Method of producing nanostructured metal oxide coatings

FIELD: chemistry.

SUBSTANCE: method comprises preparing an alcohol solution of β-diketonates of one or more p-, d- or f-metals with concentration 0.001h² mol/l; heating the solution to 368-523 K and holding at said temperature for 10-360 minutes to form a metal alkoxo-β-diketonate solution; depositing the obtained solution in droplets at the centre of a substrate being rotated at a rate of 100-16000 rpm, or immersing the substrate into said solution at a rate of 0.1-1000 mm/min at an angle of 0-60° to the vertical; holding the substrate with a film of the alkoxo-β-diketonate solution at 77-523 K until mass loss ceases, to form xerogel on the surface of the substrate; crystallising oxide from the xerogel at 573-1773 K.

EFFECT: invention enables to obtain single- or multilayer dense and porous, amorphous and crystalline nanostructured oxide coatings with ordered particle size ranging from 1 nm to 100 nm with given functional properties.

9 cl, 5 dwg, 10 ex

The invention relates to the field of synthesis of metal oxides of simple and complex composition having dielectric or semiconductor properties, in the form of thin nanostructured coatings on the surface of products of various shapes that perform safety functions during operation at high, 2300 K and higher temperatures in oxygen-containing atmosphere having an important optical, magnetic, catalytic and other functional properties, which makes it promising for their use in the fields of industry and technology as aircraft and rocket engineering, optics and electronics, nanostructured state of the synthesized coatings can be applied in catalysis and chemosensory, as well as ceramic pigments.

In the analysis of scientific publications and international achievements in the field of production of nanostructured oxide coatings confirmed the relevance of this issue, which stems from the great practical significance of the study materials.

The most common ways of obtaining nanocrystalline oxide coatings are chemical precipitation of their gas phase (CVD, including with the use of ORGANOMETALLIC compounds - MOCVD), atomic layer deposition (ALD) and the Sol-gel method. At the same time more simple and universal is the latest.

the most cases, with the development of nanostructured coatings as precursors are volatile compounds alkoxides, oxoalkoxide, chlorides, β-diketonates metals and ORGANOMETALLIC compounds.

In the known methods of obtaining oxide coatings [US 5922405, US 5998644, US 6063951] the authors proposed to use as precursors of volatile ORGANOMETALLIC compounds with the General formula R¹₂AlOR²(when receiving films of aluminum oxide; R¹, R²- C_1-10is an alkyl group), M[(µ-OR')₂M R₂]₂(upon receipt of oxide films of the composition of the MM'₂O₄where M Is Be, Mg, Zn or Cd; M' Is Al or Ga; R, R' - C_1-10is an alkyl group). The method of chemical vapor deposition (CVD) received the oxide coating by evaporation of these compounds. However, significant shortcomings of the method should include complex multi-stage methodology for the synthesis of precursors and the use of compounds containing alkali metals and Halogens, which significantly increases the requirements for the clearing of them target compounds.

In the invention [US 7501153B2, US 7714155B2] proposed when the coatings of oxides and nitrides of metals by the method of chemical vapor deposition (CVD) to use as a precursor alkoxides and mixtures of alkoxides of metals with a branched carbon skeleton. It should be noted that the use of alkoxides of metals upon receipt of an oxide or nitride coating is rather difficult their high hydrolytic activity, increasing requirements to the hardware design and the conditions of storage and transportation; upon receipt of oxide coatings containing several different metals, using a mixture of their alkoxides with different volatility due to differences in physico-chemical properties, it is difficult to obtain a given ratio of the metals, as evidenced by the examples in these publications.

A method of obtaining coatings of barium titanate BaTiO₃[EP 0079392 A1] a method of dip-coating based on the use as precursors of oxoalkoxide metals. In the described example, the coating deposited on the surface of the quartz plate when it is pulling from the alcohol solution used precursor with a speed of 40 cm/min, then was done drying and subsequent annealing at 1373 K for 3 hours, resulting in a coating BaTiO₃. The disadvantages of this method must be attributed to the difficulty of obtaining coatings of more complex composition, which is associated with the use of precursors, which is difficult to vary the ratio of barium and titanium, as well as the lack of data on the hydrolytic activity of the used connections and dependencies of the viscosity of their solutions from the time that largely determine the properties of the obtained coatings.

The authors of inventions [EP 0527661 A1] and [EP 0554246 B1] offer for the floor is possible coatings of oxides and fluorides of metals, as well as metal films by the CVD method to use as precursors of β-diketonates of the respective metals. In this case, the main difficulty is to obtain coatings of complex composition with a specified ratio of the metals that is limited to the different volatility of β-diketonates of the respective metals.

The authors of the invention [US 7592251 B2] atomic layer deposition receive a coating of oxides of tantalum, hafnium and titanium, using as precursors of nitrates, chlorides, iodides and alkoxides of metals. A method of obtaining a metal nitride coatings and multilayer combinations [US 8133555 B2] atomic layer deposition comes from the use of β-diketonates of the respective metals ([Co(DPM)₃], [Ru(DPM)₃], [Cu(hfac)tmvs] and C₁₁H₂₉N₄Ta - TAIMATA). In this and the above-described inventions, there is a limit in obtaining coatings of complex composition, which is associated with differences in the properties of the used precursors.

The authors of inventions [US 20070295273 A1, US 7648926 B2] to obtain films in the system of Al₂O₃-Y₂O₃atomic layer deposition propose to use as reagents triethylaluminium Al(C₂H₅)₃and 2,2,6,6-tetramethyl-3,5-garagentore [Y(tnd)₃]. In this case, as for the above inventions, a significant drawback I have is the use of precursors with different properties (volatility and sorption capacity), this is reflected in zatrudnienie coatings of complex composition with a specified ratio of metals.

The method of obtaining photocatalytic coatings [WO 2004014986 A1] (prototype) is the closest technical solution from a technological point of view. The authors suggest that when receiving a film-forming solution as precursors to use alkoxides of aluminum and titanium, as well as particles of titanium oxide. The methodology consists in the preparation of film-forming solution containing water, methanol, β-diketone (acetylacetone, 2,4-heptanedione, 3,5-heptanedione, 2,4-attention), an acid (acetic or nitric), which is then heated to a temperature of about 340 K, then is added to the alkoxide of aluminum (isopropoxide aluminum Al(OCH(CH₃)₂)₃or n-piperonyl aluminum Al(OCH₉)₃), the solution is maintained at boiling for about 2 hours, then cooled with stirring. In the resulting solution are added particles of titanium oxide and then it is put by a method of spin-coating onto a glass substrate and dried at a temperature of 293-303 To within 24 hours with the formation of the photocatalytic coating. You can also use isopropoxide titanium Ti(OCH(CH₃)₂)₄by inserting it into the solution together with particles of titanium oxide, for subsequent joint hydrolysis of the aluminum alkoxide. Use the W β-diketonate due to the need to reduce the hydrolytic activity of the aluminum alkoxide and improve the stability of the obtained film-forming solution. To improve the stability of the solutions proposed the use of different surfactants.

The above invention has a number of technological shortcomings. Namely, you want to use a large number of reagents, which complicates and increases the cost method. When one component is toxic alcohol is methanol. As sources of metals are encouraged to use their alkoxides, are often complicated by their instability and increased hydrolytic activity, which leads to difficulties in the synthesis of complex oxides of the composition. Alkoxides of different metals have different properties, so when receiving a mixed-forming solutions with different ratios of metals, it is difficult to predict its characteristics - viscosity, fluidity and long-term stability. The proposed methodology does not allow to vary the viscosity of the obtained solutions and its change in time to control the morphology of the resulting films.

The present invention is directed to the development of a simple and efficient way to obtain nanostructured coatings of metal oxides, including complex composition, using as precursors hydrolytically active solutions alkoxo-β-diketonates, metal-specified and controlled ordinationem environment of the Central atoms.

The technical result is achieved by the method for obtaining nanostructured coatings of metal oxides, namely, that serves alcohol solution of β-diketonates one or more p-, d - or f-metals with a concentration of 0.001÷2 mol/l, the solution is heated to 368÷523 K and maintained at this temperature for 10÷360 minutes prior to the formation of a mixture of alkoxo-β-diketonates metal, the resulting solution was dropwise applied to the Central part of the substrate which rotates with a speed of 100÷6000 rpm, or in a specified the solution immerse the substrate with a speed of 0.1÷1000 mm/min at an angle vertically 0÷60°, after which withstand a substrate coated with a film of a solution of alkoxo-β-diketonates at 77÷523 K To stop the weight loss with the formation of a xerogel on the surface of the substrate, followed by crystallization of the oxide of the xerogel at 573÷1773 K.

It is important that as alcohols sources of alkoxo group used single - and multi-atom, linear and branched alcohols.

It is possible that alcohol solution additionally contains aliphatic and aromatic hydrocarbons and their halogen derivatives, ethers, aldehydes, ketones, organic acids and other organic solvents in amounts necessary to achieve the solution boiling point in the range of 368÷523 K.

Also possible is that the resulting alcoholic solution of alkoxo-β-diketonates metal pre-hydrolized by adding a water-alcohol solution at a molar ratio of water to metal 0,5÷10.

It is advisable that the application of a film of a solution of alkoxo-β-diketonates metal on a substrate is carried out at a solution temperature of 273 to 523 K and the temperature of the substrate 273÷1273 K.

It is also advisable that the substrate material is chosen from a number of: silicon, silicon carbide, aluminum oxide.

It is preferable that the curing of the substrate coated with a film of a solution of alkoxo-β-diketonates to halting the loss of mass is carried out at pressures of 1·10^-5÷1 ATM.

It is also important that the process of crystallization of the oxide of the xerogel is carried out at pressures of 1·10^-5÷1 ATM.

It is also possible that after crystallization of the oxide of the xerogel spend additional annealing the substrate with the xerogel in a period of from 1 minute to 24 hours in an oxidizing or inert atmosphere at temperatures of 573÷1773 K.

The essence of the invention lies in the fact that hydrolytically active solutions alkoxo-β-diketonates p-, d - or f-metals with controlled coordination environment of the Central atoms derived from stable under normal conditions of β-diketonates of the respective metals allows to synthesize nanostructured thin oxide coating and multilayer materials with desired protective, optical, magnetic and other functional properties. Controlled synthesis of glycaemia in obtaining smeshanoligandnykh coordination compounds of a given composition and structure, the defining properties of a formed hydrolytically active solutions and oxide coatings.

In the synthesis of alkoxo-β-diketonates metal as alcohols sources of alkoxo group used single - and multi-atom, linear and branched alcohols. Structure used alcohol affects the degree of shielding of the Central atoms in the formed smeshanoligandnykh complexes, so you can control their hydrolytic activity. As solvents can act as themselves alcohols, and aliphatic and aromatic hydrocarbons and their halogen derivatives, ethers, aldehydes, ketones, organic acids and other organic solvents in amounts necessary to achieve the solution boiling point in the range of 368÷523 K. this temperature range is due to the fact that during the heat treatment of a solution of β-diketonates metal at a temperature below 368 destructive To the substitution of the β-diketonate ligands on alkoxo band practically does not occur, and above 523 To the high rate of substitution makes it difficult to control the degree of its passage from education smeshanoligandnykh connections required composition. Used β-diketonates metals have the composition [M(RCO)CHC(O)')_x], where M - p-, d - or f-metal, R and R' is a linear or branched alkyl radicals, including ftory the bathrooms. From the structure of the β-diketonate ligands also depends on the degree of shielding of the Central atom and, accordingly, the hydrolytic activity of generated alkoxo-β-diketonates metal. In addition to the composition and structure of the chelate and CNS fragments hydrolytic activity of the synthesized coordination compounds also determines the degree of substitution of the first on the second. This option is controlled by the heat treatment alcohol solution of β-diketonates metal. As a result, by varying the temperature of the solution in the interval 368÷523 K and the heat treatment time is from 10 to 360 minutes, controllable synthesis of alkoxo-β-diketonates metal with the desired ratio of ligands in determining their hydrolytic activity. Thus obtained solutions are used as precursors in the synthesis of simple and complex oxides of the composition in the form of thin nanostructured coatings.

Before applying a film of a solution of alkoxo-β-diketonates metal on a substrate to him can also be added gidrolizuemye component, which leads to hydrolysis smeshanoligandnykh alkoxo-β-diketonates metal, accompanied by an increase in viscosity and gel formation. As gidrolizuemye component is water or alcohol solution added to a solution of alkoxo-β-diketonato the metals in the ratio n(H ₂O/n(M)=0,5÷10. When the value of the ratio n(H₂O)/n(M)<0.5 amount of water is not enough to complete hydrolysis and increasing the viscosity of the solution, and when the ratio of n(H₂O)/n(M)>10 may precipitation and undesirable phase separation when using solutions containing complexes of different metals. Controlled degree of substitution of the β-diketonate ligands and a certain dependence of the solution viscosity with time after adding gidrolizuemye component allow direct way to vary the properties of the obtained coating thickness, morphology, porosity, adhesion and, therefore, their functional characteristics.

On the characteristics of the obtained oxide film is influenced by the temperature of the solution, alkoxo-β-diketonates metal at the time of application to the surface of the substrate. This is explained by the variation of viscosity and fluidity of the liquid by changing the temperature. The temperature of the solution ranges from 273 to 523 K. the Choice of this interval is due to the fact that when the temperature of the solution below 273 To its high viscosity makes it difficult to obtain a thin continuous coating, and the upper value 523 corresponds To its highest possible boiling point. Properties of the obtained oxide coatings also depend on the characteristics of the substrate, namely, the roughness (surface m which can be atomically smooth, and to have a height difference of up to 100 μm), porosity and temperature, the value of which ranges from 273 to 1273 K. depending on the temperature of the substrate changes its wettability when applied film hydrolytically active solution, which affects the properties of the obtained coatings. When the temperature of the substrate <273 To the low value of its wettability it difficult to obtain a uniform coating, and at a temperature of >1273 To possible unwanted chemical interaction resulting coating to the substrate.

As the substrate material, which is causing the oxide film, use sapphire, silicon, silicon carbide and other ceramic or metal material, which surface you want to protect or modify. The choice of material of the substrate, based on the possession of high melting point to reduce the likelihood of chemical interaction with the resulting oxide coating during the coating process.

When applying the film of solution on the surface of the substrate by the rotation method called by the method of spin-coating, the rotation speed of the substrate varies in the range from 100 to 16000 rpm This parameter controls the thickness, uniformity and morphology of the resulting coating. The solution in the required amount dropwise applied to the Central region of the surface of podlog and, followed by its rotation, accompanied by the distribution of fluid across the surface until formation of a uniform coating. You might also consider applying hydrolytically active solution on the surface of the substrate during its rotation. Depending on the solvent, concentration of metals and viscosity of the fluid by the rotation of the sample is from 10 seconds to 60 minutes.

In the case of deposition of a film of the resulting solution of alkoxo-β-diketonates metal by immersion of the substrate, the so-called method of dip-coating, the sink rate is from 0.1 to 1000 mm/min, which determines the thickness, uniformity and morphology of the resulting coating. The substrate during immersion has a tilt angle of the vertical from 0 to 60°. This parameter also affects the film properties, including the gradient of its thickness on the substrate surface.

After application of the film hydrolytically active solution on the substrate it is maintained at a temperature of 77÷523 K and at the pressure of 1·10^-5÷1 ATM until the cessation of mass loss, which leads to the formation of a xerogel film. Low pressure leads to the intensification of the process of solvent removal. The reduction of pressure below 1·10^-5ATM is impractical and leads to technological complexity of the process, and at a pressure above 1 ATM removing the solvent the C volume film hydrolytically active solution will slow down.

For formation of an oxide coating a substrate with a film xerogel is subjected to heat treatment at 573÷1773 K and at pressures of 1·10^-5÷1 ATM in an oxidizing atmosphere, an inert gas (Ar, N₂or in the mixture gas. The choice of temperature range due to the fact that below 573 K, the crystallization of the oxide occurs at a low speed, and the temperature increase above 1773 K leads to active aggregation of particles of the oxide coating and their interaction with the substrate material. Low blood pressure during synthesis facilitates the removal of gases released during decomposition of the organic components of the precursor. The reduction of pressure below 1·10^-5ATM and rise above 1 ATM leads to technological complexity of the process and impractical. It is also possible to conduct additional heat treatment of the substrate with the film xerogel during the time from 1 minute to 24 hours. Increasing the synthesis time is more than 24 hours leads to further aggregation of the oxide particles and is not economically justified, while less than 1 min may be sufficient for crystallization of the oxide film.

To increase the thickness of the coating or modification of its properties oxides of other compositions can be applied on its surface as described above, additional layers of oxide films. As a result of the treatment is described multilayer nanostructured oxide coating with a protective, optical, magnetic, catalytic, sensor and other functional properties, defined by combinations of oxide layers of different chemical composition.

The invention is illustrated in the following micrographs of the surface of the formed oxide coating:

Figure 1. Micrograph of the surface of the nanostructured thin film composition ZrO₂obtained at a temperature of 1473 K on the surface of the polished wafer of monocrystalline silicon (example 1).

Figure 2. Micrograph of the surface of the nanostructured thin film of the composition of 0.08 Y₂O₃-0,92 ZrO₂obtained at a temperature of 1473 K on the surface of the polished wafer of monocrystalline silicon (example 4).

Figure 3. Micrograph of the surface of the nanostructured thin film of the composition of 0.15 Y₂O₃-0,60 ZrO₂-0,25 HfO₂obtained at a temperature of 1073 K on the surface of the polished wafer of monocrystalline silicon (example 5).

Figure 4. Micrograph of the surface of the nanostructured thin film of the composition of 0.15 Y₂O₃-0,60 ZrO₂-0,25HfO₂obtained at a temperature of 1473 K on the surface of the polished wafer of monocrystalline silicon (example 6).

Figure 5. Micrograph of the surface of the nanostructured thin film of the composition of Y₃Al₅O₁₂, is received at a temperature of 1473 K on the surface of the polished sapphire wafer (example 9).

Figure 1-4 shows a micrograph obtained by scanning electron microscopy using a three-beam workstation Carl Zeiss NVision40, and figure 5 presents a topographic image of the surface of the oxide coating obtained by the method of atomic force microscopy using a scanning probe microscope Solver PRO-m. the results Obtained indicate the ordered state of oxide films consisting of nanoparticles.

Below is illustrating, but not limiting the proposed method examples of making nanostructured thin films of oxides of both simple and complex composition to various substrates.

Example 1. In 80 ml of isoamyl alcohol was dissolved 5,23 g [Zr(C₅H₇O₂)4], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 404±5 To 30 minutes. The resulting solution arcoxiazapomnit zirconium hereinafter was applied on the polished surface of a substrate of monocrystalline silicon when it is immersed in the solution at a speed of 500 mm/min. and the Temperature of the solution and the substrate during coating film was 293 K. it was Further held ageing of the substrate with the applied film of the solution at 343 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent Krista is the centralization of the oxide film when heated to 1473 K in air. As a result, the surface of the Si substrate was formed nanostructured thin film of zirconium oxide formed from particles with an average size of 42 nm, determined using scanning electron microscopy (Figure 1). X-ray surface analysis confirmed the formation phase of zirconium oxide.

Example 2. In a mixture of 70 ml of isoamyl and 10 ml of amyl alcohol was dissolved 5,23 g [Zu(S₅H₇C₂)₄], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 405±5 for 25 minutes. The resulting solution arcoxiazapomnit zirconium hereinafter was applied on the polished surface of a substrate of monocrystalline silicon when it is immersed in the solution at a speed of 500 mm/min. and the Temperature of the solution and the substrate during coating film was 293 K. Then produced artificial substrate coated with a film of the solution at 343 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1073 K in air. As a result, the surface of the Si substrate was formed nanostructured thin film of zirconium oxide formed from particles with an average size of 15 nm, determined using scanning electron microscopy. X-ray Ana is from the surface confirmed the formation phase of zirconium oxide.

Example 3. In a mixture of 35 ml of isoamyl and 5 ml n-butyl alcohol dissolved 2.25 g [Zr(C₅H₇O₂)4] and 0.88 g [Y(hfa)₃], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 403±5 To 50 minutes. The resulting solution of alkoxo-β-diketonates of zirconium and yttrium hereinafter was applied on the polished surface of a substrate of monocrystalline silicon when it is immersed in the solution at a speed of 300 mm/min. and the Temperature of the solution and the substrate during coating film was 298 K. Further was done keeping the substrate with the applied film of the solution at 323 K for 2 hours before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1073 K in air. As a result, the surface of the Si substrate was formed a thin nanostructured oxide film composition 0,08 Y₂O₃-0,92 ZrO₂formed from particles with an average size of 13 nm, determined using scanning electron microscopy. X-ray surface analysis confirmed the formation phase of zirconium oxide stabilized with yttrium.

Example 4. In a mixture of 18 ml of isoamyl alcohol and 22 ml of cumene dissolved and 2.26 g of [Zr(C₅H₇O₂)₄] and 0.44 g [Y(C₅H₇O₂)₃], p is the following which the solution was kept in a round bottom flask with reflux condenser at a temperature of 404±5 within 45 minutes. The resulting solution alkoxilierungen zirconium and yttrium hereinafter was applied on the polished surface of a substrate of monocrystalline silicon when it is immersed in the solution at a speed of 300 mm/min. and the Temperature of the solution and the substrate during coating film was 298 K. Further was done keeping the substrate with the applied film of the solution at 323 K for 2 hours before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1473 K in argon atmosphere and after cooling to remove from the scope of the oxide film of carbon, formed from the organic components of the precursor were heated to 1473 K in air. As a result, the surface of the Si substrate was formed nanostructured thin film composition of 0.08 Y₂O₃-0,92 ZrO₂formed from particles with an average size of 32 nm, determined using scanning electron microscopy (Figure 2). As can be seen, the pre-crystallization film in an inert atmosphere with the subsequent removal of carbon leads to the formation of coatings with greater porosity. X-ray surface analysis confirmed the formation phase of zirconium oxide stabilized with yttrium.

Example 5. In 72 ml of isoamyl alcohol was dissolved 2,41 g [Zr(C₅H₇ O₂)₄], 1.56 g [Hf(C₅H₇O₂)₄] and 1.36 g [Y(C₅H₇O₂)₃], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 404±5 for 40 minutes. The resulting solution alkoxilierungen zirconium, hafnium and yttrium hereinafter was applied on the polished surface of a substrate of monocrystalline silicon when it is immersed in a solution with a speed of 700 mm/min, the Temperature of the solution and the substrate during coating film was 293 K. Then produced artificial substrate coated with a film of the solution at 353 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1073 K in air. As a result, the surface of the Si substrate was formed a thin nanostructured oxide film composition of 0.15 Y₂O₃and-0.6 Zr₂-0,25 HfO₂formed from particles with an average size of 12 nm, determined using scanning electron microscopy (Figure 3). X-ray surface analysis confirmed the formation of phase oxide of zirconium-hafnium, yttrium-stabilized.

Example 6. Obtained according to the method described in Example 5, a solution alkoxilierungen zirconium, hafnium and yttrium was applied on the polished surface mean the key of monocrystalline silicon when it is immersed in a solution with a speed of 700 mm/min The temperature of the solution and the substrate during coating film was 293 K. Then produced artificial substrate coated with a film of the solution at 353 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1473 K in air. As a result, the surface of the Si substrate was formed a thin nanostructured oxide film composition of 0.15 Y₂O₃-0,60 ZrO₂-0,25 HfO₂formed from particles with an average size of 34 nm, determined using scanning electron microscopy (Figure 4). As can be seen, with increasing temperature there is an increase in the average size of particles that formed oxide film. X-ray surface analysis confirmed the formation of phase oxide of zirconium-hafnium, yttrium-stabilized.

Example 7. Obtained according to the method described in Example 5, a solution alkoxilierungen zirconium, hafnium and yttrium were applied to the surface of the polished substrate of monocrystalline silicon when it is immersed in a solution with a speed of 700 mm/min, the Temperature of the solution and the substrate during coating film was 293 K. Then produced artificial substrate coated with a film of the solution at 353 K for 1 h before the termination of the mass loss with the formation of the COP is rogala on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1473 K in argon atmosphere and after cooling to remove from the scope of the oxide film of carbon, formed from the organic components of the precursor were heated to 1473 K in air. As a result, the surface of the Si substrate was formed a thin nanostructured oxide film composition of 0.15 Y₂O₃-0,60 ZrO₂-0,25 HfO₂formed from particles with an average size of 59 nm, determined using scanning electron microscopy. X-ray surface analysis confirmed the formation of phase oxide of zirconium-hafnium, yttrium-stabilized.

Example 8. In 34 ml of isoamyl alcohol was dissolved 1,30 g [Al(C₅H₇O₂)_C] and 1,33 g [Y(tfa)₃], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 404±5 K for 5 hours. The resulting solution of alkoxo-β-diketonates of aluminum and yttrium then applied to the surface of the polished sapphire substrate when it is immersed in the solution at a speed of 250 mm/min, the Temperature of the solution and the substrate during coating film was 293 K. Then produced artificial substrate coated with a film of the solution at 343 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1273 K in air. As a result, the surface of the sapphire substrate was formed a thin nanostar churromania oxide film composition Y ₃Al₅O₁₂formed from particles with an average size of 50 nm, determined using atomic force microscopy. The maximum elevation on an area of 25 μm²was 20 nm. X-ray surface analysis confirmed the formation of phase yttrium-aluminum garnet.

Example 9. In 34 ml of isoamyl alcohol was dissolved 1,30 g [Al(C₅H₇O₂)₃] and 0.94 g [Y(C₅H₇O₂)₃], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 404±5 K for 5 hours. The resulting solution alkoxilierungen aluminum and yttrium then applied to the surface of the polished sapphire substrate when it is immersed in the solution at a speed of 250 mm/min, the Temperature of the solution and the substrate during coating film was 293 K. Then produced artificial substrate coated with a film of the solution at 343 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1473 K in air. As a result, the surface of the sapphire substrate was formed a thin nanostructured oxide film composition Y₅Al₅O₁₂formed from particles with an average size of 100 nm, determined using atomic force microscopy (Figure 5). The maximum is tional elevation on an area of 25 μm ²was 72 nm. X-ray surface analysis confirmed the formation of phase yttrium-aluminum garnet.

Example 10. In 27 ml of isoamyl alcohol was dissolved 1.08 g [Fe(C₅H₇O₂)₃] 0,76 g [Y(C₅H₇O₂)₃], after which the solution was kept in a round bottom flask with reflux condenser at a temperature of 404±5 K for 4 hours. The resulting solution alkoxilierungen iron and yttrium then applied to the surface of the polished sapphire substrate when the rotation speed of 3000 Rev/min the Temperature of the solution when applied his film was 313 K, and the temperature of the substrate was set to 303 K. Then produced artificial substrate coated with a film of the solution at 343 K for 1 h before the termination of the mass loss with the formation of a xerogel on the surface of the substrate and subsequent crystallization of the oxide film when heated to 1273 K in air. As a result, the surface of the sapphire substrate was formed a thin nanostructured oxide film composition Y₅Fe₅O₁₂formed from particles with an average size of 60 nm, determined using scanning electron microscopy. X-ray surface analysis confirmed the formation phase of the yttrium-iron garnet.

Thus, the developed method has the following pre what modestly:

- allows you to obtain nanostructured oxide coating both simple and complex composition at relatively low temperatures;

the ratio of metals in obtaining the oxide film of complex composition is set at the stage of loading β-diketonates in obtaining the solution alkoxo-α-diketonates metals; primordial differences in physico-chemical properties of the data coordination compounds do not lead to the deviation of the composition from a given;

- based on the use of stable under standard conditions reagents β-diketonates metal;

controlled synthesis of precursors - smeshanoligandnykh hydrolytically active coordination compounds (alkoxo-β-diketonates metal) allows for changes in their composition and structure of the Sol-gel method to obtain nanostructured thin oxide coatings according to functional properties (shielding, optical, magnetic, catalytic, and others);

well - known dependence of the viscosity of the hydrolytically active solutions alkoxo-β-diketonates metal from the time when the hydrolysis also gives the possibility of obtaining nanostructured oxide coatings with controlled characteristics.

The invention allows to obtain single-layer and multi-layered, dense and porous, amorphous and crystalline nanostructured oxide is ocrite with the size of the ordered particles from units to hundreds of nanometers using hydrolytically active alcohol solutions of alkoxo-β-diketonates metal with controlled coordination environment, synthesized on the basis of their β-diketonates. The resulting surfaces have a protective, magnetic, optical, sensor, catalytic and other functional properties.

1. The method of obtaining nanostructured coatings of metal oxides, namely, that serves alcohol solution of β-diketonates one or more p-, d - or f-metals with a concentration of 0.001÷2 mol/l, the solution is heated to 368÷523 K and maintained at this temperature for 10÷360 minutes prior to the formation of a mixture of alkoxo-β-diketonates metal, the resulting solution was dropwise applied to the Central part of the substrate which rotates with a speed of 100÷16000 rpm, or in the specified solution immerse the substrate with a speed of 0.1÷1000 mm/min at an angle vertically 0÷60°, after which withstand a substrate coated with a film of a solution of alkoxo-β-diketonates at 77÷523 K To stop the weight loss with the formation of a xerogel on the surface of the substrate, followed by crystallization of the oxide of the xerogel at 573÷1773 K.

2. The method according to claim 1, characterized in that as alcohols sources of alkoxo group used single - and multi-atom, linear and branched alcohols.

3. The method according to claim 1, characterized in that the alcohol solution additionally contains aliphatic and aromatic hydrocarbons and their halogen derivatives, ethers, aldehydes, ketones, organic is the cue acids and other organic solvents in quantities necessary to achieve the solution boiling point in the range of 368÷523 K.

4. The method according to claim 1, characterized in that the resulting alcoholic solution of alkoxo-β-diketonates metal pre-hydrolized by adding a water-alcohol solution at a molar ratio of water to metal 0,5÷10.

5. The method according to claim 1, characterized in that the coating film of the solution alkoxo-β-diketonates metal on a substrate is carried out at a solution temperature of 273 to 523 K and the temperature of the substrate 273÷1273 K.

6. The method according to claim 1, characterized in that the substrate material is chosen from a number of: silicon, silicon carbide, aluminum oxide.

7. The method according to claim 1, characterized in that the curing of the substrate coated with a film of a solution of alkoxo-β-diketonates to halting the loss of mass is carried out at pressures of 1·10^-5÷1 ATM.

8. The method according to claim 1, characterized in that the crystallization of the oxide of the xerogel is carried out at pressures of 1·10^-5÷1 ATM.

9. The method according to claim 1, characterized in that after the crystallization of the oxide of the xerogel spend additional annealing the substrate with the xerogel in a period of from 1 minute to 24 hours in an oxidizing or inert atmosphere at temperatures of 573÷1773 K.