DK156998B - PROCEDURE FOR MAKING TRANSPARENT FILM OF STANNOXIDE ON A SUBSTRATE - Google Patents
PROCEDURE FOR MAKING TRANSPARENT FILM OF STANNOXIDE ON A SUBSTRATE Download PDFInfo
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- DK156998B DK156998B DK469578A DK469578A DK156998B DK 156998 B DK156998 B DK 156998B DK 469578 A DK469578 A DK 469578A DK 469578 A DK469578 A DK 469578A DK 156998 B DK156998 B DK 156998B
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Den foreliggende opfindelse angâr en fremgangsmâde til fremstilling af elektrisk ledende film, der er stærkt transparente over for synligt lys og særdeles refleksive over for infrar0dt lys. Sâdanne film er anvendelige som 5 transparente elektroder til solceller, fotoledende cel- ler, flydende krystal-elektro-optiske displays, foto-elektrokemiske celler og mange andre typer optisk-elek-troniske apparater. Som transparente elektriske modstande anvendes sâdanne film til afisning af vinduer i fly, 10 biler, etc.. Som varme-reflekterende, transparente film pâ glas for0ger disse film effektiviteten af solfangere og af vinduer i bygninger, ovne, smelteovne og natrium-damplamper, og af fiberglasisolation.The present invention relates to a method of producing electrically conductive films which are highly transparent to visible light and highly reflective to infrared light. Such films are useful as 5 transparent electrodes for solar cells, photoconductive cells, liquid crystal electro-optical displays, photoelectrochemical cells, and many other types of optical-electronic devices. As transparent electrical resistors, such films are used for de-icing windows in aircraft, 10 cars, etc .. As heat-reflecting, transparent films on glass, these films increase the efficiency of solar panels and of windows in buildings, ovens, smelting ovens and sodium vapor lamps, and of fiberglass insulation.
Forskellige metaloxider, sâsom stannioxid SnC^, 15 indiumoxid og cadmiums tanna t Cd2Sn0^ har været de mest anvendte materialer til fremstilling af transparente, elektrisk ledende film eller overtræk.Various metal oxides, such as stannous dioxide SnCl3, indium oxide and cadmium tanna t Cd2SnO4 have been the most widely used materials for the production of transparent, electrically conductive films or coatings.
De tidligste metoder til pâfpring af disse overtræk har været baseret pâ pâspr0jtning af en opl0sning 20 af metalsalt (sædvanligvis chloridet) pâ en varm over- flade, sâsom glas. Pâ denne mâde fremstilledes f0rst til-fredsstillende transparente, elektriske modstands-lag til afisning af vinduer i flyvemaskiner. Ved spr0jtepro-cessen fremkaldtes imidlertid temmelig korroderende bi-25 produkter, varmt chlor og hydrogenchloridgasser, der havde tendens til at angribe den varme glasoverflade, hvilket fremkaldte et tâget udseende. Af US-patentskrift nr.The earliest methods for mounting these coatings have been based on spraying a solution of metal salt (usually the chloride) onto a hot surface, such as glass. In this way, the first satisfactory transparent electrical resistance layers were made for de-icing windows in airplanes. However, during the spraying process, rather corrosive by-products, hot chlorine and hydrogen chloride gases, tended to attack the hot glass surface, which produced a foggy appearance. From U.S. Pat.
2.617.745 fremgâr det, at denne u0nskede virkning kan mindskes ved, at man f0rst pâf0rer en film af rent sili-30 ciumdioxid pâ glasset. Men et beskyttende lag af sili- ciumdioxid er ikke særlig effektivt pâ glas med et h0jt alkaliindhold og en h0j termisk ekspansionskoefficient, sâsom almindeligt natronkalkglas. Endvidere angriber disse korroderende biprodukter apparatets metaldele, 35 og de metalliske urenheder, sâsom jern, kan sâ afsættes2,617,745, it appears that this undesirable effect can be mitigated by first applying a film of pure silicon dioxide to the glass. However, a protective layer of silica is not very effective on glass with a high alkali content and a high thermal expansion coefficient, such as ordinary soda lime glass. Furthermore, these corrosive by-products attack the metal parts of the apparatus, 35 and the metallic impurities such as iron can then be deposited.
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0 i filmen med 0delæggende virkninger bâde pâ filmens elek-triske ledningsevne og dens gennemsigtighed.0 in the film with devastating effects both on the film's electrical conductivity and its transparency.
Et andet problem har været xnangelen pâ ensartet-hed og reproducerbarhed af filmens egenskaber. Af US 5 patentskrift nr. 2.651.585 fremgâr det, at der opnâs bedre ensartethed og reproducerbarhed, nâr fugtigheden i apparatet reguleres. Anvendelsen af damp i stedet for en væskespray, sont beskrevet i f.eks. DE-patentskrift nr. 1.521.239 resulterer ogsâ i mere ensartede og re-10 producerbare film.Another problem has been the lack of uniformity and reproducibility of film properties. U.S. Patent No. 2,651,585 states that better uniformity and reproducibility are achieved when the humidity of the apparatus is regulated. The use of steam instead of a liquid spray, described in e.g. DE patent specification 1,521,239 also results in more uniform and reproducible films.
Selv med disse forbedringer har man i de senere âr foretaget fors0g med anvendelse af vakuumafsætnings-metoder, sâsom fordampning og katodeforst0vning, for at opnâ renere og mere reproducerbare film. Pâ trods af de 15 betydeligt st0rre omkostninger ved disse vakuumprocesser er reduktionen af korroderende biprodukter og u0nskede urenheder fremkaldt ved spraymetoderne betydningsfuld, især ved pâf0ringsformer, der omfatter halvledere af h0j renhed.Even with these improvements, attempts have been made in recent years to use vacuum deposition methods, such as evaporation and cathode sputtering, to obtain cleaner and more reproducible films. Despite the 15 significantly higher costs of these vacuum processes, the reduction of corrosive by-products and undesirable impurities caused by the spraying methods is significant, especially in applications involving high-purity semiconductors.
20 Den bevidste tilsætning af visse urenheder er vig- tig ved disse fremgangsmâder for at opnâ h0j elektrisk ledningsevne og h0j infrar0d refleksionsevne. Sâledes in-korporeres tinurenhed i indiumoxid, medens der sættes an-timon til tinoxid (stannioxid) til disse formâl. I hvert 25 tilfælde er disse 0nskede urenheders ("dopingmidlers") funktion at levere "ekstra" elektroner, der bidrager til den elektriske ledningsevne. Disse urenheders opl0selig-hed er h0j, og de kan let tilsættes under anvendelse af aile de ovenfor nævnte afsætningsmetoder. Fluor har en 30 fordel i forhold til antimon som dopingmiddel til tin oxid/ idet de fluor-dopede stannioxidfilms gennemsig-tighed er st0rre end de antimon-dopedes, især i den r0de ende af det synlige spektrum. Denne fordel ved fluor er vigtig ved éventuelle anvendelser til solceller og 35 solfangere. Pâ trods af denne fordel ved fluor anvendes Ο20 The deliberate addition of certain impurities is important in these methods to obtain high electrical conductivity and high infrared reflectivity. Thus, tin impurity is incorporated in indium oxide while adding antimony to tin oxide (stannic oxide) for these purposes. In every 25 cases, the function of these desired impurities ("doping agents") is to provide "extra" electrons that contribute to the electrical conductivity. The solubility of these impurities is high and they can easily be added using all of the above methods of deposition. Fluorine has an advantage over antimony as dopant for tin oxide, in that the transparency of the fluorine-doped stannic oxide films is greater than that of the antimony doped, especially at the red end of the visible spectrum. This advantage of fluorine is important in eventual applications for solar cells and 35 solar collectors. Despite this advantage of fluorine, anvendes is used
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der ved de fleste - og mâske aile - kommercielt tilgænge-lige tinoxidfilm antimon som dopingmiddel. Dette skyldes muligvis, at fluor-doping kun har været demonstreret med den mindre tilfredsstillende spr0j temetodey jf. US pa-5 tentskrift nr. 3.107.177, hvori der beskrives anvendelse af opl0sninger indeholdende organotinforbindelse, HCl og en fluorforbindelse, f.eks. HF, og TJS-pa tentskrift nr. 3.677.814 og 3.759.743, hvori der beskrives anvendelse af opl0sninger indeholdende organotinforbindelser, 10 som indeholder fluor bundet hhv. direkte og indirekte til tin, hvorimod de forbedrede afsætningsmetoder (kemisk dampafsætning, vakuumfordampning og katodeforst0vning) tilsyneladende ikke har vist sig at fremkalde fluor--doping. Endvidere konkluderer en nylig rapport fra en 15 ekspertkomité i American Institute of Physics Conférencethat most - and perhaps all - commercially available tin oxide film antimony as a dopant. This may be due to the fact that fluorine doping has only been demonstrated with the less satisfactory syringe method, cf. HF, and TJS Patent Nos. 3,677,814 and 3,759,743, which disclose the use of solutions containing organotin compounds containing fluorine bound or directly and indirectly to tin, whereas the improved deposition methods (chemical vapor deposition, vacuum evaporation, and cathode sputtering) did not appear to induce fluoride doping. Furthermore, a recent report by a 15 expert committee of the American Institute of Physics Conférence concludes
Proceedings No. 25, p. 288 (1975), at fluors ligevægts-opl0selighed i tinoxid if0lge sagens natur er lavere end antimons. Alligevel skal det bemærkes, at den laveste spe-cifikke modstand, tinoxidfilm har vist, er beskrevet af 20 Gillery i US-patentskrift nr. 3.677.814. Ved anvendelse af en spr0jtemetode fremstillede han fluor-dopede tinoxidfilm med modstande sâ lave som 15 ohm pr. kvadrat-enhed ved anvendelse som udgangsmateriale af en forbin-delse, der har en en direkte tin-fluor-binding. Den 25 laveste modstand i et kommercielt tilgængeligt tinoxid- overtrukket glas ligger for ojeblikket i omrâdet omkring 40 ohm pr. kvadratenhed. Hvis man onsker at opnâ film med sâ lidt som 10 ohm pr. kvadratenhed, har man hidtil været tvunget til at anvende meget kostbare materialer, 30 sâsom indiumoxid.Proceedings No. 25, p. 288 (1975), that fluorine equilibrium solubility in tin oxide according to the nature of the case is lower than antimony. Nevertheless, it should be noted that the lowest specific resistance, tin oxide film, has been disclosed by 20 Gillery in U.S. Patent No. 3,677,814. Using a spray method, he prepared fluorine doped tin oxide films with resistors as low as 15 ohms per minute. square unit using as the starting material of a compound having a direct tin-fluorine bond. The 25 lowest resistance in a commercially available tin oxide coated glass is currently in the range of about 40 ohms per second. square unit. If you want to get a film with as little as 10 ohms per minute. square unit, it has so far been forced to use very expensive materials, such as indium oxide.
Det er et formâl med den foreliggende opfindelse at tilvejebringe en fremgangsmâde til aflejring af et lag eller en film af fluor-dopet stannioxid med en hoj synlig gennemsigtighed, hpj elektrisk ledningsevne og hoj in-35 frarpd refleksionsevne, hvorved den elektriske lednings- 4It is an object of the present invention to provide a method for depositing a layer or film of fluorine-doped stannic oxide with a high visible transparency, high electrical conductivity and high reflectivity, whereby the electrical conductivity
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evne let kan varieres under afsætningen af en sâdan enkelt film og at g0re denne i stand til at nâ meget lave specifikke modstande og overflademodstande, og der anvendes en ikke-korroderende afsætningsatmosfære, fra 5 hvilken sâdanne film med h0j renhed let kan afsættes og uden kontaminering af substratet med urenheder eller kor-rosionsangreb pâ substratet eller apparatet, idet der gâs ud fra gasformige, snarere end flydende, midler til fremstilling af de heri beskrevne overtrukne produkter.ability can be easily varied during the deposition of such a single film and enable it to achieve very low specific resistances and surface resistances, and a non-corrosive depositional atmosphere is used from which such high purity films can be easily deposited and without contamination of the substrate with impurities or corrosion attacks on the substrate or apparatus, relying on gaseous, rather than liquid, means to produce the coated products described herein.
10 If0lge opfindelsen tilvejebringes en fremgangsmâde, ved hvilken man let kan fremstille sâdanne film med meget ensartede og reproducerbare egenskaber over store arealer uden de begrænsninger, der er forbundet med spr0jtemetoderne, og let kan aflejre sâdanne film inden 15 i rer eller pærer eller over overfladen af kompliceret formede genstande, der vanskeligt kan overtrækkes ved spr0jtning.According to the invention, there is provided a method by which such films having very uniform and reproducible properties over large areas can be readily prepared without the limitations associated with the spraying methods, and can easily deposit such films within 15 tubes or bulbs or over the surface of the film. complicated shaped objects that are difficult to coat by spraying.
Ved fremgangsmâden if0lge opfindelsen kan der tilvejebringes forbedrede artikler, sâsom solceller, 20 andre halvledere til anvendelse i elektriske kredsl0b, varmereflekterende vinduer, natrium-lamper og lignende.In the process of the invention, improved articles can be provided, such as solar cells, 20 other semiconductors for use in electrical circuits, heat reflecting windows, sodium lamps and the like.
Ved fremgangsmâden if0lge den foreliggende opfin-delse gennemf0res afsætningen af sâdanne film ved stan-dardfremstillingsmetoder inden for halvlederindustrien 25 og glasindustrien.In the process of the present invention, the deposition of such films is carried out by standard manufacturing methods in the semiconductor industry 25 and the glass industry.
Et særligt karakteristisk træk ved opfindelsen er, at reaktanterne vælges pâ en sâdan mâde, at den 0nskede tin-fluor-binding ikke dannes, f0rend aflejringen er forestâende. Derfor skal tinfluoridmaterialet helst 30 holdes i dampfase og ved temperaturer, der er tilstræk- keligt lave til, at oxidationen af forbindelsen f0rst sker efter omlejringen til dannelse af en tin-fluor-binding. Film af det sâledes fremkomne fluor-dopede tinoxid, der er fremstillet pâ denne mâde har ekstraor-35 dinær lav elektrisk specifik modstand og ekstraordinær h0j refleksionsevne over for infrar0de b0lgelængder.A particularly characteristic feature of the invention is that the reactants are selected in such a way that the desired tin-fluorine bond is not formed before the deposition is imminent. Therefore, the tin fluoride material should preferably be kept in the vapor phase and at temperatures sufficiently low for the oxidation of the compound to occur only after the rearrangement to form a tin-fluorine bond. Films of the resulting fluorine-doped tin oxide produced in this way have extraordinarily low electrically specific resistance and extraordinarily high reflectivity to infrared wavelengths.
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Opfindelsen angâr sâledes en fremgangsmâde ved hvilken formâlet opnâs og til fremstilling af transparente film af stannioxid med en sâdan koncentration af fluor-dopingmiddel, at 1-3% oxygen er erstattet med 5 fluor, pâ et opvarmet substrat under anvendelse af en gasformig blanding, der i begyndelsen indeholder (1) en f0rste fluorholdig organotin-forbindelse, der er fri for direkte tin-fluor-bindinger, (2) en oxiderbar organotinforbindelse, og 10 (3) en oxiderende gas, hvilken fremgangsmâde er ejendommelig ved, at (a) den f0rste fluorholdige organotin-komponent i den gasformige blanding omdannes til en anden gasformig organotin-fluorid-forbindelse med en direkte tin-fluor- 15 -binding ved kortvarig tilfprsel af varme fra det opvar- mede substrat, umiddelbart f0r forbindelsen kommer i kontakt med substratet, (b) den anden organotin-fluorid-forbindelse oxi-deres straks i umiddelbar nærhed af substratet til dan- 20 nelse af et fluor-dopingmiddel i den gasformige blanding, og (c) en fluor-dopet stannioxidfilm dannes pâ det opvarmede substrat ved samtidig afsaetning af den oxi-derbare organotinforbindelse og fluor-dopingmidlet derpâ.The invention thus relates to a process by which the object is obtained and to produce transparent films of stannous dioxide with such a concentration of fluorine dopant that 1-3% oxygen is replaced with 5 fluorine on a heated substrate using a gaseous mixture which initially, (1) contains a first fluorine-containing organotin compound free of direct tin-fluorine bonds, (2) an oxidizable organotin compound, and (3) an oxidizing gas which is characterized by (a) the first fluorine-containing organotin component of the gaseous mixture is converted to a second gaseous organotin fluoride compound with a direct tin-fluorine bond by briefly applying heat from the heated substrate immediately before the contact comes into contact with the substrate (b) the second organotin fluoride compound is oxidized immediately in the immediate vicinity of the substrate to form a fluorine dopant in the gaseous mixture, and (c) a fluorine d an opaque stannic oxide film is formed on the heated substrate by simultaneously depositing the oxidizable organotin compound and the fluorine dopant thereon.
25 Ved fremgangsmâden if0lge opfindelsen er det muligt at danne ovennævnte komponent (1) in situ ved processen ved opvarmning af en gasblanding indeholdende komponent (2) og en gas valgt blandt CFI3, CF3Br og homologe alkyl-a-fluorerede forbindelser af CF3I, CF3Br og CF3SF5, 30 SF5Br og SF5CI eller blandinger deraf.In the process of the invention, it is possible to form the above-mentioned component (1) in situ by the process of heating a gas mixture containing component (2) and a gas selected from CF3, CF3Br and homologous alkyl-α-fluorinated compounds of CF3I, CF3Br and CF3SF5, 30 SF5Br and SF5CI or mixtures thereof.
Produktfilmen er en ensartet, hârd, vedhaeftende, transparent film, hvis elektriske ledningsevne og in-frarpde refleksionsevne afhænger af koncentrationen af det fluorholdige dopingmiddel.The product film is a uniform, hard, adherent, transparent film whose electrical conductivity and sharp reflection ability depend on the concentration of the fluorine-containing dopant.
35 Pâ tegningen viser fig. 1 et skematisk diagram af et apparat, der er egnet til gennemforelse af en frem-35 In the drawing, FIG. 1 is a schematic diagram of an apparatus suitable for carrying out a
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0 6 gangsmâde, ved hvilken et fluor-dopingmiddel er en or— ganotin-fluoralkyldamp, der er fordampet fra sin flydende form.0 6 a process in which a fluorine dopant is an organotin fluoroalkyl vapor evaporated from its liquid form.
Fig. 2 viser et skematisk tværsnit af en solcelle 5 og illustrerer en anvendelse af fremgangsmâden if0lge opfindelsen til fremstilling af halvledere.FIG. 2 shows a schematic cross section of a solar cell 5 and illustrates an application of the method according to the invention for the manufacture of semiconductors.
Fig. 3 viser en rude 120 overtrukket med et film 118 ved fremgangsmâden if0lge opfindelsen.FIG. 3 shows a window 120 coated with a film 118 by the method according to the invention.
1Q Fig. 4 og 5 er kurver, der viser ledningsevnen og refleksionsevnen for forskellige koncentrationer af fluordopingmidlet.1Q FIG. 4 and 5 are curves showing the conductivity and reflectance of different concentrations of the fluorine dopant.
Fremgangsmâden if0lge opfindelsen har to hoved-trin: (1) dannelse af en reaktionsdygtig dampblanding, 5 der ved opvarmning tilvejebringer en forbindelse med en tin-fluor-binding, og (2) overf0ring af denne dampblanding til et opvarmet overflade, hvorpâ der aflejres fluor-dopet tinoxid.The process of the invention has two main steps: (1) forming a reactive vapor mixture, which upon heating provides a compound with a tin-fluorine bond, and (2) transferring this vapor mixture to a heated surface upon which fluorine is deposited. - doped tin oxide.
Tinnet tilf'0res i form af en flygtig, oxiderbar, 20 organisk tinforbindelse, sâsom tetramethyltin, tetra- ethyltin, dibutyltindiacetat, dimethyltindihydrid eller dimethyltindichlorid. Den foretrukne forbindelse er tetramethyltin, da den er tilstrækkelig flygtig ved stue-temperatur, ikke-korroderende, stabil og let renselig.The tin is added in the form of a volatile oxidizable organic tin compound such as tetramethyltin, tetraethyltin, dibutyltin diacetate, dimethyltin dihydride or dimethyltin dichloride. The preferred compound is tetramethyltin as it is sufficiently volatile at room temperature, non-corrosive, stable and easily cleanable.
25 Denne flygtige tinforbindelse anbringes i en boble- kolbe benævnt 10 i figuri 1/ og en indifferent bære-gas, sâsom nitrogen, bobles gennem tinforbindelsen.This volatile tin compound is placed in a bubble flask referred to as 10 in FIG. 1 and an inert carrier gas such as nitrogen is bubbled through the tin compound.
Til de meget flygtige forbindelser, sâsom tetramethyltin og dimethyltindihydrid, kan boblekolben hâve stue-3q temperatur, medens boblekolben og r0rsystemet skal op- 35 0For the highly volatile compounds, such as tetramethyltin and dimethyltin dihydride, the bubble flask may raise room-3q temperature, while the bubble flask and tube system must be heated.
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varmes beh0rigt til de andre mindre flygtige forbin-delser, hvilket er indlysende for fagmænd. Det er en af fordelene ved den foreliggende opfindelse, at man kan undgâ apparaturer med h0j temperatur, og at der 5 kan anvendes simple koldvægs-tilf0rsler.is duly heated to the other less volatile compounds, which is obvious to those skilled in the art. It is one of the advantages of the present invention that high temperature apparatus can be avoided and that simple cold wall feeds can be used.
Dampblandingen skal indeholde en oxiderende gas, sâsom oxygen eller nitrogenoxid. Oxygen er den fore-trukne gas, da det er let tilgængeligt og fungerer lige sâ godt som de mere kostbare alternative oxi-10 dationsmidler.The vapor mixture must contain an oxidizing gas such as oxygen or nitric oxide. Oxygen is the preferred gas since it is readily available and works just as well as the more expensive alternative oxidants.
Gastrykkene opretholdes af regulatorer 25, og oxygenets str0mningshastighed fra en tank 20 og bære-gassens str0mningshastighed fra en tank 21 reguleres med doseringsventiler 30 og mâles med str0mnings-15 mâlere 40. Gasstr0mmene passerer derpâ gennem énvejs- -kontrolventiler 50 ind i et blander0r 60 og et tragt-formet kammer 70. En tinoxidfilm aflejres pâ den var-meste overflade 80, der opvarmes af et varmelegeme 90, typisk til temperaturer pâ 400-600°C.The gas pressures are maintained by regulators 25, and the flow rate of oxygen from a tank 20 and the flow rate of the gas from a tank 21 are controlled by metering valves 30 and measured by flow counters 40. The gas streams then pass through one-way control valves 50 into a mixer 60 and a funnel-shaped chamber 70. A tin oxide film is deposited on the hottest surface 80 heated by a heater 90, typically to temperatures of 400-600 ° C.
20 Denne ovenfor beskrevne generelle fremgangsmâde- type er almindeligt kendt som kemisk dampafsætning. Forskellige modifikationer, sâsom vertikale og rote-rende substratoverflader eller substratoverflader, der ligger under reaktionskammeret og roterer, er kendte 25 for en fagmand og kan være særligt velegnede til an- vendelse afhængigt af substratets geometri eller andre betingelser, der pâvirker en given anvendelse.This general type of method described above is commonly known as chemical vapor deposition. Various modifications, such as vertical and rotating substrate surfaces or substrate surfaces lying below the reaction chamber and rotating, are known to those skilled in the art and may be particularly suitable for use depending on the geometry of the substrate or other conditions affecting a given application.
Rotation af substratet anbefales, sâledes at man let kan bevæge pr0ven gennem éventuelle konvektions-30 str0mme, der kan opstâ i apparatet, og derved bedst sik- re, at de afsatte lag er ensartede. Det har imidler-tid if0lge opfindelsen vist sig, at man ved at anbringe det opvarmede substrat med oversiden nedad kan opnâ sær-deles ensartede overtræk meget lettere uden rotation, 35 8 0Rotation of the substrate is recommended so that the sample can be easily moved through any convection currents that may arise in the apparatus, thereby best ensuring that the deposited layers are uniform. However, it has been found, according to the invention, that by applying the heated substrate face downwards, very uniform coatings can be obtained much more easily without rotation.
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fordi gassen, nâr den opvarmes ovenfra, ikke fremkalder besværlige konvektionsstr0mme. En anden fordel ved at hâve substratet over de reaktionsdygtige dampe er, at éventuelle biprodukter af st0v, snavs eller pulver, 5 der fremkoinraer ved homogen kimdannelse i gassen, ikke faider ned pâ den fremvoksende film.because the gas, when heated from above, does not produce cumbersome convection currents. Another advantage of raising the substrate over the reactive vapors is that any by-products of dust, dirt or powder that result from homogeneous nucleation in the gas do not fall onto the emerging film.
Ved fremgangsmâden if0lge den foreliggende opfin-delse kan regulerede mængder fluorurenheder indf0res i den fremvoksende tinoxidfilm. I den simpleste udf0-10 relsesform for fremgangsmâden er fluor-dopingmidlet en damp indeholdende 1 tin-fluor-binding i hvert mole-kyle. De andre tre tin-valenser er optaget af organiske grupper og/eller andre halogener end fluor. Et typisk eksan-pel pâ sâdanne forbindelser er tributyltinfluorid. Det 15 har vist sig, at det sâledes bundne fluor, der er tilgængeligt for en varm overflade i dampform, ikke spaltes fra tinnet under oxidation pâ en varm overflade.In the process of the present invention, controlled amounts of fluorine impurities can be introduced into the emerging tin oxide film. In the simplest embodiment of the process, the fluorine dopant is a vapor containing 1 tin-fluorine bond in each molecule. The other three tin valences are occupied by organic groups and / or halogens other than fluorine. A typical example of such compounds is tributyltin fluoride. It has been found that the thus-bound fluorine available for a hot surface in vapor form is not cleaved from the tin during oxidation on a hot surface.
Desværre er aile kendte forbindelser med en sâdan direkte tin-fluor-binding ikke særligt flygtige nær 20 stuetemperatur.Unfortunately, all known compounds with such a direct tin-fluorine bond are not very volatile near room temperature.
Det er en særlig fordel ved den foreliggende opfin-delse, at fluor-dopingmidlet dannes ud fra flygtige forbindelser, der ikke har den n0dvendige tin-fluor-binding, men som omlejres ved opvarmning, hvorved der fâs 25 en direkte tin-fluor-binding. Denne omlejring sker for- delagtigt ved temperaturer, der er tilstrækkeligt h0je (f.eks. >100°C) til at det sâledes fremstillede tin-fluorid forbliver i dampfasen, men ogsâ tilstrækkeligt lave (f.eks. < 400°C) til at oxidationen af forbindel-30 sen f0rst sker efter omlejringen. Et eksempel pâ en sâ dan forbindelse er trimethyl-trifluormethyltin, (CH3)3SnCF3· Ved opvarmning til en temperatur pâ ca.It is a particular advantage of the present invention that the fluorine dopant is formed from volatile compounds which do not have the necessary tin-fluorine bond, but which are rearranged upon heating to provide a direct tin-fluorine bond . This rearrangement is advantageously carried out at temperatures sufficiently high (e.g.,> 100 ° C) to allow the tin fluoride thus produced to remain in the vapor phase, but also sufficiently low (e.g., <400 ° C) to that the oxidation of the compound occurs only after the rearrangement. An example of such a compound is trimethyl-trifluoromethyltin, (CH3) 3SnCF3 · When heated to a temperature of approx.
150°C i en opvarmet zone, der st0der op til aflejrings-overfladen 80, omlejres denne forbindelse under dannel-35 se af en direkte tin-fluor-binding til (CH^)^SnF-damp, 9 DK 156998 8 Ο som derpâ reagerer som fluor-donor eller -dopingmiddel.150 ° C in a heated zone adjacent to the deposition surface 80, this compound is rearranged during formation by a direct tin-fluorine bond to (CH 2) Sn SnF steam, Ο reacts as a fluorine donor or dopant.
André forbindelser, der undergâr lignende omlejringer ved temperaturer, der naturligvis varierer noget fra forbindelse til forbindelse, har den almene formel 5 R^SnRF, hvori R betyder en carbonhydridgruppe, og RFOther compounds which undergo similar rearrangements at temperatures which naturally vary somewhat from compound to compound have the general formula 5 R 2 SnRF, wherein R is a hydrocarbon group and
betyder en fluoreret carbonhydridgruppe med mindst êt fluoratom bundet til det carbonatom, der er bundet til tinnet. Den st0rste fordel ved disse fluor-do-pingmidler bestâr i, at de er flygtige væsker, sâledes 10 at de let kan levere tilstrækkeligt damptryk, nâr de fordamper ved stuetemperatur. Dette forenkler appara-tets udformning, som vist i fig. 1, idet behovet for at opretholde en varm zone mellem en boblekolbe 15 og reaktionskammeret 70, for at holde fluor-dopingmidlet 15 i dampfase, elimineres. Apparatet kan sâledes være af den type, der sædvanligvis kaldes en "koldvægsreaktor til kemisk dampafsætning", og som anvendes i vid ud-strækning, f.eks. inden for halvlederindustrien, til afsætning af silicium, siliciumdioxid eller silicium-20 nitrid. Et andet vigtigt træk ved "koldvægs-reaktoren" til halvleder-anvendelsesformâl er, at den mininerer u0nskede urenheder bâde i substratet og den afsatte film.means a fluorinated hydrocarbon group having at least one fluorine atom attached to the carbon atom bound to the tin. The main advantage of these fluorine doping agents is that they are volatile liquids such that they can easily supply sufficient vapor pressure when evaporating at room temperature. This simplifies the design of the apparatus, as shown in FIG. 1, eliminating the need to maintain a hot zone between a bubble flask 15 and the reaction chamber 70 to keep the fluoride dopant 15 in the vapor phase. The apparatus may thus be of the type commonly called a "cold wall chemical vapor deposition reactor" and widely used, e.g. in the semiconductor industry, for the marketing of silicon, silica or silicon nitride. Another important feature of the "cold-wall reactor" for semiconductor applications is that it minimizes unwanted impurities both in the substrate and the deposited film.
Pâ lignende mâde kan man inden for glasfremstilling sætte gasblandingen til hærde- og k0leovnen pâ det sta-25 dium, hvor glasset har den rette temperatur, f.eks.Similarly, in glass making, the gas mixture can be added to the curing and cooling furnace at the stage where the glass has the proper temperature, e.g.
ca. 470°C for bl0dt glas. Pâ denne mâde kan man opnâ særdeles ensartede film med normalt glasfremstillings-udstyr.ca. 470 ° C for soft glass. In this way, very uniform films can be obtained with normal glass making equipment.
Den foretrukne forbindelse, nâr der anvendes 30 apparatet vist i fig. 1, er (CH^UgSnCF^, da den er mere flygtig end forbindelserne med flere carbon-atomer. Det er en stabil, farvel0s, ikke-korroderende væske, der ikke s0nderdeles i luft ved stuetemperatur og kun reagerer særdeles langsomt med vand.The preferred connection when using the apparatus shown in FIG. 1, is (CH 2) UgSnCF 2, as it is more volatile than the compounds with several carbon atoms. It is a stable, colorless, non-corrosive liquid which does not decompose in air at room temperature and reacts very slowly with water.
35 035 0
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Film fremstillet ved fremgangsmâden if0lge op-findelsen viser sig at hâve infrar0de refleksionsev-ner pâ 90% og derover, der mâles pâ kendt mâde ved den konventionelle lO^um b01gelængde af lys, der er 5 karakteristisk for termisk infrar0d strâling ved stue- temperatur. Denne 90%'s refleksionsevne skal sammen-lignes med den 80%'s refleksionsevne, der hidtil er opnâet ved anvendelse af tinoxidovertræk. Sædvanlig-vis er disse infrar0de, reflektive lag fra ca. 0,2 10 til l^um tykke. Tykkelser pâ 0,3-0,5y,um er typiske.Films made by the method according to the invention are found to have infrared reflectance of 90% and above, which is measured in a known manner at the conventional beam length of light characteristic of thermal infrared radiation at room temperature. This 90% reflectivity should be compared to the 80% reflectivity obtained so far using tin oxide coatings. Usually, these infrared reflective layers are from ca. 0.2 to 10 µm thick. Thicknesses of 0.3-0.5 µm are typical.
For mere kvantitativt at karakterisere indholdet af fluor-dopingmiddel i filmene mâles den infrar0de refleksionsevne i h0lgelængdeomrâdet fra 2,5^um til 40yUm.Ved at tilpasse disse data til teoretiske kur- 15 ver, som beskrevet nærmere af R. Groth, E. Kauer og P.C. van den Linden, "Optical Effects of Free Carriers in SnC>2 Layers", Zeitschrift für Naturforschung, bind 179, side 789-793 (1962), fâs der værdier for den frie elektronkoncentration i filmene. De opnâede vær- ?n -3 21 -3 20 dier ligger i omrâdet fra 10 cm til 10 cm og for0ges jævnt med 0gede koncentrationer af fluor-do-pingmidlet. Teoretisk skal der frig0res en fri elek-tron for hvert fluoratom, der erstatter et oxygen-atom i gitteret. Denne hypotese bekræftes ved elek-25 tronspektroskopiske mâlinger if01ge Auger af den to tale fluorkoncentration i nogle af filmene, hvilket giver fluorkoncentrationer i overensstemmelse med kon-centrationerne af frie elektroner inden for den eks-perimentelle usikkerhed. Denne overensstemmelse er 30 tegn pâ, at det meste af det inkorporerede fluor er elektrisk aktivt.To more quantitatively characterize the content of fluorine dopant in the films, the infrared reflectivity in the wavelength range is measured from 2.5 µm to 40 µm. By adapting this data to theoretical curves, as described in detail by R. Groth, E. Kauer and PC van den Linden, "Optical Effects of Free Carriers in SnC> 2 Layers", Zeitschrift für Naturforschung, vol. 179, pages 789-793 (1962), values for the free electron concentration in the films are obtained. The obtained values are in the range of 10 cm to 10 cm and are increased evenly with increasing concentrations of the fluorine doping agent. Theoretically, a free electron must be released for each fluorine atom, replacing an oxygen atom in the lattice. This hypothesis is confirmed by electron spectroscopic measurements according to Auger of the two speech fluorine concentration in some of the films, which gives fluorine concentrations consistent with the concentrations of free electrons within the experimental uncertainty. This consistency is 30 indications that most of the incorporated fluorine is electrically active.
Den infrar0de refleksionsevne ved lO^um og lige-ledes filmenes elektriske ledningsevne er maksimale ved en dopingmiddelmængde pâ 1,5-2% fluor i stedet 35 0The infrared reflectivity at 10 µm and the electrical conductivity of the films are maximized at a dopant amount of 1.5-2% fluorine instead.
il DK 156998 Bil DK 156998 B
for oxygen. Maksimumsomrâderne er meget brede, og næsten maksimale ledningsevner og refleksionsevner udvises af film med 1-2,5% fluor. Der er ogsâ en svag, bred absorption over hele det synlige b01gelængdeomrâde, 5 der 0ges direkte med fluorkoncentrationen. Til frem- stilling af film med h0j elektrisk ledningsevne og h0j synlig gennemsigtighed er derfor en fluorkoncentration i filmen pâ ca. 1% (dvs. fluor/oxygenforhold pâ 0,01 i filmen) mest 0nskelig. Dette optimum varierer imid-10 lertid noget afhængigt af den spektrale fordeling, der har interesse ved en given anvendelse. Ved at variere koncentrationen af fluor-dopingmidlet kan man ved ru-tinemæssige fors0g let bestemme den optimale procent-del til en hvilken som helst given anvendelse.for oxygen. The maximum ranges are very wide and almost maximum conductivity and reflectance are exhibited by films with 1-2.5% fluorine. There is also a weak, wide absorption over the entire visible length range, which is added directly with the fluorine concentration. Therefore, for the production of films with high electrical conductivity and high visible transparency, a fluorine concentration in the film of approx. 1% (ie fluorine / oxygen ratio of 0.01 in the film) most desirable. This optimum, however, varies somewhat depending on the spectral distribution of interest in a given application. By varying the concentration of the fluorine dopant, by routine experiments, the optimum percentage for any given application can be readily determined.
15 - o Mængder af fluor-dopingmiddel pa op til 3% kan let opnâs i filmene under anvendelse af den her omhand-lede fremgangsmâde. Resultaterne fra den kendte teknik overskrider ikke 1%, og dette har været anset for at være opl0selighedsgrænsen for fluor. Selv om sâdanne 20 . «i store mængder dopingmiddel ikke er nodvendige til til-vejebringelse af optimal infrar0d refleksionsevne eller elektrisk ledningsevne, kan de grâ film, der fremstilles ved dopingmiddelmængder pâ op til 3% være nyttige pâ bygningsglas til begrænsning af solopvarmning i bygninger 25 o med air-condition. Til sadanne anvendelser reduceres dopingmiddelmængden pâ filmens overflade fordelagtigt til ca. 2% for at fâ maksimal infrared reflektionsevne.Amounts of fluorine dopant of up to 3% can be readily obtained in the films using the method of the present invention. The prior art results do not exceed 1% and this has been considered to be the solubility limit for fluorine. Although 20. «In large amounts of dopant is not necessary to provide optimum infrared reflectivity or electrical conductivity, the gray films produced by dopant amounts of up to 3% may be useful on building glass to limit solar heating in buildings 25 o with air-conditioning . Advantageously, for such applications, the amount of dopant on the film surface is reduced to approx. 2% for maximum infrared reflectivity.
Ved anvendelse af de mâlte elektronkoncentra- tioner og elektriske ledningsevner kan man bereone elek-30 tronmobiliteten. For forskellige film er der pâ denne mâde beregnet værdier pâ fra 50 til 70 cm /volt-sek..Using the measured electron concentrations and electrical conductivity, one can calculate the electron mobility. For different films, values of 50 to 70 cm / volt-sec are calculated in this way.
Tidligere opnâede mobilitetsværdier for tinoxidfilm har ligget mellem 5 og 35 cm /volt-sek.. De forelig- 35 12Previously obtained mobility values for tin oxide films have been between 5 and 35 cm / volt-sec.
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0 gende film menes at være de f0rste, der har sâdanne 2 mobilitetsværdier, der overskrider 40 cm /volt-sek..0 running movies are thought to be the first to have such 2 mobility values exceeding 40 cm / volt-sec.
Disse værdier illustrerer pâ en anden mâde den her omhandlede fremgangsmâdes samt de derved fremstil-5 lede films overlegenhed.These values illustrate in another way the superiority of the method of the present invention as well as the superiority of the films thus produced.
Premgangsmâden if0lge opfindelsen er ogsâ sær-deles nyttig til anvendelse ved fremstilling af hid-til ukendte anordninger, som f.eks. sâdanne med elek-trisk ledende lag, inden for halvleder-fremstilling 10 (f.eks. integrerede kredsl0b og lignende) og ogsâ inden for fremstillingen af varme-reflekterende transparente genstande, sâsom vinduer.The process according to the invention is also particularly useful for use in the manufacture of novel devices, such as e.g. such as with electrically conductive layers, in semiconductor fabrication 10 (e.g., integrated circuits and the like) and also in the manufacture of heat-reflective transparent articles, such as windows.
Den inest fordelagtige udf0relsesform for frem-gangsmâden if0lge opfindelsen er den, hvor organo-15 -tin-fluorid-forbindelsen med en tin-fluor-binding s0nderdeles pâ substratet umiddelbart efter dannel-sen. Denne s0nderdeling sker fortrinsvis i en snæver reaktionszone, der overvejende opvarmes til s0nder-delingstemperaturen af varme fra selve substratet.The most advantageous embodiment of the method according to the invention is the one in which the organo-15-tin-fluoride compound having a tin-fluorine bond decomposes on the substrate immediately after formation. This decomposition preferably occurs in a narrow reaction zone which is predominantly heated to the decomposition temperature of heat from the substrate itself.
20 Nedenstâende eksempler illustrerer fremgangs- mâden if0lge opfindelsen samt de derved fremstillede produkter nærmere.The following examples further illustrate the method of the invention and the products thus produced.
Hvis intet andet er angivet, udf0res nedenstâende eksempler i overensstemmelse med f0lgende generelle 25 fremgangsmâde:Unless otherwise indicated, the following examples are carried out in accordance with the following general procedure:
Eksempel 1Example 1
Premgangsmâden eksemplificeres ved et fors0g, 30 hvor man anvender apparatet if01ge fig. 1 til frem stilling af en gasstr0m, der indeholder 1% tetrame-thyltin (CH^^Sn, 0,02% trimethyl-trifluormethyltin (CH^)3SnCF3, 10% nitrogenbæregas og resten oxygengas.The preliminary method is exemplified by an experiment using the apparatus of FIG. 1 to prepare a gas stream containing 1% tetramethyltin (CH 2 Sn, 0.02% trimethyl-trifluoromethyltin (CH 2) 3 SnCF 3, 10% nitrogen carrier gas and the residual oxygen gas.
Den fremkomne str0m ledes hen over en pyrex-glas-35 13The resulting stream is passed over a pyrex glass-13
DK 156998 BDK 156998 B
plade, der er 15 cm i diameter og holdes ved 500°C i en aflejringsperiode pâ ca. 5 minutter. Gasstrommens hast ighed er ca. 400 cm3 pr. minut. Denne hastighed er af en sâdan st0rrelse, at gasudskiftningshastigheden i 5 tragten 70 er ca. 1 gang hvert andet minut. Der afsættes en transparent film med en tykkelse pâ ca. 1 μι. Den har en elektrisk modstand pâ 2 ohm pr. kvadratenhed svarende til en specifik modstand pâ 0,0002 ohm-cm. I denne film bestemmes et fluor/oxygenforhold pâ ca. 0,017 10 og en mobilitet pâ ca. 50 cm2/volt-sek..plate that is 15 cm in diameter and kept at 500 ° C for a deposition period of approx. 5 minutes. The gas flow rate is approx. 400 cc per minute. This velocity is of such a size that the gas exchange rate in the hopper 70 is approx. Once every two minutes. A transparent film with a thickness of approx. 1 μι. It has an electrical resistance of 2 ohms per. square unit corresponding to a specific resistance of 0.0002 ohms-cm. In this film, a fluorine / oxygen ratio of approx. 0.017 10 and a mobility of approx. 50 cm 2 / volt-sec.
Eksemoel 2Example 2
Ved gentagelse af fremgangsmâden ifblge eksempel 1 under anvendelse af et natriumfrit siliciumsubstrat 15 faider modstandsværdien til ca. 1 ohm pr. kvadratenhed, dvs. ca. halvdelen af den modstandsværdi, der opnâs med et natriumholdigt substrat.By repeating the method of Example 1 using a sodium-free silicon substrate 15, the resistance value is reduced to approx. 1 ohm pr. square unit, i.e. ca. half of the resistance value obtained with a sodium-containing substrate.
Konventionelle silicium-fotoceller ("solceller") har hidtil haft typiske overflademodstande pâ 50-100 20 ohm pr. kvadratenhed. For at fâ en acceptabelt lav total cellemodstand anbringes et metalgitter med en maskevidde pâ 1 eller 2 mm pâ siliciumoverfladen. Ved afsætning af et fluor-dopet tinoxidlag med en flademodstand pâ ca.Conventional silicon photocells ("solar cells") have so far had typical surface resistances of 50-100 20 ohms per second. square unit. In order to obtain an acceptable low total cell resistance, a metal grid with a mesh width of 1 or 2 mm is applied to the silicon surface. When depositing a fluorine-doped tin oxide layer with a surface resistance of approx.
0,5 ohm pr. kvadratenhed (ca. 2 μια tyk) pâ celleover-25 fladen kan maskevidden i metalgitteret oges til ca. 10 mm med en tilsvarende reduktion af gitterets pris. Al-ternativt kan man anvende en lille gitterstbrrelse og cellen er i stand til at fungere effektivt, selv nâr sollyset er koncentreret med en faktor pâ ca. 100, for-30 udsat at cellen holdes tilstrækkeligt afkblet.0.5 ohms per square unit (about 2 μια thick) on the cell surface, the mesh width of the metal grid can be increased to approx. 10 mm with a corresponding reduction in the price of the grid. Alternatively, a small grid size can be used and the cell is able to function effectively even when the sunlight is concentrated by a factor of approx. 100, provided that the cell is sufficiently blotted.
Et skematisk tværsnit 100 af sâdan en celle er vist i fig. 2, hvor et 2 μια tykt lag 102 af n-SnC>2 (man anvender det her omhandlede fluor-dopede materiale), 0A schematic cross section 100 of such a cell is shown in FIG. 2, where a 2 μια-thick layer 102 of n-SnC> 2 (the fluorine-doped material used herein) is used, 0
DK 156998 BDK 156998 B
et 0,4^um tykt lag 104 af n-silicium (kendt phosphor--dopet silicium) og et 0,1 mm tykt lag p-silicium-lag 106 (kendt bor-dopet silicium) forenes med et aluminiumlag 108, der tjener som elektrode. Et metal-5 gitter 110 har en maskevidde pâ 10 mm. Dog opnâs der udmærkede egenskaber.a 0.4 µm thick layer 104 of n-silicon (known phosphorus-doped silicon) and a 0.1 mm thick layer of p-silicon layer 106 (known boron-doped silicon) are joined to an aluminum layer 108 serving as an electrode. A metal 5 grid 110 has a mesh width of 10 mm. However, excellent properties are obtained.
De afsatte film kan anvendes til fremstilling af andre halvleder-artikler, f.eks. ledere eller mod-stande. Tinoxidovertræk har været anvendt sâledes 10 f0r i intégrerede kredsl0b. Den forbedrede lednings- evne tillader i fremtiden et bredere anvendelsesomrâde for dette materiale. Ikke blot er flademodstanden ud-videt til meget lavere værdier (f.eks. ca. 5 ohm pr. kvadratenhed eller mindre) end hidtil muligt, men afsæt-15 ningen af laget kan ogsâ udf0res med det samme apparat, som man f.eks. anvender til dyrkning af épitaxial silicium. Dette eliminerer de bekostelige og besværlige t0mnings-, rensnings- og fyldningstrin mellem pâf0-ringerne.The deposited films can be used to make other semiconductor articles, e.g. conductors or resistors. Tin oxide coatings have been used 10 times in integrated circuits. The improved conductivity in the future allows a wider scope for this material. Not only is the surface resistance expanded to much lower values (e.g., about 5 ohms per square unit or less) than previously possible, but the deposition of the layer can also be performed with the same apparatus as . uses for growing epitaxial silicon. This eliminates the costly and cumbersome emptying, cleaning and filling steps between the fittings.
20 Modstandsværdierne, der opnâs for det fluor-dopede tinoxid pâ siliciumsubstrater, er ca. 10~^ ohm-cm, der kan sammenlignes . med værdierne for pâdampet tantalmetal, der somme tider anvendes til forbindelser i integrerede kredsl0b. Da tinoxids og siliciums termiske udvidelses-25 koefficienter passer sâ godt sammen, kan man afsætte tykke lag uden væsentlige spændinger.The resistance values obtained for the fluorine doped tin oxide on silicon substrates are approx. 10 ~ ^ ohm-cm comparable. with the values of steamed tantalum metal sometimes used for compounds in integrated circuits. Since tin oxide and silicon thermal expansion coefficients are so well matched, thick layers can be deposited without significant stresses.
Fig. 4 viser fluor-dopede stannioxidfilms elek-triske ledningsevne som en funktion af det mâlte fluor/-oxygen-forhold i filmene, ved afsætningstemperaturer 30 pâ 480°C og 500°C.FIG. 4 shows the electrical conductivity of fluorine-doped stannic oxide film as a function of the measured fluorine-oxygen ratio in the films, at deposition temperatures 30 at 480 ° C and 500 ° C.
Fig. 5 viser de fluor-dopede stannioxidfilms in-frar0de refleksionsevne som en funktion af det mâlte fluor/oxygen-forhold i filmene, ved afsætningstemperaturer pâ 480°C og 500°C.FIG. 5 shows the infrared reflectivity of the fluorine-doped stannous film as a function of the measured fluorine / oxygen ratio in the films, at deposition temperatures of 480 ° C and 500 ° C.
35 035 0
15 DK 156998 BDK 156998 B
I fig. 4 og 5 er der ligeledes angivet (1) de kendte kostbare indium-oxid-materialers ledningsevne (beskrevet i Philips Technical Review, bind 29, side 17 (1968) af van Boort og Groth) og (2) de bedst under-5 byggede kendte værdier for ledningsevne og refleksions- evne af dopede stannioxidovertræk.In FIG. 4 and 5 are also listed (1) the conductivity of the known costly indium oxide materials (described in Philips Technical Review, Vol. 29, page 17 (1968) by van Boort and Groth) and (2) the best-built known values for conductivity and reflectivity of doped stannic oxide coatings.
10 15 20 25 30 3510 15 20 25 30 35
Claims (11)
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| DK469578A DK156998C (en) | 1978-10-20 | 1978-10-20 | PROCEDURE FOR MAKING TRANSPARENT FILM OF STANNOXIDE ON A SUBSTRATE |
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| DK156998C DK156998C (en) | 1990-03-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3107177A (en) * | 1960-01-29 | 1963-10-15 | Pittsburgh Plate Glass Co | Method of applying an electroconductive tin oxide film and composition therefor |
| US3677814A (en) * | 1970-10-26 | 1972-07-18 | Ppg Industries Inc | Process for forming electroconductive tin oxide films by pyrolyzation of alkyl and aryl tin fluorides |
| US3759743A (en) * | 1971-09-17 | 1973-09-18 | Libbey Owens Ford Co | Method of applying coarings of tin oxide upon transparent substrates |
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1978
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3107177A (en) * | 1960-01-29 | 1963-10-15 | Pittsburgh Plate Glass Co | Method of applying an electroconductive tin oxide film and composition therefor |
| US3677814A (en) * | 1970-10-26 | 1972-07-18 | Ppg Industries Inc | Process for forming electroconductive tin oxide films by pyrolyzation of alkyl and aryl tin fluorides |
| US3759743A (en) * | 1971-09-17 | 1973-09-18 | Libbey Owens Ford Co | Method of applying coarings of tin oxide upon transparent substrates |
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| DK156998C (en) | 1990-03-26 |
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