发明背景Background of the invention
本发明涉及采用氧化铟进行热解涂镀的方法，还涉及使用该方法涂镀的玻璃。The present invention relates to a method of pyrolytic coating with indium oxide and to glass coated by this method.
玻璃上的氧化铟涂层，特别是掺杂的氧化铟涂层(如掺杂有氟或锡的氧化铟涂层)是公知的可见光透射性较高且导电性优良的涂层。通过反应溅射法沉积的锡掺杂氧化铟涂层被广泛地用作可加热涂层，例如用于飞机挡风玻璃，另外，已提出采用掺杂的氧化铟涂层经抛光作为建筑玻璃上的低发射性(红外反射)涂层以控制热损失。Indium oxide coatings on glass, especially doped indium oxide coatings (such as indium oxide coatings doped with fluorine or tin) are well-known coatings with high visible light transmittance and excellent electrical conductivity. Tin-doped indium oxide coatings deposited by reactive sputtering are widely used as heatable coatings, e.g. Low emissivity (infrared reflective) coating to control heat loss.
通过反应溅射法在玻璃上沉积掺杂锡的氧化铟涂层是公知技术，希望采用工业化应用方法在大气压下于热玻璃上沉积这种热解涂层。因而不仅需要避免在低压下操作，而且如果能以高速度沉积，则这种方法也可用于玻璃生产线上的热玻璃，从而涂镀过程可以连续操作而非间歇操作。Deposition of tin-doped indium oxide coatings on glass by reactive sputtering is a known technique and it is desired to employ industrially applicable methods for depositing such pyrolytic coatings on hot glass at atmospheric pressure. Thus not only does it need to avoid operating at low pressures, but if it can be deposited at high speeds, the method can also be used on hot glass on a glass production line so that the coating process can be operated continuously rather than batchwise.
U．S．4，286，009涉及一种用作太阳热收集器的吸收表面的复合涂层。该复合涂层的两层均是金属氧化物，主要是锡、锑、铟和铁的氧化物。通过将氯化铟(InCl3)和氯化锡(SnCl4)的乙酸乙酯溶液喷射至650℃的热玻璃上而沉积掺杂氧化锡的氧化铟涂层。U． S． 4,286,009 relates to a composite coating for use as the absorbing surface of a solar heat collector. Both layers of the composite coating are metal oxides, mainly oxides of tin, antimony, indium and iron. Indium oxide coatings doped with tin oxide were deposited by spraying an ethyl acetate solution of indium chloride (InCl3 ) and tin chloride (SnCl4 ) onto hot glass at 650°C.
EP 0 027，403B1涉及一种在热玻璃表面上沉积氧化锡或氧化铟的导电膜的方法，该方法包括使热表面与锡或铟化合物的蒸气接触；特别涉及使用气态的有机氟代化合物，将其加热，与催化剂接触，然后与铟或锡的氧化物的蒸气一起与玻璃接触以在形成的氧化铟或氧化锡涂层中引入氟掺杂剂。通常，涂镀过程优选在超过400℃的玻璃温度下进行，在具实例中，将包含二氯化二甲基锡((CH3)2SnCl2)和二氯二氟甲烷(CCl2F2)的气态混合物施加至550℃的热玻璃上以在玻璃上沉积掺杂氟的氧化锡涂层。EP 0 027,403 B1 relates to a method for depositing a conductive film of tin oxide or indium oxide on a hot glass surface, the method comprising bringing the hot surface into contact with a vapor of a tin or indium compound; in particular to the use of gaseous organic fluorinated compounds, It is heated, contacted with a catalyst, and then contacted with a vapor of indium or tin oxide to introduce a fluorine dopant in the resulting indium oxide or tin oxide coating. In general, the coating process is preferably carried out at glass temperatures in excess of 400°C, and in one example would include dimethyltin dichloride ((CH3 )2 SnCl2 ) and dichlorodifluoromethane (CCl2 F2 ) was applied to hot glass at 550°C to deposit a fluorine-doped tin oxide coating on the glass.
EP 0 192，009A2涉及在热玻璃上形成氧化铟涂层的方法，特别涉及包括如下方法，其中当其排出浮动浴出口处时将氧化铟的前体施加至热的浮动玻璃条板上，例如在玻璃温度为600℃时。优选使用溶液形式的铟化合物，特别是其乙酰丙酮酸盐，同时已表明，当这些化合物以粉末形式使用时是不能令人满意的。已提出使用溶液形式或粉末形式的甲酸铟，In(HCOO)3。EP 0 192,009 A2 relates to a method for forming an indium oxide coating on hot glass, and in particular involves a method in which a precursor of indium oxide is applied to a hot floating glass strip as it exits the outlet of the floating bath, e.g. When the glass temperature is 600°C. Preference is given to using indium compounds in solution form, especially their acetylacetonate salts, while it has been shown that these compounds are unsatisfactory when used in powder form. It has been proposed to use indium formate, In(HCOO)3 , in solution or powder form.
EP 0 489，621A1涉及在玻璃基质上形成氧化铝与另一种氧化物组合的涂层的方法，所说的另一种氧化物可为氧化锌、氧化锡、氧化钛或氧化铟。该涂层能在玻璃底材与低发射和／或导电覆盖层间形成中间涂层(一种抗虹彩涂层)。该涂层是通过将粉末形式的金属化合物在热玻璃表面上热解而形成的，其提出了使用粉末形式的乙酰基丙酮酸铟或甲酸铟作为氧化铟源。EP 0 489,621 A1 relates to a method for forming a coating of aluminum oxide in combination with another oxide, which may be zinc oxide, tin oxide, titanium oxide or indium oxide, on a glass substrate. The coating can form an intermediate coating (an anti-iridescence coating) between the glass substrate and the low-emission and/or conductive cover layer. The coating is formed by pyrolyzing a metal compound in powder form on a hot glass surface, which proposes the use of indium acetylacetonate or indium formate in powder form as a source of indium oxide.
EP 0 503，382A1涉及一种在玻璃基质上形成掺杂的氧化铟涂层的化学气相沉积方法。在所述方法中，铟源和氧化性气体的分开的层流暂时通过中间的惰性气体物液隔开，将上述层流与加热的底材(可为玻璃)一起通过化学反应室。铟源能吸附至被加热底材的表面，且惰性气体的中间体物流能控制氧化性气体通过后与吸附层作用而形成氧化铟的速度。可用作气相形式作为铟源的化合物的实例为三甲基铟和三甲基铟乙基乙醚配合物。EP 0 503,382 A1 relates to a chemical vapor deposition process for forming doped indium oxide coatings on glass substrates. In the method, separate laminar flows of an indium source and an oxidizing gas, temporarily separated by an intermediate inert gas liquid, are passed through a chemical reaction chamber together with a heated substrate (which may be glass). The indium source can be adsorbed on the surface of the heated substrate, and the intermediate flow of the inert gas can control the speed at which the oxidizing gas passes through and interacts with the adsorption layer to form indium oxide. Examples of compounds which can be used in gas phase form as indium sources are trimethylindium and trimethylindium ethyl etherate.
尽管人们试图在玻璃生产过程中通过在大气压下在热玻璃上的沉积来制备工业化掺杂的氧化铟涂层，但仍然未找到以此种方式如何进行氧化铟的工业化生产。Although attempts have been made to produce doped indium oxide coatings industrially by deposition on hot glass at atmospheric pressure during glass production, it has not been found out how to produce indium oxide industrially in this way.
业已发现，对于这种工业上可接受的“在线”方法而言，其突出优点是使用了化学气相沉积法；其优点还在于，由于以供应的铟前体的数量为基准，可实现涂层的高收率。因而，预混蒸气可包含准备供给热玻璃的铟源和氧源。It has been found that a significant advantage of this industrially acceptable "in-line" method is the use of chemical vapor deposition; it is also advantageous that coating high yield. Thus, the premixed vapor may contain a source of indium and a source of oxygen ready to be supplied to the hot glass.
按照本发明的一个方面，本发明提供了一种将氧化铟涂层涂镀在平板玻璃上的方法，该方法包括：使铟化合物与氧源的气态混合物射向热的玻璃表面，从而使铟化合物分解，在热玻璃表面上形成氧化铟涂层。According to one aspect of the present invention, there is provided a method of applying an indium oxide coating to flat glass, the method comprising: directing a gaseous mixture of an indium compound and an oxygen source onto a heated glass surface, thereby causing the indium The compound decomposes, forming a coating of indium oxide on the hot glass surface.
进而发现，二烷基铟化合物特别适于用作该方法中氧化铟的前体，以用于通过化学气相沉积法将氧化铟涂层涂镀至热玻璃上。It has further been found that dialkylindium compounds are particularly suitable as precursors for indium oxide in the process for applying an indium oxide coating onto hot glass by chemical vapor deposition.
按照本发明的另一个方面，本发明提供了一种将氧化铟涂层涂镀至平板玻璃的方法，该方法包括：在氧源存在下，将气态的二烷基铟化合物射向热玻璃表面，从而使铟化合物分解，在热玻璃表面上形成氧化铟涂层。虽然不是必要的，但优选在射向热玻璃表面之前使二烷基铟化合物与氧源预混合。According to another aspect of the invention, the invention provides a method of applying an indium oxide coating to flat glass, the method comprising: directing a gaseous dialkylindium compound onto a hot glass surface in the presence of an oxygen source , so that the indium compound decomposes to form an indium oxide coating on the hot glass surface. Although not essential, it is preferred to premix the dialkylindium compound with the oxygen source prior to firing onto the hot glass surface.
当在射向玻璃表面之前使铟化合物与氧源预混合时，优选将混合物在层流条件下射向热玻璃表面。When the indium compound is premixed with the oxygen source prior to being directed onto the glass surface, it is preferred to direct the mixture under laminar flow conditions against the hot glass surface.
以供给铟前体量而言，本发明的方法(特别是涉及应用在层流条件下铟前体化合物和氧源的预形成气态混合物的方法)能够使氧化铟涂层收率高。由于铟价格较贵，这一优点非常重要。The method of the invention (in particular the method involving the use of a preformed gaseous mixture of an indium precursor compound and an oxygen source under laminar flow conditions) enables high yields of indium oxide coatings in terms of the amount of indium precursor supplied. This advantage is very important since indium is relatively expensive.
按照本发明优选的实施方案，本发明提供了在稳态操作条件下，在形成的氧化铟涂层中引入作为前体供应的至少30％的铟，在特别优选的实施方案中，所述数值超过35％。According to a preferred embodiment of the invention, the invention provides for the incorporation of at least 30% of indium supplied as a precursor in the formed indium oxide coating under steady-state operating conditions, in a particularly preferred embodiment, said value More than 35%.
为了达到优良的导电性和／或低发射性(即高红外反射性)，优选氧化铟是被掺杂的。优选使用锡为掺杂剂，这是因为氧化锡在氧化铟中具有很高的溶解性，能够使载流子浓度增高。因此，优选采用气体形式的锡化合物与铟化合物结合使用，以在热玻璃表面上形成掺杂锡的氧化铟涂层。优选锡化合物与铟化合物预混合，将锡和铟化合物的气态混合物射向热玻璃表面。In order to achieve good electrical conductivity and/or low emissivity (ie high infrared reflectivity), indium oxide is preferably doped. It is preferable to use tin as the dopant, because tin oxide has a high solubility in indium oxide, which can increase the carrier concentration. Therefore, it is preferred to use a tin compound in gaseous form in combination with an indium compound to form a tin-doped indium oxide coating on the hot glass surface. Preferably the tin compound is premixed with the indium compound and the gaseous mixture of tin and indium compound is directed towards the hot glass surface.
当然，也可以使用其它掺杂剂。例如，氟源也可掺于气体中而射向热玻璃表面以形成氟掺杂的氧化铟涂层。在含铟化合物的反应物气体中可包括分开的氟源，例如氟化氢或其中卤素包括氟的卤代烷烃，或者含氟的铟化合物如三氟乙酰丙酮酸铟可同时用作铟源和氟源。Of course, other dopants may also be used. For example, a fluorine source can also be doped in a gas directed at a hot glass surface to form a fluorine-doped indium oxide coating. A separate fluorine source may be included in the indium-containing compound reactant gas, such as hydrogen fluoride or a haloalkane in which the halogen comprises fluorine, or a fluorine-containing indium compound such as indium trifluoroacetylacetonate may serve as both the indium source and the fluorine source.
涂层可在玻璃生产过程中涂镀于热玻璃条板上。如果涂层被涂镀于浮动浴中的浮动玻璃上，可实现沉积的高速度(因为玻璃高温)，并且由于玻璃仍然足够热，无需再加热玻璃即可通过热解法(优选气相沉积法)涂镀一层或多层覆盖层。氧化铟涂层可在热玻璃表面上直接形成，或者在以前形成的一层或多层涂层的上面形成，例如预先沉积于玻璃上的碳氧化硅层，抑制氧化铟涂层可能会产生的虹彩现象，和／或保护涂层以防止碱金属离子从玻璃迁移进入涂层的有害作用。Coatings can be applied to hot glass strips during glass production. If the coating is applied to floating glass in a floating bath, a high rate of deposition can be achieved (due to the high temperature of the glass) and since the glass is still hot enough to pass pyrolysis (preferably vapor deposition) without reheating the glass Apply one or more overlays. The indium oxide coating can be formed directly on the hot glass surface or on top of a previously formed coating or layers, such as a silicon oxycarbide layer pre-deposited on the glass, to suppress the Iridescence, and/or protective coatings to prevent the deleterious effect of alkali metal ions migrating from the glass into the coating.
通过下述实施例说明本发明，但它们并不构成对本发明的限定。除非另有说明，本文中所有的份数和百分数均指重量，气体体积和流量均是在1大气压及室温(通常为15-20℃)下测量的。氮气和氧气均由BOC供应，氮气为“white spot”级或“boil off”级。在实施例中，涂层被涂镀于移动的玻璃条板上，气体体积和流量(和任何其它所用试剂量)均以涂镀的玻璃每米宽度为基准。转化率是以铟为基准，是用氧化铟涂层中掺入的铟量除以铟的供应量，结果用百分数表示。铟在膜中的量(及其掺入量)是由氧化铟涂层的尺寸计算的，假设涂层完全是氧化铟组成，氧化铟的密度为7．18g／cm3。The invention is illustrated by the following examples, but they are not intended to limit the invention. Unless otherwise indicated, all parts and percentages herein are by weight, and gas volumes and flows are measured at 1 atmosphere and room temperature (typically 15-20°C). Both nitrogen and oxygen are supplied by the BOC, with nitrogen either "white spot" or "boil off" grade. In embodiments where the coating is applied to a moving strip of glass, the gas volumes and flows (and any other reagents used) are based on the width of the coated glass per meter. The conversion rate is based on indium, which is the amount of indium doped in the indium oxide coating divided by the supply of indium, and the result is expressed as a percentage. The amount of indium in the film (and its doping amount) is calculated from the size of the indium oxide coating, assuming that the coating is completely composed of indium oxide, and the density of indium oxide is 7.18g/cm3 .
实施例1-7Example 1-7
在这一组实施例中，将铟前体化合物与氧的预形成气态混合物射向4mm清洁的浮动玻璃试样(100mm×200mm)上，所述浮动玻璃安装于玻璃反应器管中的电加热石墨块上。按照EP 0 275，662B所述方法，在玻璃的主要暴露表面上预涂镀一层碳氧化硅底层，其折射率约为1．7。In this set of examples, a preformed gaseous mixture of an indium precursor compound and oxygen was shot onto a 4 mm clean sample of floating glass (100 mm x 200 mm) mounted on an electrically heated on graphite block. The major exposed surfaces of the glass are precoated with a silicon oxycarbide primer layer having a refractive index of about 1.7, as described in EP 0 275,662B.
在实施例1、4和5中，通过所谓反相打泡法(reverse bubbling)将乙酰基丙酮酸(2，4-戊二酮)二甲基铟汽化。将颗粒形式的固体铟化合物置于打泡器中，使氮气通过固体物料上的打泡器。氮气通过颗粒状固体扩散并通过一管道排出打泡器，所述管道的开口端浸在颗粒状固体的表面下面。在整个汽化过程中的各种情形下，铟化合物均被保持在80℃。在表1中示出了在各种情形下通过打泡器的氮气流速。In Examples 1, 4 and 5, dimethylindium acetylacetonate (2,4-pentanedione) was vaporized by so-called reverse bubbling. The solid indium compound in granular form is placed in a bubbler and nitrogen gas is passed through the bubbler over the solid material. Nitrogen diffuses through the granular solids and exits the bubbler through a tube with the open end submerged below the surface of the granular solids. The indium compound was maintained at 80° C. at each instance throughout the vaporization process. In Table 1 the nitrogen flow rate through the bubbler is shown in each case.
在实施例2中，将乙酰基丙酮酸二甲基铟溶解于乙酸正丙酯中，其浓度约为10％，溶液以1-5ml／min的速度被注入200℃的氮气流(3 l／min)中。In Example 2, dimethylindium acetylacetonate was dissolved in n-propyl acetate at a concentration of about 10%, and the solution was injected into a nitrogen stream at 200°C at a rate of 1-5ml/min (3 l/ min).
在实施例3、6和7中，三(四甲基庚二酮)铟(indiumtristetramethylheptanedione)(熔点约为180℃)被保持在200℃的打泡器中，氮气以0．2 l／min的速度鼓泡通过液体铟化合物。In Examples 3, 6 and 7, three (tetramethylheptanedione) indium (indiumtristetramethylheptanedione) (melting point about 180 ° C) was kept in a bubbler at 200 ° C, nitrogen at 0.2 l/min Velocity bubbles through liquid indium compound.
在各种情形下，充有铟化合物蒸气的氮气与其它的氮气和氧气(其供给流速如表1所示)混合，将气态混合物以总流速为约5／6 l／min，在层流条件下，射向热玻璃表面。将石墨块加热至625℃，玻璃温度约低10-15℃。In each case, nitrogen charged with indium compound vapor was mixed with other nitrogen and oxygen (supply flow rate as shown in Table 1), and the gaseous mixture was mixed at a total flow rate of about 5/6 l/min under laminar flow conditions. down, toward the hot glass surface. The graphite block is heated to 625°C, the glass temperature is about 10-15°C lower.
在实施例4-7中，锡掺杂剂与汽化的铟化合物混合，将气态混合物射向热玻璃表面。In Examples 4-7, the tin dopant was mixed with the vaporized indium compound and the gaseous mixture was directed towards the hot glass surface.
在实施例4中，二氯化二甲基锡(0．25g)的乙酸正丁酯溶液以0．75ml／min的速度被注入供给加热的玻璃之前所用的气态混合物中。In Example 4, a solution of dimethyltin dichloride (0.25 g) in n-butyl acetate was injected at a rate of 0.75 ml/min into the gaseous mixture used before feeding the heated glass.
在实施例5中，在30℃下，氮气以1 l／min的速度，鼓泡通过二乙酸二甲基锡。在实施例6中，在30-35℃下，氮气以0．8 l／min的速度，通过二氯化二甲基锡。在实施例7中，在30-35℃下，氮气以0．5 l／min的速度，通过二乙酸二甲基锡。在各种情形下，负载锡掺杂剂的氮气与包含铟的气体在输送至热玻璃表面之前混合。In Example 5, nitrogen gas was bubbled through dimethyltin diacetate at a rate of 1 l/min at 30°C. In Example 6, at 30-35°C, nitrogen gas passed through dimethyltin dichloride at a rate of 0.8 l/min. In Example 7, at 30-35°C, nitrogen gas was passed through dimethyltin diacetate at a rate of 0.5 l/min. In each case, nitrogen laden with tin dopants was mixed with an indium-containing gas prior to delivery to the hot glass surface.
在各种情形下，表中示出了沉积持续的时间。沉积后，使反应器冷却(在氮气流下)，冷却后，取出玻璃并对其检测。在各种情形下，形成了氧化铟涂层。测量涂层的厚度和电阻率，及混浊性(根据ASTM D1003-61测定，1988，使用D65照明剂)，而实施例2、6和7还测量涂镀的玻璃的发射性(根据BS6993，部分1)。结果见表2。在一些情形下，在涂镀表面上氧化铟的厚度有很大的变化；电阻率、混浊性和发射性值是涂层厚度如表2所测量的那些。In each case the duration of deposition is shown in the table. After deposition, the reactor was allowed to cool (under nitrogen flow), and after cooling, the glass was removed and inspected. In each case, an indium oxide coating was formed. The thickness and resistivity of the coating, and the haze (measured according to ASTM D1003-61, 1988, using the D65 illuminant), while Examples 2, 6 and 7 also measure the emissivity of the coated glass (according to BS6993, part 1). The results are shown in Table 2. In some cases, there was a large variation in the thickness of indium oxide on the coated surface; the resistivity, haze and emissivity values were those measured for the coating thickness as in Table 2.
总之，这些实施例显示了在玻璃上用于沉积氧化铟涂层的铟前体的适应能力，它们与用于提供锡掺杂的前体的相容性，以及生产导电、低发射涂层的可能性(特别是当使用掺杂剂时)。Taken together, these examples demonstrate the adaptability of indium precursors for depositing indium oxide coatings on glass, their compatibility with precursors used to provide tin doping, and the ability to produce conductive, low-emission coatings. Possibility (especially when using dopants).
结果表明，实施例2比其它实施例具有显著高的生长速度。其原因假定为，用于铟化合物的汽化方法(液体注射)可增加被汽化的前体数量，导致射向玻璃的涂层气体中铟浓度增加。The results show that Example 2 has a significantly higher growth rate than the other examples. The reason for this is assumed to be that the vaporization method (liquid injection) used for the indium compound increases the amount of precursor vaporized, resulting in an increased concentration of indium in the coating gas directed at the glass.
混浊性数值通常在工业生产可接受的范围内，尽管实施例5中该值大于其它实施例。实施例5中混浊性增加的原因并不十分清楚。如预期的那些，采用锡掺杂剂制备的涂层其片电阻(sheet resistance)和发射性大大降低，且与相应厚度用氟掺杂的氧化锡所得到的数值进行比较较合适。据信，这是由于通过掺杂涂层显示的高载子浓度和离子迁移率。实施例4、6和7涂层中离子迁移率的测量值分别为43．15、45．57和50．42cm2V-1sec-1，而载子浓度的相应值为7．38、6．19和3．42×1026M-3。The turbidity value is generally within the acceptable range for industrial production, although the value in Example 5 is greater than that of other Examples. The reason for the increase in turbidity in Example 5 is not entirely clear. As expected, the sheet resistance and emissivity of the coatings prepared with tin dopants were greatly reduced, and comparisons with the values obtained for corresponding thicknesses of fluorine-doped tin oxide were good. This is believed to be due to the high carrier concentration and ion mobility exhibited by the doped coating. The measured values of ion mobility in the coatings of Examples 4, 6 and 7 are 43.15, 45.57 and 50.42 cm2 V-1 sec-1 , respectively, while the corresponding values of carrier concentration are 7.38, 6 .19 and 3.42×1026 M-3 .
表1
1乙酰基丙酮酸二甲基铟1 Dimethylindium acetylacetonate
2三(四甲基庚二酸)铟2 indium tris(tetramethylpimelate)
3二氯化二甲基锡3 Dimethyltin dichloride
4二乙酸二甲基锡4 Dimethyltin diacetate
表1(续)
1乙酰基丙酮酸二甲基铟1 Dimethylindium acetylacetonate
2三(四甲基庚二酸)铟2 indium tris(tetramethylpimelate)
3二氯化二甲基锡3 Dimethyltin dichloride
4二乙酸二甲基锡4 Dimethyltin diacetate
表2
表2(续)
实施例8-20Example 8-20
下述实施例8-20分别包括在玻璃生产过程中，向热的浮动玻璃条板涂镀氧化铟涂层，其厚度为1．1-4mm，以退火炉速度为150-330m／h移动。The following examples 8-20 respectively consist of applying an indium oxide coating to a hot floating glass strip during the glass production process, with a thickness of 1.1-4 mm, moving at an annealing furnace speed of 150-330 m/h.
在每一种情形下，将包含铟前体化合物和氧气的预形成的气态混合物在层流条件下，射向浮动玻璃浴的表面上方，如UK专利GB1，507，996所述。In each case, a preformed gaseous mixture comprising an indium precursor compound and oxygen is directed under laminar flow conditions over the surface of a floating glass bath, as described in UK Patent GB 1,507,996.
在实施例8-16、19和20中，镀膜机朝向浮动浴的冷却端设置，其中玻璃温度约为625℃。在实施例17和18中，镀膜机位于退火炉中玻璃条板上方，其中玻璃温度约为500℃。In Examples 8-16, 19 and 20, the coater was positioned towards the cool end of the floating bath, where the glass temperature was about 625°C. In Examples 17 and 18, the coater was positioned above the glass slab in an annealing furnace where the glass temperature was about 500°C.
在实施例8中，使氮气以2-12 l／h的速度鼓泡通过超过熔点(即148℃)的铟化合物使乙酰基丙酮酸二甲基铟汽化。乙酸丙酯以180g／min的速度被注入充有铟化合物的氮气中以评价体系对乙酸丙酯(用作实施例9铟化合物的溶剂)存在的容忍度。在实施例9中，溶解于乙酸丙酯的乙酰基丙酮酸二甲基铟的浓度约为10％，该溶液以200g／min的速度被注入氮气负载气体中，其流速为45 l／min，并被加热至约160℃。In Example 8, dimethylindium acetylacetonate was vaporized by bubbling nitrogen gas at a rate of 2-12 l/h through the indium compound above its melting point (ie 148°C). Propyl acetate was injected into the nitrogen filled indium compound at a rate of 180 g/min to evaluate the tolerance of the system to the presence of propyl acetate (used as the solvent for the indium compound in Example 9). In Example 9, the concentration of dimethylindium acetylacetonate dissolved in propyl acetate was about 10%, and the solution was injected into the nitrogen-carrying gas at a rate of 200 g/min at a flow rate of 45 l/min. and heated to about 160°C.
在实施例10中，将三(四甲基庚二酸)铟保持在220-250℃的打泡机中，使氮气以2-8 l／min的速度鼓泡通过液体铟化合物。将乙酸丁酯以100ml／min的速度注入充有铟化合物的氮气中。In Example 10, tris(tetramethylpimelate)indium was kept in a bubbler at 220-250°C, and nitrogen gas was bubbled through the liquid indium compound at a speed of 2-8 l/min. Butyl acetate was injected into nitrogen filled with indium compound at a rate of 100ml/min.
在实施例8、9和10中，使充有铟化合物蒸气的氮气与附加的氮气负载气体和氧气(实施例8和10)或氧气(实施例9)(如表3所述)混合，将气态混合物通入镀膜机中。In Examples 8, 9, and 10, nitrogen charged with indium compound vapor was mixed with additional nitrogen load gas and oxygen (Examples 8 and 10) or oxygen (Example 9) (as described in Table 3), and The gaseous mixture is passed into the coater.
在实施例11-20中，通过直接液体注入系统来汽化铟化合物(氯化二甲基铟、六氟乙酰基丙酮酸二甲基铟或乙酰基丙酮酸二甲基铟的乙酸乙酯溶液)，所述系统可以是：购自Advanced Technology Materials ofBoston，USA，商标名为SPARTA 1505A的系统，或者U．S．专利5，090，985所述的系统。这些系统采用了一种泵系统，它以控制的速度向汽化前体溶液的蒸发器供给前体溶液，通常在恒定速度将负载气体加入；进而，负载气体可以在蒸发后加入以实现所需浓度和流动特性。表3示出了在实施例11-20中采用的具体的铟化合物、传输速度、负载气体和总负载气体流速。包含铟化合物蒸气的负载气体与在某些情形下包含水蒸气和／或氯化氢(见表3)的氧气流混合，再将气态混合物通过镀膜机射向热玻璃。In Examples 11-20, the indium compound (dimethylindium chloride, dimethylindium hexafluoroacetylacetonate, or dimethylindium acetylacetonate in ethyl acetate) was vaporized by direct liquid injection into the system , the system may be: a system purchased from Advanced Technology Materials of Boston, USA, with the trade name SPARTA 1505A, or U. S． The system described in Patent 5,090,985. These systems employ a pump system that supplies the precursor solution at a controlled rate to an evaporator that vaporizes the precursor solution, usually adding the load gas at a constant rate; in turn, the load gas can be added after evaporation to achieve the desired concentration and flow characteristics. Table 3 shows the specific indium compound, delivery speed, load gas, and total load gas flow rate employed in Examples 11-20. A load gas containing indium compound vapor is mixed with an oxygen stream containing in some cases water vapor and/or hydrogen chloride (see Table 3), and the gaseous mixture is directed through the coater onto the hot glass.
在实施例11-15、19和20中，向气态混合物中加入锡掺杂剂。氮气鼓泡通过95℃的液体三氯化正丁基锡或30℃的四甲基锡，其速度显示于表中，使形成的气体与供给镀膜机的氧气混合。In Examples 11-15, 19 and 20, a tin dopant was added to the gaseous mixture. Nitrogen was bubbled through liquid n-butyltin trichloride at 95°C or tetramethyltin at 30°C at the rates shown in the table to mix the gas formed with the oxygen supplied to the coater.
表3
5氯化二甲基铟5 Dimethyl indium chloride
6六氟乙酰基丙酮酸二甲基铟6 Dimethylindium hexafluoroacetylacetonate
7在实施例8和10中，为氮气附加负载气体加上充有铟化合物的氮气体积7 In Examples 8 and 10, additional load gas for nitrogen plus the volume of nitrogen filled with indium compound
表3(续)Table 3 (continued)
5氯化二甲基铟5 Dimethyl indium chloride
6六氟乙酰基丙酮酸二甲基铟6 Dimethylindium hexafluoroacetylacetonate
7在实施例8和10中，是氮气附加负载气体加上充有铟化合物的氮气的体积7 In Examples 8 and 10, is the volume of nitrogen plus load gas plus indium-compound-filled nitrogen
表4
在每种情形下，在玻璃上形成氧化铟涂层。除实施例17和18外，分别对其它实施例中涂层的厚度和电阻进行测量，如前所述，计算涂层的生长速度及前体中铟的转化率。可以理解，由于未考虑涂层中锡掺杂剂的存在，或由于未考虑上述涂层密度值7．18的变化情形，计算的转化率仅能给出近似值(但已表明其足够有用)。In each case, an indium oxide coating was formed on the glass. Except for Examples 17 and 18, the thickness and resistance of the coatings in other examples were measured, and the growth rate of the coating and the conversion rate of indium in the precursor were calculated as described above. It will be appreciated that the calculated conversions are only approximate (but have been shown to be useful enough) because they do not take into account the presence of tin dopants in the coating, or because they do not take into account the variation in the coating density value of 7.18 described above.
所达到的生长速度和转化率(特别是对二烷基铟前体而言)显示出该方法的工业适用性，而测得的涂层片电阻值显示了其电子性能，其可得到较低的发射性，即高红外反射性。The achieved growth rates and conversions (especially for dialkylindium precursors) show the industrial applicability of the method, while the measured coating sheet resistance values show its electronic properties, which can be obtained at lower Emissivity, that is, high infrared reflectivity.
实施例21-23Examples 21-23
这些实施例分别涉及将掺杂锡的氧化铟涂层涂镀至约2．5mm厚的浮动玻璃条板，退火炉的速度为155m／h。在各个实施例中，在层流条件下，使用双物流涂镀机将氦负载气体中的氯化二甲基铟、氧气、水蒸气和氯化氢的预形成气态混合物射向玻璃上，其中使涂镀气体在由来自中心供气管的分开的上游物流和下游物流中流动，所述供气管的方向与玻璃前进的方向相反(类似于国际专利申请WO 96／11802中图3所述的涂层)。The examples each involved the application of tin-doped indium oxide coatings to floating glass strips approximately 2.5 mm thick, at an annealing oven speed of 155 m/h. In various embodiments, a preformed gaseous mixture of dimethylindium chloride, oxygen, water vapor, and hydrogen chloride in a helium load gas is directed onto the glass using a two-stream coater under laminar flow conditions, wherein the coating The coating gas flows in separate upstream and downstream streams from a central gas supply pipe directed opposite to the direction of glass advancement (similar to the coating described in Figure 3 of International Patent Application WO 96/11802) .
涂镀机位于浮动浴位置玻璃条板的上方，其中玻璃温度为约625℃。The coater was positioned above the glass strip in a floating bath position where the glass temperature was about 625°C.
以30ml／min的速度汽化19mol％的氯化二甲基铟的乙酸乙酯溶液，使用实施例11-20所用的直接液体注射系统以110 l／min的速度将其并入氦负载气体中。包含铟化合物蒸气的负载气体与一种混合物流混合，所说的混合物流包含(a)10 l／min的氧气、包含17．4 l／min的水蒸气(实施例23为6 l／min)和1．1 l／min的氯化氢(实施例23为8 l／min)和(b)通过在95℃下以6 l／min(实施例22为15 l／min)鼓泡通过液体三氯化正丁基锡而产生的三氯化正丁基锡。在各实施例中，在玻璃上沉积掺杂锡的氧化铟薄膜，表5示出了所述膜的生长速度、它们的片电阻及所达到的近似铟转化率。A 19 mol% ethyl acetate solution of dimethylindium chloride was vaporized at a rate of 30 ml/min and incorporated into the helium load gas at a rate of 110 l/min using the direct liquid injection system used in Examples 11-20. The carrier gas comprising indium compound vapor is mixed with a mixture stream comprising (a) 10 l/min of oxygen, 17.4 l/min of water vapor (6 l/min in Example 23) and 1.1 l/min of hydrogen chloride (8 l/min in Example 23) and (b) by bubbling through liquid trichloride at 95°C at 6 l/min (15 l/min in Example 22). n-butyltin trichloride produced from n-butyltin. In each example, thin films of tin-doped indium oxide were deposited on glass, and Table 5 shows the growth rate of the films, their sheet resistance and the approximate indium conversion achieved.
表5
实施例24Example 24
在本实施例中，三氟乙酰基丙酮酸铟和氧气的预形成气态混合物被用于在实验室用静态炉中薄(0．070英寸，约2mm)的厚浮动玻璃样品上，形成掺杂氟的氧化铟涂层。In this example, a preformed gaseous mixture of indium trifluoroacetylacetonate and oxygen was used to form doped Fluorine indium oxide coating.
玻璃基质被放置在静态炉的耐热镍块上，其温度保持在1200°F(650℃)。一个矩形槽位于玻璃基质的上方和四周。该槽具有一个顶表面，其温度通过一个具有基于换热介质的常规油的冷却线圈保持在约500°F(260℃)。矩形槽用于涂镀设备以引导涂层前体接近玻璃基质的表面。该前体气体被引入矩形槽的顶表面与玻璃基质之间。The glass substrate is placed on a refractory nickel block in a static furnace maintained at 1200°F (650°C). A rectangular slot is located above and around the glass substrate. The tank has a top surface maintained at about 500°F (260°C) by a cooling coil with a conventional oil based heat transfer medium. Rectangular troughs are used in coating equipment to direct coating precursors close to the surface of the glass substrate. The precursor gas is introduced between the top surface of the rectangular trough and the glass substrate.
采用三氟乙酰基丙酮酸铟作前体在基质上沉积掺杂氟的氧化铟涂层。该三氟乙酰基丙酮酸铟是在366°F(185℃)下，经氦气以300cm3／min的速度鼓泡通过液体铟化合物而汽化的。A fluorine-doped indium oxide coating is deposited on a substrate by using indium trifluoroacetylacetonate as a precursor. The indium trifluoroacetylacetonate was vaporized at 366°F (185°C) by bubbling helium through the liquid indium compound at a rate of 300 cm3 /min.
充有铟化合物的氦气与附加的氦气(2．5 l／min)和氧气(4．5 l／min)混合，气态混合物(总流速约为7．3 l／min)射向热的玻璃表面上。在约2分钟后，切断铟和氧气物流，使炉冷却，取出玻璃，检测。以3．1nm／sec的生产速度形成掺杂氟的氧化铟涂层，其片电阻为27欧姆／平方。Helium filled with indium compound is mixed with additional helium (2.5 l/min) and oxygen (4.5 l/min), and the gaseous mixture (total flow rate is about 7.3 l/min) is injected into the hot on the glass surface. After about 2 minutes, the indium and oxygen flows were shut off, the furnace was allowed to cool, and the glass was removed for inspection. A fluorine-doped indium oxide coating was formed at a production rate of 3.1 nm/sec, and its sheet resistance was 27 ohms/square.
| Application Number | Priority Date | Filing Date | Title |
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| CN 97191358CN1204974A (en) | 1996-08-13 | 1997-08-12 | glass coating |
| Application Number | Priority Date | Filing Date | Title |
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| US08/694,435 | 1996-08-13 | ||
| CN 97191358CN1204974A (en) | 1996-08-13 | 1997-08-12 | glass coating |
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| CN1204974Atrue CN1204974A (en) | 1999-01-13 |
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| CN 97191358PendingCN1204974A (en) | 1996-08-13 | 1997-08-12 | glass coating |
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| CN112955413A (en)* | 2018-10-08 | 2021-06-11 | 皮尔金顿集团有限公司 | Method for preparing coated glass substrate |
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| CN110208997A (en)* | 2019-05-31 | 2019-09-06 | 广东旗滨节能玻璃有限公司 | A kind of intelligent color-changing glass and its preparation method and application |
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