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    公开号:NL9000320A
    申请号:NL9000320
    申请日:1990-02-09
    公开日:2001-02-01
    发明作者:
    申请人:Dow Corning；
    IPC主号:
    专利说明:

    Method for forming ceramic coatings at low temperature.
    It is desirable that electronic circuits and devices and other non-metallic substrate materials be useful under widely varying conditions. Moreover, for many applications of electronic devices, a premium is imposed on dimensions and weight. For example, electronic circuits used in aerospace, satellites, and aviation must not only withstand widely varying conditions, but must also be compact and lightweight in use. In order to protect such devices and substrates from heat, from moisture and from abrasive forces, the art industry has sought all kinds of methods for coating the devices and substrates in order to avoid exposing the devices or substrates to these conditions or at least to a minimum.
    Early attempts to protect electronic circuits include incorporating (embedding) the circuits in polymeric resins. However, these techniques significantly increase the thickness and weight of the circuits. In addition, the polymeric coatings tended to absorb moisture from the environment, which could eventually lead to damage or complete circuit failure. Today, some circuits are incorporated into ceramic packaging materials to protect them from environmental exposure. Although the ceramic packages are relatively safe, they do significantly increase the thickness and weight of the circuit. In addition, their manufacture is relatively expensive, and generally the air must be removed (evacuated) from the package, the device placed in it, and the package then closed.
    Commonly accepted causes for the failure of electronic devices include the formation of micro-cracks or openings in the surface, passivation of the device, for example a semiconductor "chip", the possibility of introducing contaminants from the environment. For example, sodium (Na +) and chloride (Cl *) ions can enter electronic devices and degrade the transmission of electrical signals. In addition, the presence of moisture and / or volatile organic chemicals can also adversely affect the operation of electronic devices. A single cladding material or layer may be insufficient to meet the increasing demands placed on the material in the electronics industry. A wide variety of coating properties, such as micro-hardness, moisture resistance, ion barrier, adhesion, ductility, tensile strength, and appropriate thermal expansion coefficient must be achieved by applying a number of thin protective layers to the electronic device.
    Recently, single-layer and multi-layer ceramic coatings of low weight have been developed for coating electronic devices. Haluska C.s. for example, in U.S. Pat. Nos. 4,753,855 and 4,756,977 describe the formation of ceramic coatings by preparing a solvent mixture of a hydrogen silesesquioxan resin alone or in combination with a metal oxide precursor which is then coated on the surface of an electronic device . The coating layer is converted to a ceramic material (ceramic) at temperatures between about 200 and 1000 ° C to form a silicon dioxide-containing ceramic coating. It is described that further coatings of ceramic materials provide additional protective and coating properties. These additional layers may consist of further ceramic or ceramic-type coatings containing silicon, silicon and carbon, or silicon, carbon and nitrogen.
    Although the techniques described in the above two patents of Haluska et al. Are effective in producing silicon dioxide-containing ceramic coatings at about 200 to 1000 ° C, the ceramic process of the hydrogen silesquioxane resin is quite slow at the lower end of the temperature stage, so that for practical production purposes, temperatures of at least 400 ° C must be used. While some electronic devices can withstand these higher temperatures, other devices, such as those containing gallium arsenide components, are often unable to withstand temperatures of 400 ° C and above. In addition, the length of time the device is exposed to a given temperature can be critical in that short heating times at a given temperature may be acceptable, while longer heating times at the same temperature may cause deterioration in quality and failure of the electronic devices.
    Therefore, there is still a need in the art for a thin ceramic coating with a low weight and a method of its application that can be applied to heat-sensitive electronic devices and other heat-sensitive substrates. Furthermore, there is still a need for a ceramic process which proceeds rapidly at temperatures below about 400 ° C.
    The present invention meets this need by providing a single or multi-layer ceramic or ceramic-like coating that can be applied to heat-sensitive substrates such as electronic devices. Furthermore, the invention provides a method by which the coating is ceramic-coated at temperatures as low as only about 40 ° C.
    According to one aspect of the present invention, there is provided a method of forming a ceramic or ceramic-like coating on a substrate, comprising the following steps: coating the substrate with a solution comprising a hydrogen silesquioxane resin diluted in a solvent and then evaporate the solvent to deposit a pre-ceramic coating on the substrate. The solution containing hydrogen sil-sesquioxane can be coated on the substrate by any suitable conventional technique, such as by spray coating, dip coating, liquid coating or rotary coating. In a preferred embodiment of the invention, the substrate is an electronic device or a silicon wafer.
    The pre-ceramic coating is then ceramicized to a silica-containing ceramic material by heating the pre-ceramic coating to a temperature between about 40 and about 400 ° C in the presence of ozone. It has been found that the presence of ozone increases the rate at which the ceramic is progressed and allows the coating to be ceramicized at lower temperatures than previously thought possible in the art. Ozone can be generated in an electric discharge or by using a source of ultraviolet light in the presence of oxygen. The ultraviolet light should preferably have a wavelength of less than 200 nanometers, and preferably a wavelength in the range of 185 to 200 nanometers.
    The ceramicization step must be performed in the presence of an atmosphere containing oxygen as a source of ozone. Air under normal atmospheric pressure is (for that) suitable. An oxygen processed atmosphere or an atmosphere of pure oxygen can also be used, although it is not necessary to do so. It has further been found that the presence of water vapor in the atmosphere also accelerates ceramicization. In a preferred embodiment, ceramic coating of the coating is performed in the presence of both ozone and water vapor.
    It has further been found that the presence of certain metal oxide precursors in the coating solution, alone or in combination with a small amount of platinum catalyst, also increases the rate of lower temperature ceramicization. The metal oxide precursors suitable for use in the practice of the present invention include soluble compositions in which the metal in the metal oxide precursor consists of aluminum, titanium or zircon and wherein the metal is an alkoxide, ketonate, diketonate, silanolate or glyco plate substituent. The platinum catalyst may optionally be present in the coating solution in an amount between about 15 and about 200 ppm. Another possibility is that the coating solution contains the platinum catalyst and hydrogen silesesquioxane resin without additional metal oxide precursors.
    The ceramic silicon dioxide coating deposited from the solution containing hydrogen silesesquioxane resin can act as a smoothing layer on the surface of an electronic device. Additional ceramic coatings can be deposited over the first layer and act as passivating and / or barrier protective layers. Such further layers can be deposited by a number of different techniques including, but not limited to, this deposition of vapor phase chemical deposition, plasma enhanced vapor phase chemical deposition, metal assisted vapor phase chemical deposition, thermal deposition deposition techniques or laser deposition techniques. Another method that can be used is to apply a solution of the ceramic precursor material to the surface of the substrate, followed by pyrolysis to convert the material into a ceramic material. For heat sensitive substrates, the pyrolysis temperature should be kept as low as possible, preferably below 400 ° C.
    For example, the second layer of a two-layer coating system may comprise a passivating coating selected from the group consisting of a silicon and nitrogen-containing coating, a silicon and carbon-containing coating, and a silicon, carbon and nitrogen-containing coating. The silicon and nitrogen-containing coating can be applied to the first smoothing coating by chemical vapor deposition of a silane, halosilane, halodisilane, halo polysilane or mixtures thereof in the presence of ammonia; plasma enhanced chemical deposition from the vapor phase of a silane, halosilane, halodisilane, halo polysilane or mixtures thereof in the presence of ammonia, or by ceramic coating of a silicon and nitrogen-containing ceramic precursor polymer.
    The silicon, carbon and nitrogen-containing coating layer can be applied to the smoothing coating by chemical vapor deposition of hexamethyldisilazane; plasma enhanced chemical deposition from the vapor phase of hexamethyldisilazane; by chemical deposition from the vapor phase of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms or of an alkyl silane and further in the presence of ammonia; or by plasma enhanced chemical deposition from the vapor phase of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms or an alkyl silane and further in the presence of ammonia. The silicon and carbon-containing coating can be deposited by chemical vapor deposition of a silane, halosilane, halo-polysilane, or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms to form the passivating coating.
    A further barrier layer to impart hermetic properties to the coating system can be applied over the passivation coating. This barrier layer preferably includes a silicon-containing coating selected from the group consisting of a silicon coating, and a silicon and carbon-containing coating, a silicon and nitrogen-containing coating, and a silicon, carbon and nitrogen-containing coating. The silicon coating can be applied to the passivating coating by chemical vapor deposition of a silane, halosilane, halopolysilane or mixtures thereof; Plasma-enhanced chemical deposition from the vapor phase of a silane, halosilane, halo-polysilane or mixtures thereof; or with metal assisted chemical vapor deposition of a silane, halosilane, halogen polysilane or mixtures thereof. The silicon and carbon-containing coating can be applied by chemical deposition from the vapor phase of a silane, alkyl silane, halosilane, halo disilane, halo polysilane or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms or an alkyl silane; or plasma enhanced chemical vapor deposition of a silane, alkyl silane, halosilane, halo disilane, halo polysilane or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms or an alkyl silane.
    The silicon and nitrogen-containing coating can be deposited by chemical vapor deposition of a silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of ammonia; plasma enhanced chemical deposition from the vapor phase of a silane, halosilane, halodisilane, halo polysilane or mixtures thereof in the presence of ammonia; or by ceramicizing a silicon and nitrogen-containing pre-ceramic polymer. The silicon, carbon and nitrogen-containing coating layer can be deposited by chemical vapor deposition of hexamethyl-disilazane; plasma enhanced chemical deposition from the vapor phase of hexamethyldisilazane; chemical deposition from the vapor phase of a silane, alkyl silane, halosilane, halodisilane, halo polysilane or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms or an alkyl silane and further in the presence of ammonia; or by plasma-enhanced chemical vapor deposition of a silane, alkyl silane, halosilane, halodisilane, halopolysilane or mixtures thereof in the presence of an alkane of 1 to 6 carbon atoms or of an alkyl silane and further in the presence of ammonia.
    It is therefore an object of the present invention to provide a single or multi-layer ceramic or ceramic-type coating that can be applied to heat-sensitive substrates such as electronic devices. Furthermore, it is an object of the present invention to provide a method by which the hydrogen silsesquioxane coating layer is ceramic-coated at temperatures as low as only about 40 ° C. These and other objects and advantages of the present invention will become apparent from the following detailed description and the appended claims.
    The present invention relates to the finding that a silicon dioxide-containing ceramic or ceramic-like coating can be obtained on a substrate at temperatures below those described in the prior art literature by exposing the pre-ceramic coating to ozone during ceramicizing. The present invention is particularly useful to provide a protective single or multiple coating on heat-sensitive substrates such as electronic devices and circuits. This is accomplished by coating a hydrogen silesesquioxane resin on the surface of the substrate and then heating the coating in the presence of ozone to ceramic the coating to a silicon dioxide-containing material. Additional layers of ceramic or ceramic-like materials can then be applied over the first layer to provide further protection of the substrate.
    The coatings of the present invention are useful not only as protective coatings to protect electronic devices from the environment, but also as protective layers on other heat-sensitive non-metallic substrates, such as plastic materials, including, for example, polyimides, epoxides, polytetrafluoroethylene, and copolymers thereof , polycarbonates, acrylic resins and polyesters. The coatings can also function as dielectric layers, doped dielectric layers to form transistor-like devices, pigment filler-containing binder systems for manufacturing capacitors and capacitor-like devices, multi-layer devices, 3-D devices, silicon on an insulator (SOI ) devices, superlattice devices and the like.
    The term "ceramic-like" used in the present invention refers to those pyrolized materials which are not completely free of carbon and / or hydrogen residues but which are otherwise ceramic in nature. The terms "electronic device" and "electronic circuit" further include, but are not limited to, the invention such gallium arsenide silicon based devices and circuits, focal plane systems, optoelectronic devices, on exposure (photovoltaic) cells, optical devices, dielectric layers, doped dielectric layers for the manufacture of transistor-like devices, pigment filler-containing binder systems for the manufacture of capacitors and capacitor-like devices, multi-layer devices, 3- D devices, silicon on an insulator including devices and super lattice devices.
    The present invention is an improvement over the coating methods described and claimed in U.S. Patent No. 4,756,977 to Haluska, et al. And in U.S. Patent No. 4,753,855 to Haluska. By exposing the hydrogen silesquioxane coatings to ozone, the coating or coatings are ceramicized at lower temperatures and / or at higher rates. The method of the present invention makes it possible to ceramic the coating at temperatures as low as even about 40 ° C. Furthermore, the method of the present invention results in the ceramicization taking place at a significantly faster rate at a given temperature than is achieved with the previous methods of Haluska et al. At that given temperature.
    According to the present invention, the first flattening layer is formed from a hydrogen silesesquioxane resin (HSiO3 / 2) n wherein n is an integer between 10 and 1000 and wherein the resin has a number average molecular weight of 800 to 2900 and a weight average molecular weight of between 8000 and 28000 The resin is diluted with a solvent such as n-heptane or toluene so that the concentration of hydrogen silesesquioxane in solution is about 0.1 to about 25% by weight. The hydrogen silesquioxane resin can be prepared according to the teachings of Frye et al., U.S. Patent No. 3,615,272 and of Fraye et al., J. Am. Chem. Soc. 92, p. 5586 (1970). In the preparation of the hydrogen silsesquioxane resins by the reactions described in the publications of Frye et al., It is generally preferred to use toluene as a solvent to operate in a manner that avoids temperature rise above ambient conditions or minimized and to neutralize with a mild (neutralizing) agent such as calcium carbonate rather than washing to neutral. The pre-ceramic solution in a solvent is coated on a substrate and then the solvent is allowed to evaporate under ambient conditions. The pre-ceramic coating can be applied by any of a variety of suitable techniques, including, but not limited to, the method of application, rotary coating, dip coating, spray coating, or liquid coating.
    With these agents, a smoothing pre-ceramic polymer coating is deposited which is then ceramic-coated by exposing the coating to ozone at a temperature between about 40 and about 400 ° C. The ozone can be suitably developed by exposing oxygen to a source of ultraviolet light. The ultraviolet light source may be any available source capable of emitting ultraviolet light in the wavelength range from about 185 to about 200 nanometers, such as, for example, a quartz mercury vapor lamp. In this way, a thin ceramic or ceramic-like flattening coating is formed on the substrate.
    During the ceramic coating process, an oxygen-containing atmosphere is used to provide a source of ozone. A normal ambient atmosphere (air) can be used. However, it has been found that oxygen-enriched atmospheres or an atmosphere of pure oxygen help to increase the rate of ceramicization. It is believed that the action of the ultraviolet light on the oxygen in the atmosphere decomposes the oxygen gas into atomic oxygen and ozone. It is believed that the atomic oxygen and ozone thereafter accelerate the oxidation of the hydrogen silesquioxane during heating to form a silicon dioxide-containing coating at the low temperatures employed in the practice of the present invention. It was further found that the presence of water vapor in combination with ozone also increases the rate of ceramicization.
    Furthermore, it has also been found that the presence of small amounts of platinum catalyst in the coating accelerates the rate of ceramicization of the hydrogen silesquioxane to silicon dioxide. Platinum can be added to the coating solution in the form of an organoplatinum compound and can be present in an amount between about 15 and 200 ppm based on the weight of the resin in the solution. The presence of these small amounts of platinum is believed to catalyze the oxidation of the hydrogen silesquioxane during heating.
    The present invention can also take advantage of the presence of certain metal oxide precursors in the first smoothing layer. For example, the hydrogen silesquioxane resin can be diluted in solution with zirconium, titanium and / or alumina precursor compositions which can be converted to ceramic or ceramic-type smoothing coatings at low temperatures with relatively high reaction rates in the presence of ozone. The term "metal oxide precursors" is a term which also includes metal compounds having alkoxy, acyloxy or other oxygen-containing organic groups which are bonded to the metal via oxygen and which can be hydrolyzed and then pyrolysed under said ceramic conditions to metal oxide.
    In practice, the hydrogen silesesquioxane resin is diluted in a solvent as described above and mixed with a zirconium, titanium and / or aluminum oxide precursor such as tetra n-propoxy zirconium (Zr (OCH2CH2CH3) 4 or tetraisobutoxy titanium (Ti [OCH2CH (CH3) Preferably, the amount of metal oxide precursor added to the solution is such that it provides about 0.1 to 30% by weight of metal oxide in the ceramic coating layer, The solution in the solvent is then dissolved in the manner described above. is coated on a substrate and the solvent is evaporated The coating is then ceramicized in the presence of ozone, at a temperature between about 40 and about 400 ° C.
    In this way, ceramic or ceramic-like coatings of Si02 / Zr02, Si02 / Ti02, Si02 / Ti02 / Zr02,
    SiO 2 / Al 2 O 3 and the like are made. By varying the mixture of hydrogen silsesquioxane using different metal oxide precursors, ceramic or ceramic-like coatings with varying thermal expansion coefficients can be made, as taught in the aforementioned U.S. Patent No. 4,753,855 to Haluska et al. to match thermal expansion properties of the substrate material and that of the coating to minimize the formation of cracks or holes during heating cycles.
    It will be appreciated that smoothing ceramic coatings can be formed by applying multiple layers of solution of hydrogen silesesquioxane resin, either prior to the ceramicization process or by ceramicization prior to application of a further layer of hydrogen silesquioxane resin. Of course, when multiple layers are applied, the ceramic layers can all be the same or they can be varied by including other metal oxide runners in the coating solution. Such a multi-layer application method can be used to produce ceramic coatings up to about 2 microns thick.
    The smoothing coating so formed can then be further coated with one or more further ceramic or ceramic-type coatings which can act as passivating layers, as diffusion barrier layers, as abrasion resistant layers, or the like. Such further coatings also resist ionic impurities such as chlorides. They can contain silicon, silicon and carbon, silicon and nitrogen or silicon, carbon and nitrogen and can be applied by chemical vapor deposition, plasma enhanced chemical vapor deposition or other suitable techniques.
    For use of a silicon and nitrogen-containing coating, pre-ceramic silicon and nitrogen-containing polymers suitable for use in the present invention are well known in the literature and include silazanes, disilazanes, polysilazanes and cyclic silazanes. Other suitable materials that can be used are those described in the above patents of Haluska et al. Such pre-ceramic polymers must be convertible into a ceramic or ceramic-like material or other substrate at temperatures acceptable for the particular electronic device being used. lined. In general, such pre-ceramic polymers are most effectively converted to ceramic at temperatures of about 400 ° C and above.
    A coating of the pre-ceramic silicon and nitrogen-containing polymer can be applied by first diluting the polymer to a low solids solution (i.e., 0.1 to 10.0 wt%) in an organic solvent such as n-heptane or toluene. The polymer-containing solution is then applied to the surface of the silica-containing smoothing layer by some suitable coating technique, such as rotary coating, dip coating, spray coating, or flow coating, and the solvent is allowed to evaporate (then). The pre-ceramic coating thus deposited is then ceramicized by heating the coating. Thin ceramic or ceramic-type coatings with a thickness between about 1 and 1500 nanometers can be produced by this method.
    Alternatively, techniques such as vapor phase chemical deposition, plasma enhanced chemical vapor deposition and metal-assisted vapor phase chemical deposition may be used to deposit the second and subsequent coatings on the substrate material. For example, coatings containing silicon, silicon and carbon, silicon and nitrogen and silicon, carbon and nitrogen can be deposited with these techniques. A preferred method of depositing a silicon-containing top layer at a relatively low temperature is by the vapor phase metal-assisted chemical deposition method described in U.S. Patent Application Serial No. 8,35029, filed February 2, 1986, by Sudarsanan Varaprath, entitled "Silicon-containing Coatings and a Method for Their Preparation". The high temperatures in conventional vapor phase chemical deposition techniques may limit the type of substrate that can be coated. For example, electronic devices that cannot withstand temperatures in excess of 400 ° C without being damaged should be coated using other than conventional vapor phase chemical deposition techniques, such as the previously described metal assisted vapor phase chemical deposition technique.
    The practice of the present invention makes it possible to apply ceramic and ceramic-like coatings to substrates that are heat sensitive. For example, some of the latest electronic devices containing gallium arsenide components are extremely sensitive to heat so that they can withstand a maximum temperature of about 350 ° C for only about 30 minutes. Thus, the lower temperatures of the present invention and the faster ceramization rates are extremely useful for applying protective coatings to such devices.
    For easier understanding of the invention, reference is made to the following examples which are intended to illustrate the invention, but should not be construed as limiting the scope of the invention.
    Example 1
    A pre-ceramic polymer containing hydrogen sesesquioxane resin, (HSiO3 / 2) n, made by the aforementioned method of Frye et al., Was diluted in n-heptane solvent to a solids content of 0.75 wt%. Furthermore, 18 ppm of platinum (based on the weight of resin in the solution) in the form of bis (diethylthio) platinum dichloride [(CH3CH2) 2S] 2PtCl2 were also added to the solution. The solution was then flow-coated on a 38.5mm x 19.5mm x 4mm potassium bromide crystal substrate and then the solvent was allowed to evaporate at room temperature.
    The deposited pre-ceramic coatings were then ceramicized in a reaction chamber under normal ambient atmosphere conditions for a period of about 9.5 hours at a temperature in the range of 20 to 40 ° C. During the ceramicization, the coating was also exposed to ozone using an ultraviolet light source emitting light in the 185 to 366 nanometer wavelength range to form ozone. The UV light source was a quartz mercury vapor lamp, model T0606B manufactured by UVOCS Ine. at Montgomeryville, Pennsylvania.
    Infrared spectral analyzes were performed at 90 minute intervals on the coating at the times indicated in Table 1 during the treatment. The conversion of the hydrogen silesesquioxane resin to silicon dioxide was measured by the presence and strength of a peak in the spectrum at about 2245 cm -1. The percent conversion was determined by calculating the ratio of the strength of the peaks in the spectrum at 2245 cm 1. The presence of SiH groups in the product causes the occurrence of a peak at this wavelength, while the absence of this peak indicates oxidation of all SiH groups to SiO groups. As can be seen, almost completely ceramic coating took place in about 8.0 to 9.5 hours at a maximum temperature of 40 ° C.
    Table 1 treatment time conversion of (HSiO3 / 2) n at 20 ° C-40eC. in SiO2 0.5 h 18.4 2.0 36.7 3.5 50.0 5.0 64.3 6.5 88.0 8.0 96.9 9.5 100.0
    For comparison, it is noted that the infrared spectrum of a coating of the same composition pyrolysed without ozone in a normal atmosphere at 400 ° C indicated that it is nearly completely ceramic (i.e., lack of SiH groups in the spectrum) about 4.25 h of heating were required.
    Example 2
    The same pre-ceramic polymer solution as in Example 1, but now with 9 ppm of platinum in it, was layered on a potassium bromide crystal substrate and the solvent was allowed to evaporate. The coating was heated in a 1 inch tubular reactor over a period of 8 hours to a maximum of 55 ° C while being exposed to ozone generated by a quartz mercury vapor lamp emitting ultraviolet light with a wavelength of 185 to 579 nanometers . Analysis of the coating spectrum indicated that almost complete ceramic of the sample had taken place in 8 hours, as shown in the results shown in Table 2.
    Table 2
    Treatment time at% conversion of (HSiO3 / 2) n 55 ° C (max.) To SiOz 1 h 21.2 3 63.6 6 97.0 8> 99.0
    Example 3
    The same pre-ceramic polymer solution as in Example 2 was flow-coated on a substrate of potassium bromide crystal and the solvent was allowed to evaporate. For comparison, the same pre-ceramic polymer solution but without platinum was flow-coated on a second substrate of potassium bromide. The coatings were exposed in a reaction chamber at 200 ° C to ozone generated by ultraviolet light from a quartz mercury vapor lamp (100 watt, model 7825-30 Ace Glass immersion lamp from Conrad Hanovia). The conversion results are shown in the following Table 3. As can be seen, the presence of platinum in the coating led to a faster rate of ceramicization.
    Table 3
    Sample% conversion of (HSiO3 / 2) n to SiO2 1 h 2 h 3h (HSiO3 / 2) n + Pt 72.6 98.1 100.0 (HSiO3 / 2) n 45.2 73.1 91.2
    Example 4
    The same pre-ceramic polymer as in Example 3 was flow-coated on a 1 inch square silicon wafer and the solution was allowed to air dry for 20 minutes. Furthermore, the same pre-ceramic polymer, but with the addition of 12 ppm Pt (in the form of [(C2H5) 2S] 2PtCl2) (based on the weight of the resin) was also applied by liquid coating. a 1 inch square silicon wafer followed by air drying for 20 minutes.
    The coatings were then heated at 200 ° C in air for three 1-hour periods, but without the presence of ozone or a source of ultraviolet light to generate ozone. An infrared spectrum was initially recorded, and then the spectrum was recorded at 1 hour intervals to measure the ceramics of the coatings.
    As can be seen from the figures in Table 4, the ceramics in the absence of ozone determined from the peaks in the spectrum at 2245 cm -1 (conversion of SiH bonds to SiO bonds) was negligible and significantly lower than found for the same resin coatings in the presence of ozone.
    Table 4
    Sample% conversion of (HSio3 / 2) n to SiO2 1h 2h 3h (HSi03 / 2) n <10 <10 <10 (HSi03 / 2) n + Pt <10 <10 <10
    Example 5
    A first pre-ceramic polymer solution of hydrogen silsesguioxane resin (0.75 wt% solid) was prepared and mixed with Al (C5H702) 3 (0.75 wt% solid) in a molar ratio (i.e. ratio of the number of atoms Si to atoms A1) of 75/25 to form a solution in methyl ethyl ketone. A second pre-ceramic polymer solution of hydrogen silesesquioxane (0.75 wt% solid) was prepared and mixed with Zr (C5H702) 4 (0.99 wt% solid) in a molar ratio (i.e. ratio of a number of Si atoms) to atoms Zr) of 75/25 to form a solution in methyl ethyl ketone with a solids content of 1% by weight. The second sample also contained 60 ppm of platinum (as Pt (02C5H7) 2). Individual substrates of potassium bromide crystal were liquid-coated with each solution. Infrared spectra were recorded after air drying for 20 minutes. The samples were then exposed to ozone in a reaction chamber at 200 ° C as described in Example 3. Infra-red spectra were periodically recorded and the results are shown in Table 5 below.
    Table 5
    Sample% conversion of (HSi03 / 2) n SiO2 1h 2h 3h HSi03 / 2) n / Al (02C5H7) 3 46.9 70.3 95.3 (HSi03 / 2) n / Zr (02C5H7) 4 + Pt 91, 5 97.9 100.0
    Example 6
    The pre-ceramic polymer solutions in methyl ethyl ketone containing hydrogen silsesquioxane resin mixed with A1 (C5H702) 3 and Zr (C5H702) 4, respectively, from Example 5 were liquid coated onto 1 inch square silicon wafers and the layers were allowed to air for 20 minutes to dry. For this example, the Zr (C5H702) 4 sample (also) contained 12 ppm Pt (as Pt (02C5H7) 2). The coated plates were heated in air at 200 ° C for three hours over a period of 1 hour, but in the absence of ozone or a source of ultraviolet light. Infrared spectra were taken at 1 hour intervals. As can be seen from the figures in Table 6, the ceramification in the absence of ozone, measured by the peaks in the spectrum at 2245 cm -1 (conversion of Si-H bonds to SiO), was negligible and significantly slower than for the same resin coatings at presence of ozone (see example 5).
    Table 6
    Sample% conversion of (HSi03 / 2) n into SiO2 1 h 2 h 3 h (HSi03 / 2) n / Al (02C5H7) 3 <10 <10 <10 (HSi03 / 2) n / Zr (02C5H7) 4 + Pt 15 25 40
    Example 7
    A pre-ceramic polymer solution of hydrogen silesesquioxane resin was prepared and diluted to a solution with a solid content of 10 wt% in n-heptane. 173 ppm of platinum (as Pt (02C5H7) 2) was also added to the solution. The solution was applied to a 1 inch square silicon wafer and to a GaAs gigabit Logic 10G001-4F device by rotating coating the parts with the solution for 10 seconds at 3000 rpm. The coatings were air dried and then heated in air at 300 ° C while being exposed to ozone generated by UV light from a quartz mercury vapor lamp, as in the previous examples. The GaAs device had retained its functions after ceramic coating. Infrared spectral analyzes of the conversion of the coatings are listed in Table 7.
    Table 7
    Sample% conversion of (HSiO3 / 2) n to SiOz 1 h (HSiO3 / 2) n + Pt> 90%
    Example 8
    The same pre-ceramic polymer solution as in Example 5 was prepared and rotary coated onto a 1 inch square silicon wafer and onto a GaAs device of the same type, coated at 3000 rpm for 70 seconds. The coatings were air dried and then heated at 300 ° C in an oxygen atmosphere saturated with water vapor (O 2 was bubbled through H 2 O) while ozone exposure was as described in Example 5. The GaAs device had its function retained after ceramic coating. Results of infrared spectral analyzes of the conversion of the coatings are shown in Table 8 below. As can be seen, ceramicization proceeds faster in the presence of an oxygen atmosphere and of water vapor.
    Table 8
    Sample% conversion of (HSiO3 / 2) n to SiO2 1 h (HSiO3 / 2) n + Pt 100%
    A 1 inch square silicon wafer was liquid coated with a pre-ceramic polymer solution of 0.8 wt% (HSiO) 3/2) n and 0.85 wt% Ti (OC4H9) 4 at 12 ppm Pt (as Pt (02C5H7) 2) in n-heptane and allowed to air dry for 2 minutes. A Motorola 14011B CMOS device was spin coated with the pre-ceramic polymer solution by coating at 2000 rpm for 15 seconds. A 1.5 x 2.0 inch polyimide circuit board (280 ° C thermal stability) was also spin coated for 15 seconds at 2000 rpm. coated with the same solution. Both samples were allowed to air dry for about 20 minutes.
    All coated parts were heated in air at 200 ° C for three periods of 1 hour while exposed to ozone generated by UV light from a quartz mercury vapor lamp, as in the previous examples. Infrared spectra of the samples were taken prior to heating and at 1 hour intervals. The change in Si-H absorption at 2245 cm -1 indicated that in all cases a significant conversion to Si-0 had occurred after 3 hours (conversion at least 70%).
    For comparison, the same pre-ceramic polymer solution was flow-coated on a 1 inch square silicon wafer, air dried for 20 minutes and then heated in air at 200 ° C for three periods of 1 hour. Infra-red spectra were also recorded first before heating and then heating at 1 hour intervals. The spectral data indicate that the conversion of Si-H bonds to Si-0 bonds was slower compared to the samples exposed to ozone.
    While certain representative embodiments and details have been given by way of illustration of the invention, it will be apparent to those skilled in the art that a variety of changes in the method and devices disclosed may be practiced without departing from the scope of the invention defined in the claims. come.
    权利要求:
    Claims (10)
    [1]
    A method of forming a ceramic or ceramic-like coating on a substrate, comprising the following steps: (a) coating the substrate with a solution containing a hydrogen silesesquioxane resin diluted in a solvent; (b) evaporating the solvent to deposit a pre-ceramic coating on the substrate, and (c) ceramicizing the pre-ceramic coating to a silicon dioxide-containing ceramic coating by heating the pre-ceramic coating at a temperature between about 40 and about 400 ° C in the presence of ozone.
    [2]
    The method of claim 1 wherein the ozone is generated by a source of ultraviolet light.
    [3]
    The method of claim 1 wherein the ozone is generated by a source of electrical discharges.
    [4]
    The method of claim 1, wherein the ceramic step is performed in the presence of water vapor.
    [5]
    The method of claim 1 wherein the solution also contains a soluble metal oxide precursor wherein the metal oxide precursor metal is aluminum, titanium or zircon and wherein the metal has an alkoxide, ketonate, diketonate, silanolate or glycolate substituent.
    [6]
    The method of claim 1 wherein the solution also contains platinum.
    [7]
    The method of claim 1 wherein the substrate is an electronic device.
    [8]
    The method of claim 1 wherein the substrate is a silicon wafer.
    [9]
    A method of forming a multilayer ceramic or ceramic-like coating on a substrate, comprising the following steps: (I) (a) coating the substrate with a flattening coating comprising a solution of a hydrogen silesquioxane resin diluted in a solvent, (b) evaporating the solvent to deposit a pre-ceramic coating on the substrate and (c) ceramicizing that pre-ceramic coating to a silica-containing ceramic material by heating the pre-ceramic coating to a temperature between about 40 and about 400 ° C in the presence of ozone to form the smoothing coating, (II) applying to that smoothing coating a passivating coating selected from the group consisting of (i) a silicon and nitrogen containing coating (ii) a silicon and carbon containing coating, and (iii) a silicon, carbon and nitrogen containing coating, and (III) applying to that pass ivory coating of a silicon-containing coating selected from the group consisting of (i) a silicon coating, (ii) a silicon and carbon-containing coating, (iii) a silicon and nitrogen-containing coating and (iv) a silicon, carbon and nitrogen-containing coating , whereby a multilayer ceramic or ceramic-like coating is obtained.
    [10]
    A method of forming a two-layer ceramic or ceramic-like coating on a substrate, comprising the following steps: (I) (a) coating the substrate with a smoothing coating, comprising a solution of hydrogen silesquioxane resin diluted in a solvent, (b) evaporating the solvent to deposit a pre-ceramic coating on the substrate, and (c) ceramicizing that pre-ceramic coating to a silicon dioxide-containing ceramic material by heating the pre-ceramic coating to a temperature between about 40 and about 400 ° C in the presence of ozone to form the smoothing coating, and (II) applying to the smoothing coating a passivating coating selected from the group consisting of (i) a silicon and nitrogen containing coating, (ii) a silicon and carbon-containing coating, and (iii) a silicon, carbon and nitrogen-containing coating, with which a two-layer structure is formed Your ceramic or ceramic-like coating is obtained. o-o-o-o-o
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    同族专利:
    公开号 | 公开日
    NL194796B|2002-11-01|
    DE4005472C2|1995-04-13|
    US5336532A|1994-08-09|
    FR2704355B1|1996-05-31|
    IT9019237A1|1990-08-22|
    CA2007726A1|1994-05-27|
    AU649215B1|1994-05-19|
    DE4005472A1|1994-11-10|
    IT9019237D0|1990-02-02|
    NL194796C|2003-03-04|
    FR2704355A1|1994-10-28|
    GB2280203B|1995-06-28|
    GB9002497D0|1994-10-26|
    IT1259407B|1996-03-18|
    GB2280203A|1995-01-25|
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    法律状态:
    2001-02-01| A1B| A search report has been drawn up|
    2001-03-01| BC| A request for examination has been filed|
    2005-11-01| V1| Lapsed because of non-payment of the annual fee|Effective date: 20050901 |
    优先权:
    申请号 | 申请日 | 专利标题
    US31245789|1989-02-21|
    US07/312,457|US5336532A|1989-02-21|1989-02-21|Low temperature process for the formation of ceramic coatings|
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