline conductive base, said'seini-conducting layer being covered with a dielectric. film forming a strainer or perforated layer, and a metallic film of counter-electrode applied over this dielectric layer and contacting the semi-conductive layerat a plurality of points of contact completed through the ope'nings in the strainer layer; a In such a structure,
  • Fig. 3 is a' j-fl ow diagram which diagrammatically illustrates the order of steps involved in forming the, new
  • FIG.1 4 is a diagram iiia'tic enlarged cross-sectional view of articles prepared in acepiaa'ace *With the invention, the plurality of layers involved 'Withtlie newarticles beingdesignatedby legends which indicate the materials involved. j
  • Thejar l j is js eated upon and hermeticallysealed to the' base 6.
  • This jig or holder is made up of a frame having two lateral uprights 15 and 16 between which are stretched metal conductor ribbons 17 which are 'to serve ported on base 6 at the four corners of the orthogonal projection of the frame on the plane of the crucibles.
  • a second set of crucibles 20 is associated withthe set of; crucibles l8, for example off-set laterally from the set 18, as shown in Figure 2, where these sets are indicated in; dotted lines.
  • Each set of crucibles can be heated by passage of an electric current supplied through conductor 19 for crucibles 18, and through conductor 21 forcrucibles 20.
  • the upright bracket 8 is insulated from the base 6 at 22, and bracket 7 is grounded to the base.
  • a current for heating the frame and the ribbons which it supports is supplied by connection 8a leading to the insulated upright 8.
  • the ribbous17 intended to form the base of the diodes are made of an alloy of iron and nickel, the coefiicient of expansion of which is strictly identical with that of germanium which will be used as the semi-conductor.
  • the surface of these ribbons has been preliminarily treated to cover it with a layer of alloy of gold and bismuth of several molecules in thickness, which alloy layer has been thermically treated on the ribbons.
  • the system of crystallization of the nickel-iron alloy belongs to the same spatial group as that of germanium and, the ratio of meshes is a whole number.
  • the gold-- bismuth alloy alsohas a crystal form comparable with that of the preceding but allows, further, at the time of the formation of the germanium crystalline layer, the attainment of an automatic alignment of the crystallographic axis 110 of the germanium with the crystallographic axis alignment of the alloy Au Bi, servingas an epitaxic reference which leads to a distribution of net like planes on the iron-nickel base which contains the axes100 and from whencea better orderedstat'e of the crystallography of the diodes is obtained.
  • the ribbons can have an individual width of 3 mm. and a length of lOtl minL, for example.
  • A' grouping of 33 ribbons in the frame then forms a plane surface area of about 100 mm on the side.
  • This :mask M may consist of"parallel"ribbons 23 stretchedtransversely to the'ribbons17 and theare'a of each diode can; for example, be reduced to'4.
  • Thedi stance of the crucibles is rrbm was the "molecules. Theoccurrence of oxidation during the amount.
  • the crucibles 18 are heated to 1400 C. until the germanium has substantially evaporated and deposited on the ribbons'17 which are maintained ata temperature close to theuteeue point, that is, about 325" C., by sup lying heating current to lead 8a. ;
  • the alloys do not dilruse and their cr stalline structure is not modified;
  • the germanium coating. is applied to a thickness of about microns, and the coating is quite uniform be cause of the uniform disposition of the crucibles with respect to theribbon assembly and the uniform temperature conditions.
  • the electromagnet 13 is not energized; Without interrupting the vacc'um at this time and keeping the heating'reduced on the ribbons 17, the frame is turned through 180 so that the face covered with germanium may be turned up. This is done by turning the electro-mag'net 13' which is being fedby alter nating current to assure a lateral periodic vibration of' the frame carrying the ribbons 17. Then the valve 4 is opened to cause to fall upon the exposed area of rib; bons 17 a rain of granules of enamel 3.
  • the receptacle 2 may contain an atmosphere of helium, for example.
  • the granules of enamel have been screened'so as to present tor between the barrier and the resistance contact practically'r'nakes the storage capacity of the holesnegligibl'e.
  • the capacity of the barrier is reduced and, consequently, the diodes obtained permit efficient rectification of very high rr equency currents.
  • the effect of temperature upon the inverse voltage is particularly reduced sinceiher'adiating surfaceof the counter-electrode is large as compared :with that of the points of contact.
  • the fact that the operative process is carried on entirely in a controlled 1 vacuum assures the production of diodes with a surface grains of a diameter between 20 and 40 microns at most.
  • the material of the granules can be of the following composition (by way of illustration):
  • the granules because of the vibration of the frame, are distributed over the ribbons in a layer which is very uniform.
  • the enamel softens at the low temperature of strips 17 and is formed on the germanium as a coarse porous layer of a thickness of 10 to 25 microns.
  • the frame is then reversed to its first position, whereupon .the; excess granules fall, leaving the germaniumcovered surfaces of the ribbons covered with a veritable :strainer of enamel, the holes or pores of which, after heating, scarcely exceed 5 to 7 microns in diameter at the maximum; Further spreading of the granules and consequent reduction of the hole size can, if desired, be madeqbycontinued heating.
  • the crucibles 2.0 are heated to. a temperature in the neighborhood of 850 C. toevaporate the alloy of tin and cadmium which deposits upon the strainer layer, andv this alloy deposit fills the holesof the porous layer and forms'wa counter-electrode layer.
  • Each filled holeor pore in theporous layer leading to the germanium-covered portions provides a filamentary connection between the germanium-and the, counterrelectrode.
  • the electro-rnagnet 13 is not energized during formation of the counter electrode. a a p ⁇ The ribbons 17, may now-be removed from the vacuum jar...
  • the diodes are, tobe used separately, they are separatedfrom each other by severing the ribbons 17 along the, transverse areas which were shielded by the shielding strips 23z. 'Upon'providing the individual elements with conventional terminal connections, the diodes are'finished, I i H v The intrinsic characteristics of the diodes depend fundamentally on'the thickness of the layer of germanium and the'nuniber' of points of contactper unit areaof surface.
  • each diode comprising a metallic ba'se' having for'rned thereon a first layer of semi-conductorma terial selected from the group consisting of silicon and germanium, a second layer of porous ceramic'dielectric material, and a third layer of conductive metal
  • said process comprising enclosing a metallic ribbon in a vacuum chamber maintained at a pressure of theor'der of '10- of mercury, heating a semi-conductor ma terial within said chamber to produce thermal radiation of said material, subjecting said ribbon to said radiation through a shield to deposit a layer of said semi-conduc tor only upon spaced linear portions of said ribbon, heating said semi-conductor layer to effect crystallization thereof, applying a porous ceramic layer over said layer of semi-conductor material, and subjecting said ribbon to radiation froma source of vaporized metal transmitted through said shield to form separate conductive layers over the linear sections of said ribbons which arecovere'
  • I 3 A process according to claim 2, in which the-dielectric granules have a: grain size between 20 and- 40 microns, the porous ceramic layer finally obtained; having athickness'of the order of 25 microns.
  • 4 A process according. to claim 1, in, which the said ribbonis initially coated with. an alloy:v of gold-bismuth. 5.
  • a processaccording-toclaim,4, in-which theribbon I is of metal selected from theugroup consisting OfIiIOIl and nickel. I r
  • said dielectric layer is formed by flowing granules of enamel over the surface, of said metallic ribbons supported uponsaid a aem a including the step of vibratingfsaid frame to effect ,unifor'rnldistributionfof the ,granules over-lithe p faces of'said ribbons.
  • porous dielectric 'layerfis formed by flowing granules of enamel 0 overthe surface, of sai'd ribbon, and the enamel is heated a point or contact, and the approximate diameter of this tact oiiit;
  • the of the barrier isabout 300 to melt the granules, said heating being continuedlto spread the: granules "and reduce the hole size of'the result! ing porous layer to less than about 7 microns in diameter.
  • porous dielectric layer is formed by, flowing granules; of enamel over the surface of said metallic ribbon, said ribbon is vibrated to obtain uniform distribution of the granules over the ribbon and the distributed granules are heated to melt them and form a porous dielectric layer.
  • a diode comprising a metallic base of conductive metal having formed thereona plurality of separate thin layers, the first layer being substantially continuous and formed of semi-conductor material selected from the group consisting of silicon and germanium, the second layer being porous and formed of ceramic dielectric material and the third layer being substantially continuous and formed of conductive metal, the pores of said second layer being filled with the metal of said third layer, the metal filling said pores being in electrical contact with the top surface of said first layer, said metal filling said pores further being integral with the metal of said third layer.
  • a diode comprising a metallic base of conductive metal, a layer of gold-bismuth alloy several molecules in thickness formed upon said base, a layer of semi-conductive material selected from the group consisting of silicon and germanium formed upon the gold-bismuth alloy coated base surface, said semi-conductive layer being substantially continuous and of a thickness of about 5 microns, said conductive metal of said base being an iron-nickel alloy having a coefficient of expansion identical to the coefficient of expansion of said semi-conductive material, a porous layer of ceramic dielectric material formed upon said semi-conductive material layer, said porous layer having a thickness of about 10 to 25 microns With the pores thereof being less than about 7 microns in diameter, and a substantially continuous top layer formed upon said porous layer of cadmium-tin alloy, the pores of the porous layer being filled With the alloy of said top layer, the alloy filling said pores being in electrical contact with the top surface of said semi-conductive material layer, said alloy filling said pores further being integral with the alloy of said top layer.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Vapour Deposition (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
US790280A 1958-02-10 1959-01-30 Method for making diodes and products resulting therefrom Expired - Lifetime US2983631A (en)

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Application Number Priority Date Filing Date Title
FR1105068X 1958-02-10

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US (1) US2983631A (de)
DE (1) DE1105068B (de)
FR (1) FR1191404A (de)
GB (1) GB852713A (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151004A (en) * 1961-03-30 1964-09-29 Rca Corp Semiconductor devices
US3166448A (en) * 1961-04-07 1965-01-19 Clevite Corp Method for producing rib transistor
US3258359A (en) * 1963-04-08 1966-06-28 Siliconix Inc Semiconductor etch and oxidation process
US3271201A (en) * 1962-10-30 1966-09-06 Itt Planar semiconductor devices
US3287186A (en) * 1963-11-26 1966-11-22 Rca Corp Semiconductor devices and method of manufacture thereof
US3304469A (en) * 1964-03-03 1967-02-14 Rca Corp Field effect solid state device having a partially insulated electrode
US3304471A (en) * 1963-01-28 1967-02-14 Hughes Aircraft Co Thin film diode
US3331716A (en) * 1962-06-04 1967-07-18 Philips Corp Method of manufacturing a semiconductor device by vapor-deposition
US3409483A (en) * 1964-05-01 1968-11-05 Texas Instruments Inc Selective deposition of semiconductor materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2702259A (en) * 1951-08-09 1955-02-15 Emi Ltd Manufacture of electrodes which are sensitized so as to be emitters of photoelectrons or secondary electrons
US2766144A (en) * 1955-10-31 1956-10-09 Lidow Eric Photocell
US2768098A (en) * 1950-09-12 1956-10-23 Siemens Ag Method and apparatus for precipitating metal from the vaporous state onto plates, particularly for the production of selenium coated rectifier plates
US2789062A (en) * 1952-04-03 1957-04-16 Gen Electric Transparent fluoride luminescent screen and method for preparing same
US2818831A (en) * 1955-02-18 1958-01-07 Rca Corp Means for obtaining a uniform evaporated deposit

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL98697C (de) * 1952-08-20

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2768098A (en) * 1950-09-12 1956-10-23 Siemens Ag Method and apparatus for precipitating metal from the vaporous state onto plates, particularly for the production of selenium coated rectifier plates
US2702259A (en) * 1951-08-09 1955-02-15 Emi Ltd Manufacture of electrodes which are sensitized so as to be emitters of photoelectrons or secondary electrons
US2789062A (en) * 1952-04-03 1957-04-16 Gen Electric Transparent fluoride luminescent screen and method for preparing same
US2818831A (en) * 1955-02-18 1958-01-07 Rca Corp Means for obtaining a uniform evaporated deposit
US2766144A (en) * 1955-10-31 1956-10-09 Lidow Eric Photocell

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151004A (en) * 1961-03-30 1964-09-29 Rca Corp Semiconductor devices
US3166448A (en) * 1961-04-07 1965-01-19 Clevite Corp Method for producing rib transistor
US3331716A (en) * 1962-06-04 1967-07-18 Philips Corp Method of manufacturing a semiconductor device by vapor-deposition
US3271201A (en) * 1962-10-30 1966-09-06 Itt Planar semiconductor devices
US3304471A (en) * 1963-01-28 1967-02-14 Hughes Aircraft Co Thin film diode
US3258359A (en) * 1963-04-08 1966-06-28 Siliconix Inc Semiconductor etch and oxidation process
US3287186A (en) * 1963-11-26 1966-11-22 Rca Corp Semiconductor devices and method of manufacture thereof
US3304469A (en) * 1964-03-03 1967-02-14 Rca Corp Field effect solid state device having a partially insulated electrode
US3409483A (en) * 1964-05-01 1968-11-05 Texas Instruments Inc Selective deposition of semiconductor materials

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Publication number Publication date
GB852713A (en) 1960-10-26
DE1105068B (de) 1961-04-20
FR1191404A (fr) 1959-10-20

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