EP0260223B1 - Verfahren zur Herstellung polykristalliner Siliziumschichten durch elektrolytische Abscheidung von Silizium - Google Patents

Verfahren zur Herstellung polykristalliner Siliziumschichten durch elektrolytische Abscheidung von Silizium Download PDF

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Publication number
EP0260223B1
EP0260223B1 EP87810460A EP87810460A EP0260223B1 EP 0260223 B1 EP0260223 B1 EP 0260223B1 EP 87810460 A EP87810460 A EP 87810460A EP 87810460 A EP87810460 A EP 87810460A EP 0260223 B1 EP0260223 B1 EP 0260223B1
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EP
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Prior art keywords
silicon
iodide
process according
component
aluminium
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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
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EP87810460A
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German (de)
English (en)
French (fr)
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EP0260223A1 (de
Inventor
Hans Rudolf Dr. Grüniger
Rudolf Dr. Kern
Paul Prof.Dr. Rys
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Prof Dr Paul Rys Te Zuerich Zwitserland
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Ciba Geigy AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • 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
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/915—Electrolytic deposition of semiconductor

Definitions

  • the present invention relates to the production of thin layers of elemental silicon on electrically conductive materials by electrolytic deposition of the silicon from low-melting mixtures which contain covalent silicon compounds.
  • the materials thus coated can be used in the manufacture of photoconductive or photovoltaic devices, e.g. of solar cells.
  • silicon deposit by melting electrolysis at temperatures of approximately 700 to 1500 ° C from melts containing silicon fluorides and oxides as well as aluminum, alkali metal and / or alkaline earth metal salts.
  • the disadvantage of this process is the high temperatures, which cause considerable material problems.
  • Another method relates to the electrochemical silicon deposition from solutions of suitable silanes, for example tetrahalosilanes or trihalosilanes, which are dissolved in polar organic solvents.
  • suitable silanes for example tetrahalosilanes or trihalosilanes, which are dissolved in polar organic solvents.
  • the purity of the silicon layers deposited by this process, as well as their continuity and adherence to the electrically conductive base, cannot be fully satisfied; thus the use of the materials coated in this way is also impaired for the stated purposes. Attention is also drawn to the possible but undesirable chemical reaction of the halosilanes mentioned with the polar organic solvents.
  • the process according to the invention does not require high-temperature melt electrolysis or silicon deposition from an organic electrolysis bath, but rather uses a melt of a certain composition from which polycrystalline silicon can be electrochemically deposited in thin, continuous layers on suitable, electrically conductive material at relatively low temperatures.
  • the covalent silicon compound (a) provides the silicon which e.g. can be deposited cathodically.
  • Component (b) is used to produce a homogeneous melt (good miscibility with the silicon compounds)
  • component (c) is the conductive salt, which e.g. with component (b) (AlJ3) can go into solution with complex formation
  • component (d) represents the so-called catalyst, which reduces the silicon deposition and the quality of the silicon layers on e.g. Copper, chromium, molybdenum, nickel, iron and chromium steel or inorganic glasses e.g. from tin dioxide or tin dioxide / indium oxide mixtures, significantly improved and silicon layer formation on a silicon substrate under the conditions of the method according to the invention is made possible in the first place. Without this catalyst, no silicon deposition could be observed in the latter case.
  • the molten salt (the electrolyte) for the anodic silicon deposition contains components (a) to (c).
  • This electrolytic silicon deposition is carried out at temperatures of 100 to 350 ° C in an inert atmosphere and optionally under pressure, e.g. 1 to 5 bar.
  • An anode made of aluminum is used, and suitable cathode materials are made of silicon or graphite.
  • Suitable halogen-containing compounds and halides which are present as components (a) to (d) or (a) to (c) in the melt for carrying out the process according to the invention, are, in particular, the chlorides, bromides and iodides, the latter are preferred.
  • Component (a) is silicon tetrahalide of the formula (1) SiX4, wherein X is chlorine, bromine, preferably iodine or mixtures thereof, such as silicon tetrachloride, silicon tetrabromide or preferably silicon tetrajodide, also for example SiClBr3, SiCl2Br2, SiCl3Br, SiCl2J2, SiCl2J2, SiBr3J, SiBr2J2 or SiBrJ3; Halogen silanes can also be used of the formulas (2) H n SiX 4-n and (3) Si m X ′ 2m + 2 , wherein n and m are integers from 1 to 3 and 2 to 6, X is chlorine, bromine, iodine or a mixture thereof and X 'is chlorine, bromine or iodine. Examples include HSiCl3, H2SiCl2, HSiBr3, H2SiBr2, HSiJ3 and H2Si
  • di- and polysilanes of the formula (3) are Si2Cl6, Si3Cl8, Si4Cl10 and other homologues and the corresponding bromine and especially iodine compounds.
  • Component (b) is aluminum trihalides such as aluminum trichloride, aluminum tribromide or preferably aluminum triiodide; with component (c), the so-called conductive salt, around the chloride, bromide or preferably iodide of sodium, potassium or preferably lithium; ammonium halides, such as ammonium chloride, bromide or iodide, and also lower (C1-C4) tetraalkyl or alkanolammonium halides (tetraethylammonium, tetrabutylammonium halides); and in component (d), the so-called catalyst, chlorides, bromides or preferably iodides of transition metals.
  • component (c) is aluminum trihalides such as aluminum trichloride, aluminum tribromide or preferably aluminum triiodide
  • component (c) the so-called conductive salt, around the chloride, bromide or preferably iodide of sodium, potassium or preferably lithium
  • transition metals are to be understood as the metals which are in the so-called subgroups (B groups, IB-VIIB and VIII) of the periodic system of the elements.
  • Representatives of these groups include copper, zinc, scandium and the lanthanides, for example erbium or gadolinium; Titanium, vanadium, chromium, manganese, iron, cobalt and nickel (see NA Lange, Handbook of Chemistry, 10th Ed. 1961, Mc Graw Hill Book Co.).
  • halides of these transition metals which can be used as catalysts are chromium (II) iodide (CrJ2), manganese (II) iodide (MnJ2), iron (II) iodide (FeJ2), nickel iodide (NiJ2), copper (I) iodide ( CuJ), hafnium (IV) iodide (HfJ4) or vanadium (II) iodide (VJ2).
  • Mixtures of the halides mentioned as component (d) can also be used, e.g. those of VJ2 and NiJ2, NiJ2 and FeJ2, FeJ2 and CrJ2, VJ2, NiJ2 and FeJ2 or NiJ2, FeJ2 and CrJ2, the mixing ratios of which can have a wide range.
  • the molten salts used in the process according to the invention preferably contain silicon tetrabromide or silicon tetraiodide as component (a), aluminum triiodide as component (b), lithium iodide as component (c) and vanadium (II) iodide or in particular the aforementioned salt mixtures as component (d).
  • Components (a) to (c) can also be mixtures of the specified halides.
  • Components (a) to (d) are used in the melt in approximately the following amounts: 20 to 90, preferably 20 to 75% by weight of component (a), 20 to 60% by weight of component (b) , 1 to 20% by weight of component (c) and 0.1 to 10% by weight of component (d).
  • the melt contains the components in the following amounts: 40 to 75% by weight of component (a), 20 to 50% by weight of component (b), 1 to 12% by weight of component (c) and 0 , 1 to 5 wt .-% of component (d).
  • Components (a) to (d) must have a very high chemical purity.
  • Corresponding processes for producing such high-purity compounds are known from the literature (cf., for example, RC Ellis, J. Elektrochem. Soc. 107, 222 (1960) -production of silicon tetraiodide and use for the production of silicon).
  • the method according to the invention can be carried out in a conventional type of electrolysis vessel.
  • the vessel can e.g. be made of glass, in particular quartz glass or of a non-corroding metal and optionally contain a porous sintered plate made of quartz, a metal or ceramic material as a partition between the anode and cathode spaces.
  • a partition can e.g. prevent the conversion of the halogen (e.g. Cl2 or J2) formed anodically (using an inert anode) on the cathode.
  • the escaping gaseous halogens can be collected and separated in a fractionation column connected to the electrolysis vessel.
  • a reference electrode is generally used, which is separated from the cathode space by a diaphragm (porous sintered plate).
  • a suitable reference electrode is e.g. Made of high-purity aluminum (99.999%), which is in an aluminum halide / alkali metal halide melt (e.g. AlJ3 / LiJ) (reference element).
  • the reference electrode is used as the third currentless electrode. With it you can e.g. check the electrical conditions (e.g. potential changes) during the electrolysis process.
  • Suitable electrode materials for cathodic silicon deposition are: Under the conditions of electrochemical deposition, corrosion-resistant metals / alloys or semimetals or non-metals, such as copper, chromium, molybdenum, nickel, iron, platinum or stainless steels, such as chromium steel, and preferably aluminum, silicon or graphite as cathode material and platinum, silicon or graphite as (inert) anode material. Molybdenum, platinum, graphite and silicon are particularly corrosion-resistant materials.
  • the anode material is made of aluminum, as indicated, while the cathodes are preferably made of graphite or silicon.
  • the silicon anodes can be etched with a mixture of 5 parts nitric acid, 3 parts concentrated hydrofluoric acid, 3 parts acetic acid and 0.1 part bromine before use. Their surfaces are then designed in such a way that they are hardly attacked anodically and can thus serve as inert anodes.
  • the working temperature for carrying out the method according to the invention from 100 to 350 ° C is by indirect heating of the electrolysis vessel, e.g. achieved with a suitable, electrically heated heating bath.
  • temperature ranges from preferably 200 to 350 ° C and in particular from 260 to 320 ° C can be specified.
  • the electrochemical deposition of the silicon is carried out at a current density of approximately 0.5 to 20, preferably 1 to 20, in particular 1 to 10 or 1 to 5 mA / cm 2.
  • the electrochemical silicon deposition can be carried out galvanostatically or potentiostatically using a conventional energy source.
  • the power yield (power consumption) is in the range of about 50 to 100%, usually 100%, i.e. corresponds to the theoretical value and indicates that there are practically no side reactions, e.g. Dimer or polymer formation takes place, which could reduce the current efficiency.
  • the duration of the electrochemical deposition depends on the thickness of the desired silicon layer and thus fluctuates within wide limits. A period of about 1 to 24, preferably 1 to 10 hours can be mentioned as an example.
  • the thickness of the silicon layer on the electrically conductive bodies used as electrodes can be specified as 0.01 to 300, preferably 0.01 to 100 ⁇ m.
  • the electrochemical silicon deposition is carried out in an inert atmosphere at normal pressure, optionally also at about 1 to 5 bar gauge pressure.
  • the electrolytic cell is filled with an inert gas, e.g. Flushed with nitrogen or argon, creating an inert gas atmosphere that remains throughout the process.
  • Components (a) to (d) are also usually filled into the electrolytic cell under inert conditions (dry box).
  • the process according to the invention can be used to produce relatively large-area, uniform polycrystalline silicon layers which are firmly bonded to the electrically conductive base.
  • the coated materials thus obtained show very good electrical and thermal dissipation, so that they e.g. can be used for the production of or in photoconductive or photovoltaic devices.
  • Photovoltaic devices are e.g. (Silicon) solar cells that are capable of converting light energy into electrical energy (photo volta effect).
  • Aluminum iodide is usually made from the elements (aluminum and iodine) at higher temperatures and in an inert atmosphere. As by-products it contains iodine and certain impurities from the starting components. The cleaning of the aluminum iodide thus obtained is very cumbersome. If very pure starting materials (aluminum and iodine) are used, the conversion takes place only very slowly and incompletely.
  • very pure aluminum iodide can be produced from aluminum and hydrogen iodide, the hydrogen iodide being expediently formed in situ from iodine and hydrogen.
  • the hydrogen iodide can be produced from iodine and hydrogen in the presence of a platinum catalyst at around 500 ° C.
  • the hydrogen iodide is expediently prepared in-situ from iodine and hydrogen at temperatures from 600 to 800 ° C. and in the presence of catalytic amounts of water and used directly for the further reaction with aluminum.
  • the catalytic amounts of water are introduced into the process, for example, by passing the hydrogen through a wash bottle of water before the reaction with the iodine.
  • the preferred component (c) _ lithium iodide _ can be present as mono-, di- or trihydrate and is usually purified by recrystallization of the trihydrate (LiJ ⁇ 3H2O) from water.
  • the mono- or dihydrate mentioned can also be used for the zone melting process, temperatures of 50 to 140 ° C. being possible.
  • a rectangular silicon wafer (dimensions 40/8/2 mm), which has been sawed off from a silicon single crystal, is treated in a 20% strength alkaline aqueous solution of a commercial surfactant for 1 hour at 90 ° C., washed with bidistilled water and then at 150 ° C air dried.
  • the silicon single crystal is drawn from a silicon melt by known methods; by appropriate doping, it is made p- or n-type and has a resistance of 0.04 ohm cm.
  • the silicon wafer cleaned as stated is installed as a cathode in an electrolysis cell.
  • the anode is made of graphite or silicon.
  • Anode and cathode compartments can be separated from one another by a porous sintered plate in order to prevent a possible conversion of the halogen at the cathode.
  • the halogen iodine
  • the escaping halogen can be recovered, for example, by condensation.
  • a compound mixture consisting of 73 wt .-% SiJ4, 22 wt .-% AlJ3, 3.5 wt .-% LiJ and 1.5 wt .-% VJ2 is added, which is then at 310 ° C and a current density of 2 mA / cm2 is electrolyzed for 4 hours.
  • the voltage depends on the distance between the electrodes. It is in the range of 300 to 500 mV.
  • the electrolysis is carried out under inert conditions in a closed system. For this purpose, the electrolysis cell is flushed with nitrogen or argon before the electrolysis; the inert gas atmosphere is maintained during the electrolysis.
  • the measured current yield is slightly higher than 100%, probably due to a certain thermal decomposition of SiJ4 during the electrolysis.
  • the silicon deposits more or less easily.
  • the current yields therefore fluctuate between 50 and 100% and more or less large amounts of the catalyst can also be separated.
  • a disc of high-purity aluminum (99.99%) is treated in a 20% alkaline aqueous solution of a commercially available surfactant for 1 hour at room temperature and then dried in air at 150 ° C.
  • the aluminum disc is then anodically polarized at 260 to 270 ° C. for 20 minutes at a current density of 2 mA / cm 2 and then used as the cathode in an electrolysis process according to Example 1 (a).
  • the anodic polarization of the aluminum cathode accelerates the silicon deposition and improves the quality of the silicon layer. There is probably a (partial) exchange of aluminum for silicon on the aluminum surface before the actual deposition of the silicon. The cathodically deposited silicon adheres better to this surface than to aluminum itself.
  • This coated material also exhibits the properties given in Example 1 (a).
  • a rectangular rolled aluminum disc (purity: 99.99%, dimensions 40/8/2 mm) is cleaned with methylene chloride in an ultrasonic bath and then rinsed with methylene chloride. Then it is sanded dry with emery paper and finally polished with a slurry of aluminum oxide in isopropanol. The polished disc is cleaned with isopropanol in an ultrasonic bath, rinsed with acetone and dried at room temperature.
  • the aluminum disk cleaned in this way is installed as an anode in an electrolysis cell according to Example 1 (a).
  • the cathode is made of graphite or silicon.
  • a compound mixture consisting of 74.2% by weight SiJ4, 22.1% by weight AlJ3 and 3.7% by weight LiJ is placed in the electrolysis cell under inert conditions in a suitably closed housing (dry box).
  • the electrolytic cell is then removed from this housing and heated to about 320 ° C. until the mixture boils. Inert conditions are maintained in the electrolysis cell by introducing nitrogen (slight excess pressure). After thorough mixing of the electrolyte, the mixture is cooled to 260 to 270 ° C.
  • electrolysis is carried out for 20 minutes with a current density of 10 mA / cm2 and then for 5 hours with 1 mA / cm2.
  • the electrodes are then cooled by a stream of nitrogen and cleaned with propionitrile and alcohol.
  • a continuous, well adhering silicon layer of about 50 ⁇ m thick has formed on the aluminum disc. The material coated in this way shows very good electrical and thermal dissipation.
  • the aluminum iodide formed can be separated off and split back into aluminum and iodine by electrolysis.
  • a heatable piston for receiving the iodine and provided with a gas inlet tube is connected to a vertically arranged reaction tube made of quartz glass, which is surrounded by a heating jacket.
  • the hydrogen iodide is synthesized in this tube.
  • a fractionation column filled with glass bodies is connected to the reaction tube. This fractionation column is kept at about 120 ° C. during the reaction.
  • the reflux from this fractionation column flows back through a heatable feed line (likewise heated to about 120 ° C.) into the heatable flask, in which the iodine boils at the reflux temperature (185 ° C.).
  • At the top of the fractionation column is a cooler which is kept at room temperature to condense residual iodine.
  • the cooler is heated to temperatures above the melting point of the iodine in order to melt the condensed iodine, which then flows back into the heatable flask via the fractionation column.
  • Behind the cooler is a cold trap (_20 ° C) in which the last traces of iodine and impurities are separated.
  • iodine Since the reaction of iodine with hydrogen does not proceed completely at the specified temperatures, iodine can be separated from hydrogen iodide and hydrogen with the aid of this device and flow back into the heatable storage flask. In this way, continuous hydrogen iodide synthesis is possible.
  • the iodine in the flask constantly boils under reflux (185 ° C) and a continuous stream of hydrogen is introduced through the gas inlet pipe.
  • the cold trap is followed by a second reaction tube which contains the aluminum and in which the reaction with the hydrogen iodide to aluminum iodide (AlJ3) takes place.
  • the aluminum iodide formed flows with the gas stream (hydrogen) to the end of the reaction tube and condenses there in a flask.
  • the hydrogen recovered from the reaction and the unreacted hydrogen are discharged at the end of the apparatus through wash bottles (sulfuric acid or paraffin oil) or returned to the flask containing the iodine.
  • the dried aluminum chips and the iodine are placed in the heated flask in the second reaction tube.
  • the apparatus is then purged with argon for one hour to remove the air.
  • the first reaction tube is then heated to 750 ° C and the second to 400 ° C and the heatable flask containing the iodine to the reflux temperature (185 ° C) of the iodine. Weak iodine reflux is maintained in this flask.
  • the inert argon atmosphere inside the reaction apparatus is then displaced by a stream of hydrogen.
  • hydrogen is first passed through a wash bottle containing water and from there into the heated flask containing the iodine.
  • the hydrogen flow is regulated so that it flows through the first reaction tube in about 30 seconds. From time to time, the hydrogen flow is passed through the wash bottle mentioned in order to reactivate the formation of hydrogen iodide and aluminum iodide.
  • the colorless AlJ3 thus obtained is spectroscopically pure. No disturbing impurities could be detected.
  • Milled lithium iodide trihydrate is filled into a quartz tube under inert gas.
  • the salt is melted into a coherent block using the industrial blow dryer.
  • the tube is closed and fastened horizontally in a zone melting apparatus.
  • the quartz tube is only about half full, so it cannot break during the melting process.
  • the zone melting is carried out by passing the heating ring slowly (about 1-2 cm / h) over the quartz tube.
  • the contaminants in the lithium iodide migrate with the melting zone during zone melting (70 to 80 ° C) and collect at the ends of the quartz tube. After about 20 melting cycles, the process is ended, the tube is broken into several pieces after cooling, the salt is melted out in an inert atmosphere and the solidified melt is finally ground.
  • the lithium iodide trihydrate thus obtained is spectroscopically pure and contains no troublesome impurities.
  • the trihydrate is then dried in vacuo (10 _ 3 Torr ⁇ 1.3 ⁇ 10 _ 3 mbar) as follows: 24 hours at room temperature, 12 hours at 50, 100, 150 and 200 ° C and finally 48 hours at 250 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP87810460A 1986-08-19 1987-08-13 Verfahren zur Herstellung polykristalliner Siliziumschichten durch elektrolytische Abscheidung von Silizium Expired - Lifetime EP0260223B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH332086 1986-08-19
CH3320/86 1986-08-19

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EP0260223A1 EP0260223A1 (de) 1988-03-16
EP0260223B1 true EP0260223B1 (de) 1991-04-10

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EP87810460A Expired - Lifetime EP0260223B1 (de) 1986-08-19 1987-08-13 Verfahren zur Herstellung polykristalliner Siliziumschichten durch elektrolytische Abscheidung von Silizium

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US (2) US4759830A (ja)
EP (1) EP0260223B1 (ja)
JP (1) JPS6350496A (ja)
AU (1) AU587713B2 (ja)
DE (1) DE3769252D1 (ja)
ES (1) ES2021751B3 (ja)
IL (1) IL83570A (ja)
ZA (1) ZA876100B (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5270229A (en) * 1989-03-07 1993-12-14 Matsushita Electric Industrial Co., Ltd. Thin film semiconductor device and process for producing thereof
US6039857A (en) * 1998-11-09 2000-03-21 Yeh; Ching-Fa Method for forming a polyoxide film on doped polysilicon by anodization
US6214194B1 (en) * 1999-11-08 2001-04-10 Arnold O. Isenberg Process of manufacturing layers of oxygen ion conducting oxides
EP1780803A1 (en) * 2005-10-28 2007-05-02 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO A method for applying at least one silicon containing layer onto an electron conductive layer
DE102013201608A1 (de) 2013-01-31 2014-07-31 Wacker Chemie Ag Verfahren zur Abscheidung von polykristallinem Silicium

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3983012A (en) * 1975-10-08 1976-09-28 The Board Of Trustees Of Leland Stanford Junior University Epitaxial growth of silicon or germanium by electrodeposition from molten salts
US4192720A (en) * 1978-10-16 1980-03-11 Exxon Research & Engineering Co. Electrodeposition process for forming amorphous silicon

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DE3769252D1 (de) 1991-05-16
JPS6350496A (ja) 1988-03-03
ES2021751B3 (es) 1991-11-16
AU587713B2 (en) 1989-08-24
IL83570A0 (en) 1988-01-31
ZA876100B (en) 1988-02-19
IL83570A (en) 1991-01-31
EP0260223A1 (de) 1988-03-16
US4773973A (en) 1988-09-27
AU7715587A (en) 1988-02-25
US4759830A (en) 1988-07-26

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