DD152532A5 - METHOD FOR PRODUCING AN ELECTRICALLY CONDUCTED ARTICLE - Google Patents

Abstract

The invention relates to a method for producing an electrically conductive article made of glass or another mineral material. The aim of the invention is to provide an electrically conductive article with good Leitfaehigkeit, high transparency for visible light, high reflectivity for infrared and high mechanical resistance. According to the invention, an adhesive layer of tin oxide with a lower than 10 & exp -2! Ohms times cm specific resistivity on a substrate made of glass, ceramic or other mineral substance deposited, one reacts on the surface of the previously preheated to at least 500 degrees C substrate, a volatile compound in a Traegergas verduenntem tin and water vapor, so, that this gas contains at least 30% hydrogen. According to the invention, the article produced in this way has the following properties for a tin oxide coating of 1 to 3 μm thickness: surface resistance = 1 to 10 ohm transparency = 60 to 95% IR reflectivity> equal to 50%.

Description

222 96 9 - ^A -

Berlin, 16.12.1980

AP H 01 L / 222 969 57 839/18

Method for producing an electrically conductive article

Area of application of

The present invention relates to a method for producing an electrically conductive article, which consists of a substrate of glass or other mineral material, which is covered by a Zinno ^ id conductor layer, according to which one on the surface of the substrate, a compound in a Carrier gas diluted tin and water vapor can react. The invention also relates to such a conductive article. Preferably, the substrate is a silicon glass sheet, silicon boro-silicon or sodiocalcique, and the article is an electrically conductive glass suitable for a glass Large number of industrial Anwendungsunrs forms, as will be seen below.

The substrate may also be composed of other mineral materials which are transparent or not, such as porcelain, faience, metal-ceramic composites or enamels *

The article produced according to the invention is used, for example, as a glass for motor vehicles and buildings.

Characteristic of the known technical solutions

The use of tin oxide to make a glass or ceramic substrate is known and is the subject of this invention

12/16/1980

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numerous publications, including: "Physical Properties of SnO ₂ Materials" by Z. M, üarzebski and O, P. Marton, 3. Electrochem. Soc. 1976, 199; 299C; 333c. "Chemical Vapor Deposition of Antimony" Doped Tin Oxide Films Formulated from Uibutyl Tin Diacetate "by O, Kane, H. P ₀ Welders, E. Kern, 3, Electrochem. Soc. 1976, 123, no. 2,270; "Composition and Conductivity of Tin Oxide Films Prepared by Pyrohydrolytic Decomposition of Tin (IV) Compounds" by H, Kim H and ₉ A, Laitinen, 3 "Amer, Ceramic Soc, 58, 23 (1975); BE-PS 869 062. In this latter patent, a glass is described, which is coated with a layer whose resistance (R ₈ ) is below 50 Π- and has an increased reflectance in infrared. However, the patent does not give any exact indication of the manufacture of such a glass, and therefore this publication does not contribute to technical progress. "So far, it had not yet come so far, a conductor glass with electrical and optical properties according to the present Erf 1" Φ '"ο to manufacture, that can withstand ol.re change at the same time the curing and shaping operations as well, which are required in the production of glass for buildings and automobiles' either have the coatings of known type with tin oxide is a lack of conductivity or transparency and are too fragile to withstand the mechanical and thermal stresses caused by the hardening and shaping of the glass plates to which they are applied.

At present, various methods and devices are known, Gis for coating a substrate, for example a glass plate, with a tin oxide layer

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serve, a layer which should have at the same time one of the substrate sufficiently equal transparency, a relatively low specific electrical line resistance and an increased mechnischen resistance.

In this way, in addition to other methods, use has already been made of the vapor deposition (CVD) technique for this purpose. Are known in particular from d 'm article by H. Kock "Electrical tests on Zinndioxidschichten" (Phys. Stat. 1963, Vol. 3, pp 1059 and 55) discloses a method and apparatus for depositing a thin layer on a SnO ₀ Glass plate by reaction of SnCl. and H "0, the Sn-diluted form was applied in a carrier gas in the presence of air in contact with the surface of the glass plate preheated to a temperature on the order of 200 to 400 ^° C. These two gaseous reactants are applied to the glass by means of a fan with two coaxial nozzles, from which the central nozzle receives the gaseous solution of the SnOp, while the outer nozzle is fed with the gaseous HUO solution.

There has also been provided a method and a device which are very similar to those mentioned above, in particular in DE-OS 21 33 174, which also makes it possible to provide doping on a substrate, in the present case also a glass plate, applied SnOp layer with antimony to reduce the specific electrical conduction resistance of this layer. For this purpose, use was made, in particular, of SbCl or SbCl 3 in diluted form in a carrier gas, in this case nitrogen, which in the presence of SnCl ₄ and H 2 O by means of

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a fan with three coaxial nozzles is placed over the substrate, each receiving one of the aforementioned compounds. The combination action takes place so close to the substrate and at a certain distance from the three nozzles of the fan One can also mention U.S. Patents 3,850,679, 3,888,649 and British Patent 1,507,996.

Incidentally, it is known that the incorporation of a reducing compound in the reaction of tin oxide formation of a tin compound and water vapor increases the conductivity of the resulting layer. "Thus, Kuznetsov (Fizika Fverdogo TeIa, Vol. 2, No. 1, 35-42 (I960) the hydrolysis of SnCl in solution in alcohol by sputtering of water and such a solution on a heated to 500 ⁰ C surface, the conductivity

-2 - 1 of the layer thus obtained (S _x Um) 10 -A- was, ie a specific conduction resistance ρ in the order of magnitude

~ 2

from 1.0 jik. cm had. However, the transparency of a coating obtained under such conditions is not: satisfactory.

Furthermore, the use of hydrogen in the deposition processes of SnO_djrch CVD is not unknown per se. In the journal of the Eloctrochemical Society 120 (5), 701-2 (1973) the deposition of SnOp grains on a substrate of oxidized silicon by CVD is described. The reagents are SnCl. and water vapor, and the carrier gas is nitrogen. In this article, it is shown that the reaction was carried out in the additional presence of oxygen or hydrogen. But it is not possible to loading after the description of g given in this comparison öffentlicK experimental conditions ..

16.12.1980 AP H 01 L / 222 969 2 2 2 9 6 9 - 5 - 57 839/18

agree which relative hydrogen amount is used. It is likely that ё.е would have to be weak because the publication only states that the presence of hydrogen resulted from some increase in the conductivity of the SnO 2 layer. On the other hand, FR-PS 1 207 231 (Philips) describes a method for depositing layers of metal oxide, in particular SnO 2, by CVD on a substrate where SnCl 2, water vapor and optionally hydrogen intervene, this latter gas being intended for the hydrolysis of Stanni tetrachloride required water duroh reaction with the oxygen (of which the air, for example) to form. However, the examples of this patent show that the percentage of hydrogen in the gaseous mixture used is relatively low (about 7.5%) ♦

The aim of the invention is to provide an improved method for producing an electrically conductive article having good conductivity and high mechanical resistance as well as good heat reflectivity.

Essence of the invention

The invention is based on the object zujn applying an electrically conductive layer on sin Mineralsubstarat suitable © reagents and conditions.

According to the present invention, an adhesive layer of tin oxide having a resistivity of less than 10-Ω · cm on a substrate made of glass, ceramic or another

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Deposited mineral substance by previously on the surface de © previously at least 500 ⁰ C preheat substrate a volatile compound from in a carrier * gas diluted tin and water vapor react, such that this gas contains at least 30 % hydrogen.

The substrate may be, for example, a glass sheet 1 to 15 mm thick. It may, for example, also be a float glass glass of 2 to 7.4 mm thickness.

The article produced according to the invention has the following properties at coating thicknesses of between 1 and 3 μm: surface resistance Rq = 1 to 10 Si, transparency 70 %, IR reflectance ъ 50 %, and the fact that preferably this coating undergoes no significant change when subjecting the article to heat and bending under heat. For curing, the substrate is heated to about 700 ⁰ C and then cooled at a rate of 5 to 10 ° C / s. As regards the Biogefähigkeit, so heating the article up to the melting temperature and bends it preferably from the side where the coating is exposed to the pressure _o In this operation can be achieved radii of curvature in the order of 15 cm without destruction of the conductive coating. The resistance of the SNOG coating of the present article is of the order in front of "at least 10" ² Xl, cnu

The disadvantages of the known processes are now eliminated by the process according to the invention, which relates to the so-called CVD (Chemical Vapor Deposition) process and which consists on the surface of the heated glass

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reacting a volatile tin compound with water vapor and a reductant reactant.

The reasons why the offer of a hydrogenation compound is likely to convert part of the tetravalent tin to divalent tin and increase the conductivity are not very clear, because it is less likely that in such a case metallic Sn will form, the presence of which would be easily detectable. because it would cause the translucent layer to become matted. On the other hand, it does not seem to be excluded that the SnO "could form a molecule with the SnC resulting from the reduction, which is electronically poorly excited (for example, I Sn ₂ O J ⁴ **), the presence of which can be transmitted by hole transmission conductivity).

However that may be, it has been found that, as mentioned above, for the reaction between SnCl. and the! -LO relies on the CVD technique, the addition of alcohol as a reducing agent in a simple mixture with dsm SnCl. does not produce conductor layers with very appreciably improved properties, demonstrating that premixing of the reactants is not suitable.

According to the ancestor of the invention, by means of a carrier gas which contains at least 30% by volume of hydrogen, which causes a partial reduction of the SnO "or the reaction of SiPittel in its reaction on the substrate"

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In methods known in the art, the percentage of hydrogen in the gaseous mixture used is relatively low and, at about 7.5 %, is well below that of the mixtures suitable for the present invention where at least 30 % of hydrogen is required in the gaseous volume to impart a sufficiently low specific line resistance to the SnO 2 bake direction.

In carrying out the process of the invention, the techniques known in the art for coating mineral substrates with tin oxide may be used by the vapor deposition (CVD) technique. As stated in the introduction, see © such equipment prior to have simultaneously impinge on to a suitable temperature (400 to 600 ⁰ C) heated substrate gas streams which contain Roaktionsrnittel (SnCl. + Carrier gas and HgO + Trägorgas). The process according to the invention is likewise carried out using a hydrogen mixture and an inert gas, for example nitrogen, as the carrier gas. Preferably, this mixture contains 30 to 80% by volume of hydrogen or more. However, in certain special cases, it is possible to use virtually pure, for example 99.9.degree.

The tin compound is preferably taken to be pure SnCl 2 or dissolved in an inert solvent. but it is also possible to use other volatile tin compounds, for example of the Sn (Alk) type, in which Alk denotes a lower alkyl radical, and dibutyl-diacetyl-tin.

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Vorzugsweioe is used to carry out the present method ѳіпѳ means for coating by CVD, as described by the applicant in the IT patent application 1412 / 79-6. As will be seen below, such a device allows to perform at very high speed effectively the coating of glass flakes and plates with a SnOp layer of excellent homogeneity, which according to the product of the invention achieves very high levels of mechanical performance and performance ensures the electrical and optical properties of any kind.

In the process according to the invention, the hydrogen acts as a reducing agent for the reactants or the reaction product. In addition, the hydrogen also acts as a reaction moderator,

In the process according to the invention, the hydrogen can also be produced on contact with the substrate by thermal decomposition of a hydrogen-containing compound diluted in the carrier gas, for example methanol. The gas can also be added to the mixture from the reaction of the hydrogen fluoride, the treatment with this constituent the effect is that the parasitic dispersion of light in the SnO ₂ coating is reduced. The Fluorwasserr.toffgas is delivered in admixture with water in the ratio of 0.1 to 5 wt .-%. According to the invention one can repeat the deposition process a second or multiple Маіѳ sequentially after receiving a erston SnO ₂ coating, and then the coating thus obtained of two or more superimposed layers of tin oxide is _e The thickness of each of the elementary layers is preferably between 10 and 500 nrn "

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Outsourcing з.Ье i play

The invention is explained in more detail below with reference to some examples.

In the accompanying drawing, which represents, for example and very schematically, an embodiment of the device which is the subject of the present invention, show:

Fig. 1: an overall view;

Fig. 2: a perspective © partial view with vertical section of an element of the device of Fig. 1 on an enlarged scale.

The device visible in the drawing is intended to apply a tin oxide layer SnO ₂ by means of the so-called CVD technique on a substrate, in the present case a glass plate V heated to a high temperature, by utilizing the following chemical reaction:

SnCl ₄ + 2 H ₂ O -_? SnO ₂ + 4 HCl

For this device above all a Reiho of rolls l, -i which the panel V rests and shifts in the direction F, rollers which are driven counterclockwise by a (not shown) electric motor in rotation and of course a me the width of the zm supporting glass plate have comparable length. The rotational speed of the rollers 1 is chosen so that the displacement of the plate V at a linear speed of several meters per minute on the order of 1 to 15, according to the case, stctt-

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place. Of course, this measure of speed is only an example. "If necessary, one can provide much higher displacement speeds for the glass. _E

Above this row of ribs 1, the illustrated device has a blower 2, the basic structural principle of which is the subject of FIG. 2, to which reference is now made. This blower has three distinct nozzles 3; 4 and 5, which extend over a Lenge corresponding to the width of the glass sheet V long side parallel to the mentioned rollers 1. Such nozzles may have a width of several mats. As can be seen in the drawing, the nozzles 3 to 5 are by assembling elongate rolling profiles 6a and 6b; 7a and 7b; 8a and 8b formed, in turn, by any suitable means in two pairs of profiles 9a and 9b or, iOa and 10b, the between them passages 11; 12 and 13 limit, with the nozzles 3; 4 bz '5 related.

The side walls 3a and 3b; 4a and 4b; 5a and 5b of the nozzles 3 to 5 converge to form a common line L which is spaced from the plane comprising the lower- side profiles 6a and 6b in a length of the order of, for example, 3 to 6 mm. In addition, the outlet openings of the nozzles 3; Figures 4 and 5, which are in the form of three oblong slots extending over the entire length of the profiles 6a; 7a 7b and 6b, a width of a few tenths of a millimeter, for example, about 1/10 to 5/10.

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The width of the underside of the profiles 6a and 6b is preferably between 10 and 2., iü1 the total width of the exit slots of the nozzles 3 to 5.

Preferably, but not exclusively, the underside of the profiles 6a and 6b is coated with a chemically inert metal layer or an alloy of such metals or even metal oxides. The metal may be, for example, gold or platinum "Oie oxides can be SiO ₂ or Al ₀ O selected SnO ^, Of course, one could provide these organs also made of solid inert metal, provided however, did not speak their cost price.

In fact, the common metals and alloys such as steel or brass in the presence of hydrogen have catalytic properties which are likely to interfere with the control of the desired reaction to achieve deposition of SnO ₂ hu which is to have the desired mechanical, physical and optical properties.

The assembly of profiles forming the fan 2 is covered at each end with a non-illustrated sealing cup, which is mounted so as to ensure complete sealing and thus to pass 3; 4 and 5 and passages 11; Channels 14a and 14b formed in the upper part of the profiles 10a and 10b along the entire length thereof allow fluid circulation, for example of D1, to reach the blower 2 at an optimum operating temperature hold.

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Another plate 15 covers the top of the blower 2 over its entire extent, sealing each orifice between the passages 11; 12 and 13 is excluded _e

It should also be noted that the general profile and the surface condition of the walls defining the nozzles 3 to 5 and the passages 11 to 13 (FIG. 2) as well as the cross sections of this oil are such that for gaseous throughputs of the order of 3 to 6 l / h μτο centimeter length of the fan, the streams at the exit of the nozzles are "laminar".

On both sides of the blower 2 and along its entire length, the apparatus shown has two square-section intake ducts 16 and 17 (Figures 1 and 2), the underside of which runs coplanar with the underside of the above-described profiles 6a and 6b in each case two longitudinal slots 16a and 16b for the channel 16 or, 17a and 17b for the channel 17. The channels are connected via a line system 18 to the inlet of an anisage pump 19, via the outlet to the lower part of a refractory material (Raschigingen). filled V.'aschturms 20 is connected.

The illustrated apparatus further comprises two thermostated agitator tanks 21 and 22, of which the first liquid tin chloride SnCl. and the second contains methanol, two flow meters 23 and 24 each having a flow control valve 23a and 24a fed with a mixture of nitrogen and hydrogen in a variable ratio of 20:80 to 80:20,

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while two valves 25 and 26 arranged on pipeline systems 27 and 28 connect the flow meters to the agitator vessels mentioned above * Two lines 29 and 30 connect the outlet of the tanks 21 and 22 to the passage 13 and the passages 11 and 12 of the blower 2, d , h, finally with nozzle 5 of this fan, as far as the line 29, and with the nozzles 3 and 4, as far as the line 30 is concerned,

Di © lines 29 and 30 pass through a container E, which is schematically shown by an outline in phantom lines, and the eina heating fluid, includes, for example, Dl, which is suitably held at a constant temperature of about 110 ⁰ C.

The device further comprises a water-containing container 31, wherein the water is pumped according to a measurable flow rate with accuracy by a metering pump 32 and injected into an evaporator 33, which is heated to a temperature above 100 C,

The evaporator 33 wxrd also fed with a mixture of N ₂ / H ₂ in the ratio of 20: 80 to BO: 20 by means of a Rotamessers 34 and with Fluorhydrid Gos by means of a Rotamessers 35 whose tube extension 36 at the output to a point 37 opens, which lies between the pump and the evaporator 33. The device also includes a conduit system 38 for carrying the mixture of water vapor and HF (about 98: 2 to 99: 1), and valves 39 and 40 which enable or control the respective flow rates of HgO / HF and methanol solutions completely exclude one of these.

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The device described above makes it possible, for example, to treat a glass plate with a tin oxide layer having a thickness in the order of 0.5 to 3 μm, at the same time a very good transparency, a relatively low specific electrical resistance, a remarkable adhesion to the glass urd an increased resistance of mechanical nature and gecjer acids has _t

An experimental device of this type, provided with a fan of 50 cm in length, in which the opening of the nozzles 3; and 5 sine widths of 0.1 to 0.1 and 0.2 mm thick, allowed to treat fine glass plate of 50 cm width and 4 mm thickness, which was heated to about 600 ⁰ C and at a speed of 2 m / min in the direction F {Fig, i and 2) was taken. The distance separating the bottom of the fan and the glass surface was 4 mm

There were containers with a capacity of about one liter of SnCl. used for the container 21 and a liter of H ₀ O for the container 31. The container 2i was heated to a suitable temperature, that is, at a flow rate of carrier gas Ν _? / Η _? of 60 l / h for the container 21 and 120 l / h for the evaporator 33 with a flow rate of the pump 32 of one mole of I-LO per hour, a flow rate of 2 mol / h Zinnchlcrid received. Moreover, the temperature of the blower cJurch Olzirkulation in the channels ІДа and 14b thereof _(Fig's 2) was maintained at a value of about 110 ⁰ C.

Due to the nozzles 3; 4 and 5 of the blower 2 given profile, in particular due to the fact that with

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When they converge towards a common line L, the gaseous streams emerging from these mouthpieces, ie, the stream of SnCl. with respect to the nozzle 5 and the flow of water vapor with respect to the laminar nozzles 3 and 4 in mutual contact, by touching each other slightly laterally and then always immediately as they approach the aforementioned line L. The combined flow of these three gaseous streams becomes less and less laminar as these flows into one another. However, this actually takes place only very close to the surface of the glass V, which is heated to about 600 ⁰ C as described above, so that the combination reaction

SnCl ₄ + 2 H ₂ O> SnO ₂ + 4 HCl

"It should be noted that if no special precautions were taken, this reaction would be very vigorous, producing a large amount of tin oxide SnO ₂ and hydroxides of the SnO ₀ " nH _o 0 type at the exit of nozzles 5 to 5 of the Blower 2 would take place, which would entail the risk of partially or completely clogging the nozzles to deposit the same tin oxides on the glass in the form of a white veil and not in the form of the desired semiconductive transparent layer.

With the described device, this risk has been eliminated by using two gaseous streams of SnCl. and steam was added with a reducing agent in the form of Hp trapped in the carrier gas. The hydrogen is actually a reducing gas to the SnCl, is a hydrolysis moderator and also acts as a catalyst,

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The combination reaction of SnCl. and ЬЦО does not take place only in the middle area of the blower 2, i. h, near the part of this fan in which the nozzles 3; 4 and 5 open. This reaction takes place while the pump 19 is acting so that through the channels 16 and 17 arranged on both sides of the fan at the right and left ends in the drawing in the space between the crack plate V and the underside of the profiles 6a and 6b of the Blower creates a negative pressure. For this reason, a gaseous water vapor flows from the central part of this space to the already mentioned channels 16 and 17. This stream mainly contains a part SnO. and HO ₁ which are dispersed in the carrier gos and have not yet reacted, the HCl vapors already formed and a certain amount of carrier gas freed from the reactants which have already reacted "The reaction between SnO" and t-UO may be c ^. So continue to take place with the remaining reaction gases over a certain length on both sides of the line L of the convergence of the nozzles.

The suction force realized by means of the channels 16 and 17 is chosen so that the reaction gases emitted by the fan in this space are maintained only during the time strictly necessary to achieve deposition of SnO "on the glass, a deposit, which takes the form of a transparent layer and not in the form of a powdery increase in SnOp. Of course, the suction should not be too strong, because otherwise the emitted from the fan reaction gases would not have time to reach the surface of the glass. The intensity of the suction force is therefore decisive for the quality and the speed

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the growth of the layer. It should also be emphasized that, thanks to this suction, in some way the space between the fan and the glass plate is isolated from the ambient atmosphere, a space in which the desired reaction takes place, thus preventing on the one hand any possible entry of additional Moisture in that space which could affect the combination reaction, and on the other hand any escape of harmful vapors, for example HCl or hydrogen, into this ambient atmosphere, the ambient atmosphere tending to flow to the slots 16a and 16b υζιν, 17a and 17b, by passing between the channel 16 and the channel 17 of the glass plate V and the blast 2.

The sucked with the pump 19 gaseous products are, as described, passed to the scrubbing tower 20, that the volatile residual acids of a filtering and entrainment

are subjected to water, whereby the resulting acid solution is separated from the washed gases and removed through the conduit 20a.

Under the above operating conditions concerning-jg the reaction yield about 70% _t smoothing do was on its entire surface with a SnO ^ layer of _О г 5-3 дш thickness, a review of jkeit before 60 to 95% corresponding to the patterns and an average Conductivity of R ₀ = 1 to 1С-L, preferably 2 bia 5 Sx- covered at a thickness of 1 to 2 ^ m.

In addition, it has been found that the SnOp layer obtained in this way had a particularly high hardness.

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which was above the glass to which it was applied. Therefore, their resistance was extremely significant both in relation to the most intense mechanical stresses, such as shock, alo also against attacks by acids, "this glass could be subjected in particular a Bombageverfahren with a radius of curvature of ± 5 cm, having brought it to a temperature between GOO and 700 ⁰ C. without any damage to the SnOo layer. It was also possible to cure under standard glass glass conditions, d, h, to cool it from 700 C at a rate of several degrees per minute. Finally, it should be noted that a glass plate coated with a SnG ₉ layer can be cut with a diamond under the conditions and modalities described by attacking the front or back of the plate without peeling off the coating.

With the same device and under working conditions different from those described only with regard to the; Speed of entrainment of the glass plate V differ _f this speed was increased to about 10 m / min, we obtained a SnO ₉ -AbIage tion with a thickness of about 0D ^ m, an average conductivity of R ₀ = 500 j "i- , a transparency of almost 100 % for the visible radiation and mechanical properties practically equal to those obtained by taking the glass plate at a speed of 2 m / min.

The immediate addition of H ₀ to mitigate the combination reaction of SnCl. and water vapor is not the only measure. According to a modification of

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To carry out the process according to the invention, it is necessary to use a carrier gas consisting exclusively of nitrogen and to generate the hydrogen required for the reaction in situ from a volatile, hydrocompatible solvent, such as Nethanol CH OH. In such a case, reference is made to the contribution of the agitator vessel 22, wherein the methanol is entrained by N_ alone in accordance with a flow rate controllable by the valve 40. In this case, the carrier gas passing through the evaporator 33 is also N _? ,

In view of the relatively high temperature at the outlet of the nozzles, the methanol can decompose the following reaction:

CILOII ? 2 M ₂ + CO

Ee can also be used with H "0 according to the reaction

CH ₃ OH + H ₂

react.

In the same way as in the other case, in sit'U one experiences a production of dos for the control of the essential reaction of orfordoric hydrogen already described:

GnCl ₄ + 2 H ₂ O-j, SnO ₂ + 4 HCl

It should be noted that dd ^r ; The search did not allow to determine which of the two above-mentioned reactions to CH OH is preferable. It has already been noted that, under the conditions described below,

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In fact, the introduction of the methanol into the deposition process of the desired SnOp requirement made it possible to control this process in the same manner as in the case of using hydrogen mixed with nitrogen as a carrier gas (Figure 1). If desired, it is also possible to use the mixture Ng / hL at the same time in order to take along water and HF and methanol diluted by Np, the corresponding flow rates of the solutions being controlled by the valves 39 and 40 *.

With the present pilot device and in the presence of Ch OH a glass plate of 20 cm width, covered with a transparent deposit of SnO _? to obtain, was through each of the two containers 21 and 22, a flow rate of about SO l / h nitrogen run tm, wherein the flow rates were regulated by acting on the valves 23 a and 24 a, with which the flow meter 23 and were provided, and 60 l / h N ^ in the evaporator 33, the pump 32 2 mol H _? 0 per hour delivered. The containers were brought to appropriate temperatures so that their respective fluxes of reshaping agent would be 1 mole per hour of SnCl ₄ and 0.5 moles per hour of CH ₃ OH. Di {,> temperature of the fan that was "maintained by oil circulation, was as before 110 ⁰ C, while cio glass plate to a temperature of about 600 ⁰ C vorg ^ was eizt. The glass was taken at a speed of 2 m / min in the direction F, keeping it at a distance from the bottom of profiles 6a and 6b of the blower. "

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The SnCU coating obtained has been found to be virtually identical to the above-described methanol-free coating in terms of thickness, quality and mechanical, electrical or physical properties.

It should be noted that one can perform the present invention perfectly without making use of the gaseous HF. In this case, the coating has electrical and reflectance properties in the IR corresponding to those of the coatings obtained in the presence of HF, but it may happen that the thus coated glass has a somewhat less clear appearance and is less smooth than when working in the presence of HF.

When operating in the presence of this gas, one can also use daa HF directly in aqueous solution in the vessel which serves to deliver the water vapor for the reaction. As a ratio, 0.1 to 5% by weight of HF can be used in the water. A glass with a thickness of 4 mm, which was brought to a Tamperatur of about 600 ⁰ C, was covered with a layer of 0.9 m ^ SnO "treated in HF by passing by in front of the blower at a speed of 2 m / min and at a distance of about 6 mm from this. The flow rates of carrier gas (a mixture of 40 % N 2 and 60 % H _Q ) lagan at 60 l / h for the SnCl and the water vapor,

The SnO 2 deposit obtained in the presence of HF according to the present invention is particularly effective. In the case described above, it was more specific

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Line resistance R ₀ = 4 .Λ-, and its reflectivity to infrared was on the order of 74%,

In addition, their transparency to visible light was 90 %, with their surface being particularly smooth and not causing diffusion of the light (no milky appearance).

The mechanical resistance properties were also very high: The coated glass thus treated with SnOp? N HF could endure a thermal treatment for curing corresponding to those which are usually subjected to certain vehicle windows, for example the side windows of automobiles. It was also possible »to bump such a plate under heat with radii of curvature of 15 cm (temperature about 650 ⁰ C), without affecting the properties of the HF-treated SnO ₂ coating. In addition, a glass plate coated in the manner described could be treated in the usual manner (cutting, grinding, etc.) without damaging the deposit.

The HF treated SnO 2 coating had a hardness higher than that of the supporting glass and could not be scratched; In addition, their chemical resistance to acids and their resistance to impact proved to be particularly hc.n. Incidentally, such a glass is completely resistant to curing, according to which it is cooled from 700 C at a rate of 5 to 10 ⁰ C per second.

It is also noted that a HF-treated coating applied to a glass plate under the

16.12.1930 AP H 01 L / 222 969 222969 -24- 57 839/18

deposited silver or a silver paint "deposited at 600 ^° C", for example, to form electrical contacts * Such deposition of silver adheres very well to the surface of the SnO ₂ deposit at about 15 kg / sec. cm ² .

With the present device and operating conditions differing from those described above only insofar as the speed of entrainment of plate V is concerned, with this speed increased to about 10 m / min, an HF-treated SnO _{2 was obtained} Deposit, which has a thickness of about 1 nm, a mean conductivity of Ra * -200 «a transparency of almost 100 % for visible radiation, a reflection power for infrared of 25 % and mechanical properties corresponding to those, Uie with the also treated with HP treated SnO ^ deposit was obtained by taking the glass plate at a speed of 2 m / min «

The uses of glass plates of all sizes, which are covered with layer зіпег SnO ₂ were Urd treated with HF or without, can according to their performance, and in particular physical electrical nature erhwb- 1 \ c \\ be modified.

obtained according to the present invention, with

? ^{к г 5Су} "layer coated glass plate, for example, VJU ^ 'be iilet * to Insulating for window or Ре ^ с * ^ * - ^^""- of apartments" of ships or WOULD CHOOSE hither "ste -. ·' · ο-uv »d though due to their high transparency for

16.12.1980 AP H 01 L / 222 969 222969- 25- 57 839 / 3.8

visible light, its weak radiation power and its relatively high reflectivity for infrared. Such a plate has a sufficiently large athermal force (K = 2, 3) to reduce, to a sufficiently great extent, the amount of heat-generating radiation which can pass through this plate. Such discs advantageously replace the classical double-windows in proportion more expensive and more fragile are »

It is possible to use SnOp-coated glasses which are treated as heating disks or not, for example as rear windows of motor vehicles. In addition, as far as other carriage covers are concerned, the disks according to the invention are also suitable because of their excellent reflectivity for IR contribute to improve the efficiency of air conditioning of the vehicle.

It could be observed that a glass plate with SnO "coating used in an atmosphere of very substantial humidity did not cover with a uniform condensation layer, but rather with a plurality of droplets covering the visibility capacity by the deposit as such and the Glass plate changed considerably less.

This property is obviously particularly advantageous in the case of glass plates which are to form panes, in particular of vehicle windows * and more particularly windscreens and rear windows of motor vehicles, buses or trucks.

16L2.1980 AP H Ol L / 222 969 222969 - 26 - 57 839/18

It should be noted that the slices according to the invention can be advantageously used in horticulture (production of greenhouse slices or cold covers),

It should be noted that the present process can be repeated on a given substrate as desired, such that a combined coating of various successive layers is formed, the composition of which need not be equal. If desired, an uncoated SnO 2 layer may be coated with a second HF treated layer. Similarly, one can make a coating of 1 nm through ten successive layers of 100 nm each, wherein the optical and electrical properties of each layer need not necessarily be the same.

It will be understood that for a given flow rate of coagulant, the thickness of a capping layer depends on the rate of passage of the substrate. Under these conditions, if desired, the reaction items can be multiplied by placing two or more coating devices such as those shown in the drawing built next to each other. In this way, a second layer is deposited on the first one before it has the time to cool off and so on, resulting in a particularly homogeneous overall coating.

Although in the foregoing description to Auöt, ¹ runge "forms of entities respect wurda taken in which is to be covered with a SNOG-Sehicht glass plates are always arranged at a distance from the fan, corresponding to that of this fan and the convergence

222969- 27

16.12,1980

AP H 01 L / 222 969

57 839/18

In practice, this edge can be slightly reduced so that the mixture of reactant ejected from these nozzles hits a relative local swirling motion on the glass which favors this mixture.

The following example shows the differences that result when using SnO ₂ on эіпег glass plate in the presence and in the absence of hydrogen »

The device shown in Fig _s 1 without using the methanol agitators One used, the valve was closed 40th It was performed under the following conditions:

Reaction temperature working pressure

Flow rate of the pump 32nd

HF concentration in H ₂ O composition of the carrier gas

Temperature of the evaporator 33 Flow rate of gas in the container 21st

Temperature of? Container 21 Flow rate at SnCl Running speed of the glass V Suction rate of the reaction gas Overage amount of carrier gas in the evaporator 33

590 ⁰ G

Ambient pressure 10 mol HUO / h Cb 250 l / h Steam 2/98 (vol / vol) Н ^ / ЬЦ 40/60 (vol / vol) 140 ⁰ C

370 l / h 90 ⁰ C 10 mcl / h i, k m / min 1,500 l / h 500 l / h

16.12.1980 AP H 01 L / 222 222969 "28" 57 839/18

In this way, a deposit was obtained with the following properties:

Thickness: 0.6 ,around Resistance _: Ro = 20. Transparency: 80 <V / a

Then the methanol Hp / N "(carrier gas) was replaced by nitrogen alone and under the same operating conditions it was given a coating with the following properties:

Thickness: 0.7 pm

Resistance: R ₀ = 1.000 Λ Transparency: 80 %

When the above-mentioned working conditions approximately moliot the molar ratios of H _g 48 HgO molf 26 ^ and SnCl corresponded ₄ 26 molfb, it was calculated thermodynamically the ratios of the reactants and reaction products at equilibrium at 500 and 600 ⁰ C and at normal pressure, and found the following Values:

ingredients With hydrogen without hydrogen (Тоій) 500 ° C 600 ⁰ C 500 ° C 600 ⁰ C HCl 43.7 43.8 64.17 67.26 H ₂ 40.66 40.6 - H ₂ O 15.6 15.6 9.91 8.37 SnCl ₂ (g) 13.1 21.9 0.0 SnCl ₂ (S) 8.7 0.0 0.0 0.0 SnCl ₄ 0.06 0 _v 02 41.45 41.17 SnO ₂ 0.0 0.0 16.1 16.8

HpO 42 mol%, SnCl. 58 mol% (starting composition)

16.12.1980 AP H 01 L / 222 969 222969- 29- 57 839/18

It is typical that at equilibrium the reaction carried out in the presence of H _{2 gave} no SnO ₂ and little SnCl 2. It is therefore understandable that under the irreversible working conditions a considerable reduction of the Stanni compounds on Stanno compounds was observed e. 'ner forms a significant increase in the conductivity of the deposits,

Example 2 File of a multiple description;

A coating device having a group of five fans of 1 m in parallel was arranged in cascade form, each of which generally corresponded to the description given above. The intake ducts for emptying the exhaust gases were arranged so that each fan was surrounded by a channel, as shown in the drawing (15; 17), The blowers were fed iHt reactants, ι as described above, with the difference that the four first Blowers were fed together in relation to HpO, and the last blower separated with a 50% solution HF / H "O. The central nozzles of the five blowers were used together with SnCl. fed "

It was worked under the following conditions:

Reaction temperature: 590 ^° C

Pressure: ambient pressure

Flow rate of the water pump:

(a single one for the first four

Blower): 80 mol / h

Flow rate of the pump for water

+ HF (five times the solution): 20 mol / n

222 S6 9

«- 30 -

Composition of the mixture f-UO / HF;

Composition of the carrier gas

(together for the five blowers):

Total flow rate of carrier gas

for water in the first four blowers;

Flow rate of inert gas for

Water + HF:

Temperature of the evaporator;

Flow rate of carrier gas in

the SnCl. container;

Temperature of the SnCl 2 container:

Flow rate of SnCl.

Gesamtansaugmenge

Shifting speed of the glass:

In this way, a coating was obtained with five superimposed layers of 0.1 1 m ₁₁ each, with only the last being treated with fluorine. This coating had the following properties:

16 .12.1980 500 l / h ΛΡ h 01 L / 222 969 ⁰ C 57 839/18 mol / h 98 : 2 (mol / mol) m ³ / h H ₂ / N ₂ 50:50 (vol / vol) m / min 7th 000 l / h 1. 800 l / h 140 ⁰ C 3, 90 50 15 10

Ra = 20 yes

IR Reflectance «55 % Transparency = 85 %

Claims (12)

Inventions пер г и с j ι 1 »Process for depositing an adhesive layer of tin oxide with a lower than 10 ~ IL . cm lying specific
Line resistance on a substrate of glass, ceramic or other mineral substance, after which on the surface of the previously preheated to at least 500 ⁰ C substrate from a volatile compound
in a carrier gas diluted tin and water vapor
reacts, characterized in that this gas
contains at least 30 % hydrogen. Method according to item 1 for producing a laminar, electrically conductive article, characterized by
that its tin oxide coating at thicknesses of 1 to
3 / Jm the following features:
Surfaces; ', iderstand = 1 to 10L
Transparency = 60 to 95 IR 'reflectivity "Ъ 50 %, tv, 0 3, method according to item 1, characterized in that the hydrogen acts as a reducing agent for the reactants or the reaction product. 4. The method according to item 3, characterized in that the hydrogen also acts as a reaction moderator. 5. The method according to item 1, characterized in that the hydrogen is generated on contact with the substrate by thermal decomposition of a dilute in the carrier gas hydrogen-containing compound. .16.12,1980
AP H 01 L / 222 969
222969 "32-57 839/18 6. The method according to item 5, characterized daduich that the hydrogen-containing compound is methanol. 7. The method according to item 1, characterized in that one adds to the mixture gas from the reaction of the hydrogen fluoride, wherein the treatment with this component
the effect is that the parasitic dispersion of the
Light in the SnOg coating is reduced, 8. The method according to item 7, characterized in that the hydrogen fluoride gas is supplied in admixture with water in the ratio of 0.1 to 5 parts by weight Jo, 9. The method according to item 1, characterized in that after receiving a first SnOp coating, the deposition process is repeated a second or more times in succession, in which case the resulting coating consists of zv egg or more stacked Zinnoxidschicbten. 10, method according to item 9, characterized in that the thickness of each of the elementary layers is between 10
and 500 nm. 11. Laminar, electrically conductive article from a
Substrate made of glass, corundum or another mineral material »that with an adhesive layer of tin oxide
coated, characterized in that the coating at thicknesses of 1 to 3, to the following
Features: Surface resistance R _ß - ι to 10.ru
Transparency = 60 to 95 % IR reflectance >, 50; ό. 16.12.1980 AP H 01 L / 222 969 222969_zs_ 57 839/18 12. Electrically conductive article according to item 11, in the preparation of which one for the deposition of the adhesive layer of tin oxide on the surface of previously heated to 550 to 650 ⁰ C substrate reacts a volatile compound diluted in a carrier gas tin and water vapor, characterized in that this gas contains at least 30 % hydrogen. о Lead article of item 11, characterized in that d: e coating undergoes no substantial change when subjecting the article to curing, in which he starting cooled from "ingefähr 700 ⁰ C at a rate of 5 to 10 ° C / s becomes, 14. The conductive article of item 13, characterized in that the SnOp coating has such extensibility that when the article is subjected to bending under the action of heat, the radius of curvature of the article thus bent can reach about 15 cm without substantially changing the coating. 15. Conductive article according to item 11, characterized in that for thicknesses of the coating between 1 to 3 jam, the resistance R _{0 is of} the order of 2 to 5 <Ί 16. Leitendor article according to item 11, characterized in that the substrate is a glass sheet of 1 to 15 mm thickness. 1/. Conductive article according to item 16, characterized in that the substrate is a "float" glass ribbon of 2 to 7.4 mm thickness. For this .... ALSeiten Drawings