JPS59502062A - Chemical vapor deposition method for titanium nitride film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Titanium nitride and its equivalents How to wear film chemistry Background of the invention Adjusting the amount of solar energy that enters windows helps maintain comfortable indoor conditions in warm regions. is important. Window materials have also been developed to reduce intense light. solar heat Conditioning is commonly accomplished by adding absorbing colorants to the glass. deer However, the tinting of the glass by this means may take a long time or change the shade. This is disadvantageous in manufacturing as there may be problems. Recently, reflective and absorbing films have been developed on glass. It is applied to make the sun transparent and to regulate solar heat. Reflection completely eliminates radiation Reflection of unwanted radiation is even more effective than absorption because it eliminates absorption, whereas absorption The final part is ultimately brought to the building.

The method of applying reflective and absorbing solar control films is well known in the field of glass manufacturing. well known. For example, films of metals such as chromium or nickel are commercially available. , and evaporate or spray onto the glass in a vacuum using equipment well known in the art. ter) to be done.

Good quality reflective and absorbent films are produced by vacuum methods, but the cost is rather expensive. Examples of metal oxides include mixtures of chromium oxide, cobalt oxide, and iron oxide. Spray pyrolysis (5p ray pyrolysis). A similar film is Chemical vapor deposition methods such as those described in U.S. Pat. No. 3,850,679 and U.S. Pat. By pyrolysis of fine powder materials as described in U.S. Patent No. 4,325.988 It is formed.

These films are not as reflective as vacuum-deposited metals, but are cheaper to produce. be able to. These have limited sources and must be imported into the United States. Requires materials such as free cobalt and chromium. Chromium and nickel also cause cancer. are suspected of occurring and therefore pose a safety risk for widespread use of such coated products. Integrity is being questioned.

U.S. Pat. No. 3,885,855 describes metals TI, Zr, llf, V, Nb, T a, Reactive sputtering of nitride, carbide or boride of Cr, Mo or W It is also proposed to produce solar thermal control films by effective optical Although properties are known for some of these materials, reactive sputtering Large-scale production of architectural glass by vacuum-electrical methods is rather expensive.

The machine tool industry takes advantage of titanium nitride's hard, relatively thick, opaque, wear-resistant coating. I am using it. These coatings are exposed to nitrogen, hydrogen and and titanium tetrachloride reaction mixture. However, Japanese Patent 74-83 No. 679 and Zuicho Patent No. 397,370 disclose such wear-resistant coatings, and All of them are functionally opaque and combust with ammonia at temperatures within the range of 550°C. produced by reaction with titanium tetrachloride and at least about 3 microns thick. be.

U.S. Pat. No. 4.31.0.567 describes the formation of nitride films, but solar heat There is no disclosure of how a thin transparent film can be provided for use.

Bitzer, U.S. Pat. No. 4,196,233 also describes a nitride coating method. It is listed.

Summary of the invention Chemical vapor deposition by reactive vapor mixture onto the surface of heated glass It is an object of the present invention to provide a very fast method for depositing control coatings.

Another purpose is to add a line to the float glass line if such a combination is desired. Depositing solar control films quickly in a continuous process including methods suitable for combinations It is in.

Furthermore, the objective is to provide a solution to atmospheric pressure without the need for complex and expensive vacuum and electrical equipment. The purpose of this method is to carry out the precipitation process using simple and inexpensive equipment that operates in a controlled manner.

Yet another objective is to produce products that are inexpensive and do not require rare, imported or expensive raw materials. By using abundant raw materials, we can achieve the goals listed in item 1.

A particular object of the present invention is the high speed formation of titanium nitride films on glass substrates. By developing a reaction with ammonia that allows titanium chloride to The purpose is to take advantage of the volatility and reactivity of um.

Another object of the present invention is solar control. There is a film to offer.

Other objects of the invention will become apparent to those skilled in the art after reading the invention.

The present invention utilizes a metal-containing compound such as titanium tetrachloride and a reducing gas such as ammonia. Take advantage of the reaction between you and your partner. The metal-containing compound and the reducing gas are each It is contained in the carrier gas and reacts close to the heated glass surface.

The temperature of the glass surface is 400°C or higher, preferably about 600'C or higher. When the precipitation rate is the fastest and the quality is optimal. Of course, many glass substrates are soft. and has a practical processing limit of about 700°C. The borosilicate glass of the present invention It appears to be a particularly desirable substrate for the production of products. Titanium tetrachloride and A preferred reactant combination of ammonia is a film that reacts quickly and adheres strongly. The composition of the film is similar to that of some chlorine which is also included in the film. The main material is titanium nitride, TiN. The deposition atmosphere is free of oxygen and water vapor. Otherwise, the deposited film will be the desired titanium nitride layer. It will consist primarily of titanium oxide rather than aluminum. very small amounts of oxygen and Water and water appear to be tolerated when excess ammonia is used. Chi dioxide Tanium increases the number of reflections from the glass surface, but titanium nitride does not allow much light to pass through. Doesn't absorb much.

The film should be smooth, mirror-like, and free from fog. thin film, example For example, films with a thickness of about 200 angstroms have a reflective silver color, but thicker films have a silver color. As the thickness approaches 0.1 micron, the color changes to gold, light blue, gray, black, reddish, and brown. It's a color. Transmitted color is achromatic color (neu tral), gray, pale yellow, pale green, pale blue, and brown.

The mechanical properties of the film are good. Abrasion and scratch resistance compared to commercially available glass Comparable or better than solar thermal control films. The chemical resistance of the film is Excellent against water, soap, bases, and acids excluding hydrofluoric acid, which corrodes both film and glass. Endure.

Titanium nitride films are also electrically conductive. This property is better than solar heat control film. It has other uses. This is used to detect broken windows, such as in a burglar alarm system. It can be used as part of an electrical circuit to generate electricity.

Drawing description The drawing is a sectional view of a device suitable for carrying out the coating method.

The new method involves careful heating of the reaction between a metal-containing halogen reactant and a reducing gas. degree control is achieved with film-forming reactants, and normal adducts of such reactions. 5 to avoid the formation of powder Most importantly, it is avoided since it imparts undesirable haze to the transparent glass substrate.

The final method uses an extremely large excess of reducing gas to minimize the amount of halogen remaining in the film. It can be made easier by using some amount of oxygen remaining and halogens do not have a detrimental effect on the properties of the coating. In fact, small amounts of halogen are In rare cases, it promotes color regulation and electrical properties. For example, the internal properties of the film In a film thick enough to have a color dominated by It has a tendency to change color from gold to red to black.

Titanium tetrachloride and ammonia react at room temperature to form a solid addition compound. Therefore, these reactants are mixed very close to the heated glass surface to be coated. must be The temperature of the gas at the mixing point is over 200°C, but about 40°C. It should be less than 0'C. If the mixing temperature is too low, some solids addition may occur. The compound coats or blocks the coating equipment. On the other hand, if the temperature exceeds about 500°C, Mixing the gas at a higher temperature will result in a film sticking on the glass rather than the device. Second, powdered titanium nitride products and/or films are likely to result. Mixed The preferred temperature range for this is about 250-320°C.

The apparatus for carrying out the mixing and coating is shown in cross-section in FIG. heated glass The ribbon 10 is placed on a roller, such as in a cooling layer (LEHR) during glass manufacturing. - (not shown)" 2 to the side. 4 mixed with a carrier gas such as nitrogen. Titanium chloride vapor is introduced into a distribution conduit 12 across the width of the heated glass ribbon 10. .

The titanium tetrachloride vapor mixture is then passed through the flow const The narrow distribution line elongated hole 16 (distribution slot 'l and then sent to mixing zone 18. Inert gas such as nitrogen The ammonia, which has also been diluted with the rear gas, enters the distribution conduit 22 and enters the medium narrow opening 24 and and is sent to the mixing zone 18 through the distribution line slot 26. Narrow opening 14.24 in the flow is gas of the glass ribbon to provide a uniform distribution of reactants and a uniform thickness of the coating. Evenly distributed across the width. Layer 28 is a thermally insulating layer whose thickness is equal to that of the distribution line. It is chosen so that the temperature of the gas in the elongated hole 16.26 is maintained within the desired range.

The gas mixture in band 18 flows over the surface of heated glass 10 and is directed to exhaust conduit 30. It will be done. During this flow process, a film of titanium nitride is deposited on the surface of the heated glass. Served. Several coating steps are applied in a series to form the desired film thickness. The glass ribbons are placed side-by-side during their single passage through the capping device. In fact, the use of multi-stage coating equipment In some applications, non-uniformity in one coating device is usually inconsistent with the others or in different coating devices. It tends to eliminate some of the thickness error from the coating, thus promoting uniform coverage.

Air and water vapor must be excluded from the deposition area where drying agents such as nitrogen A flow of inert gas is provided through conduits 32 on all sides of the coating apparatus.

The coating device is also reversed and placed under the glass. placed under glass The advantage of having a coating WW is that the coating or powder by-products that are formed remain on the surface of the coating equipment. This means that such materials have no chance of reaching the surface of the glass and therefore This will impair the uniformity of the coating. Thus, the time between cleaning the coating equipment is longer when the coating device is below the glass than when it is on the top surface of the glass.

The coating equipment is corrosive, including the reactant titanium tetrachloride and the by-product hydrogen chloride. exposed to gas. Therefore, the coating device should be constructed of corrosion-resistant materials. Nike and nickel-based alloys containing Ni, Cr, Mo, and W (e.g. Hastero Cabot (trademark of Cabot Corporation) is a particularly suitable construction material.

The concentration and flow rate of the reactant vapors are such that a large stoichiometric excess of ammonia is present. are selected as such. Otherwise, large amounts of chlorine will be retained within the coating. For example, 5~ 50 moles of ammonia are used for each mole of titanium tetrachloride. mixed moth Typical concentrations of titanium tetrachloride are 0.1-0.5 mol% and 1-5% ammonia. It is in the near range. Lower concentrations result in lower coating rates, while higher concentrations result in excess powder. give rise to formation.

Another feature is that the coating is mixed very close to the glass on which it is deposited. patent The treatment described in No. 3.979.500 produces the desired film formation without haze or powder. can be avoided to achieve.

The temperature of the glass is typically 400-700°C when the coating is applied. low Temperatures produce very slow reaction rates - powdery or coarse, hazy coatings generate. The preferred temperature range is about 500 to 650 degrees Celsius.

Articles formed in accordance with the present invention are suitable for solar radiation, where light transmission in the range of 1 to 40% is typically desired. It is of particular value in thermo-conditioning operations. This is a metalloceramic hard alloy (cement). early wear-resistant coatings used on ed carbide) and other mechanical materials. More than the transmitted non-sensible light (t) It is an order of magnitude.

Illustrative embodiments of the invention The present application and accompanying drawings illustrate and describe preferred embodiments of the invention and various aspects thereof. Although variations and modifications are suggested, these are not intended to be exhaustive and may be helpful to others. Changes and modifications may be made within the scope of the invention. In this , these suggestions may be used by others skilled in the art to fully understand the invention and its principles. selected and included for the purpose of explanation for understanding the , each of which can be modified and implemented to best suit the conditions of a particular case. It is something that

Example 1 Three pieces of borosilicate glass heated to about 590°C are placed in series as shown in Figure 1. The coating equipment was moved at a speed of 20 am/sec.

Each coater was coated with a mixture containing 0.4 mole percent titanium tetrachloride vapor in nitrogen. through conduit 12 and through conduit 22 with a mixture of 4 mole percent ammonia in nitrogen. Supplied. The total flow rate of all gases entering each coating device is Approximately 2507 per meter inside! /min.

The inlet slot 16.26 of each coating device terminates approximately 3 cm above the surface of the glass to be coated. ing.

The coated glass is transparent brown in color and has a visible light transmittance of approximately 10%. coating has a conductivity of about 100 ohms per square and a low infrared reflectance of about 6 00 people thick.

Example 2 of the claims using a concentration of 0.5% titanium tetrachloride and 0.5% ammonia. The method described in Range 1 was repeated. The film is heated to 600°C. Deposited with a 4 second exposure of an acid glass (Pyrex glass) substrate. total solar radiation A film was formed that allowed transmission of only 20% of the radiation.

It is. However, these metals are more expensive than Ti and are less abundant.

Therefore, titanium nitride is Zr, Hf', V, Nb, Ta, It is more preferable than nitrides of Cr, Mo, and -. salt to transport these metals Bromide or iodide can be used instead of chloride, but the high cost and Low volatility makes chloride advantageous in this process.

Carbides and borides of the metals mentioned above can be used in place of the nitrides. Some carbides are Formation by known chemical vapor deposition methods requires high reaction temperatures; These carbide precipitations are made incompatible with conventional glass processing methods. metal boride Although materials such as diborane can be formed by chemical deposition at temperatures suitable for glass processing methods, Preferred, more reactive sources of boron are expensive. Therefore, the nitride More preferred than carbides and borides.

In all cases of the above compounds, the mixing temperature should be below the reaction temperature and the mixing should be This should be done just before the glass is near the heated glass surface, and the temperature of the glass should be The height should be high enough to form the desired inorganic product just as precipitation occurs. There must be.

The glass-coated film of the present invention has particularly desirable properties, including Used to block solar radiation. For example, to block 85% of all solar heat, A sufficiently thick film blocks only 75% of visible light. This is according to the present invention. Many solar control films produced block even 75% of visible light. Even thin enough to block less than 75% of total solar radiation.

Additionally, the titanium nitride films of the present invention can be used in the thermal infrared range of wavelengths, e.g. At 10 microns, it has an emissivity of 0.3 or less, typically 0.1 to 0.2. Ru. Therefore, they are used in air conditioning whose main purpose is to reduce solar radiation entering windows. It has good thermal insulation properties when used as architectural glass for building windows. discount rate It is comparable to These ranges are typically 0.5 to 0.9.

Such films deposited by the method of the invention not only possess the above-mentioned advantages. (type K based on chromium, silicon or mixed oxides of cobalt, chromium, iron) It has better abrasion resistance than commercially available solar control films.

The following claims cover all the general and specific features of the invention as set forth herein. It is intended to encompass all descriptions of the scope of the invention that fall therein. It should also be understood that

Submission of translation of written amendment (Article 184-7, Paragraph 1 of the Patent Act) Mr. Manabu Shiga, Commissioner of the Patent Office 1. Indication of patent application PCT/US 831016 '783, patent applicant Mr. Gorton Roy Gierardo 6. List of attached documents (1 translation of the 11th Amendment Scope of request for amendment 1. a) Gas of titanium tetrahalide vapor reactant and inert carrier gas produces a mixture of b) an ammonia reactant such as a nitrogen donor and a reducing gas; and C) two of the aforementioned gases. of the glass substrate on which the gas mixture is heated (nearby the reaction products are formed on said glass substrate). The glass substrate is heated by the mixing process so that A method of depositing solar control films consisting of tanium.

2. The method according to claim 1, wherein the halide is a tetrachloride.

3. The final mixing of the tetrachloride and the ammonia is in the range of about 200-400°C. 2. The method of claim 1, which is carried out within the scope of the present invention.

4. The method according to claim 1, wherein the substrate is heated to a temperature of 500°C or higher.

5. Claim in which 25 to 50 moles of ammonia are mixed with 1 mole of titanium tetrachloride The method according to item 2 of the scope of the invention.

6. The titanium tetrahalide is titanium tetrabromide or titanium tetrahydride. A method according to claim 1.

7, a) Metal Ti,, Zr, 1(f1ν, Nbs Tas Cr, Mo-, , one or more halide reactants of W in an inert carrier gas. produces a gaseous mixture that b) a second gas mixture of a nitrogen donor reactant, a reducing gas and an inert carrier gas; generate things, c) in the immediate vicinity of the glass substrate on which the two said gas mixtures are heated, the reaction products are Gold is heated on a glass substrate by a mixing process to form on a glass substrate. Genus Ti, Zr, Hf, ν, Nb, Ta, Cr, Mo, W transparent absorbing and reflective solar control films of one or more nitrides. How to precipitate.

8. The film transmits more visible light than total solar radiation, and about 0.3 A nitride produced by the method according to claim 3 characterized by the following emissivity: A transparent glassware containing a titanium solar control film thereon.

9. The thick material according to claim 8 comprising sufficient residual halogen to modify the color. Solar control film.

10. Improved abrasion resistance comparable to silicon- and chromium-based solar control films The solar heat regulating film according to claim 8, characterized in that:

11. The final mixing of the tetrachloride and the ammonia is in the range of about 200-400°C. 3. The method of claim 2, wherein the method is carried out at a temperature within the range.

12. The method according to claim 3, wherein the substrate is heated to a temperature of 500° C. or higher.

13. The titanium tetrahalide is titanium tetrabromide or titanium tetrahydride. A method according to certain claim 3.

Mr. Manabu Shiga, Commissioner of the Patent Office 1. Indication of case PCT/US 831016783, person making amendment Relationship to the case: Applicant Name Gorton Roy Gerald 5. Date of amendment order: September 11, 1981

Claims (1)

[Claims] 1.8) Gathering of titanium tetrahalide vapor reactant and inert carrier gas producing a slushy mixture; b) an ammonia reactant and a reducing gas such as a nitrogen donor and an inert carrier; G) a gas mixture capable of heating the two said gas mixtures; The reaction products are mixed in close proximity to the glass substrate so that the reaction products are formed on said glass substrate. A solar heat treatment consisting mainly of titanium nitride on a glass substrate that is heated by a process of Method of depositing conditioning film. 2. The method according to claim 1, wherein the halide is a tetrachloride. 3. The final mixing of the tetrachloride and the ammonia is about 200-400"C. 2. The method of claim 1, wherein the method is carried out at a temperature within a range. 4. The method according to claim 1, wherein the substrate is heated to a temperature of 500°C or higher. 5.5 to 50 moles of ammonia are mixed with 1 mole of titanium tetrachloride. The method described in Scope 1. 6. The titanium tetrahalide is titanium tetrabromide or titanium tetraiodide. A method according to claim 1. 7.8) Metal Ti, Zr, tlf, V,, Nb, Ta, C Inert cap of one or more halide reactants: r, Mo, W producing a gaseous mixture in the rear gas; b) a second gas mixture of a nitrogen donor reactant, a reducing gas and an inert carrier gas; generate things, cLIn the immediate vicinity of the glass substrate where the two gas mixtures are heated, the reaction products are The gold on the glass substrate is heated by a mixing process so that it forms on the glass substrate. One or more of the genus Ti, zr, V, Nb, Ta, Cr, Mo SH For depositing more nitride transparent absorbing and reflective solar control films Law. 8. The film transmits more visible light than total solar radiation, and about 0.3 Titanium nitride solar control film characterized by the following emissivity: 9. The thick material according to claim 7 comprising sufficient residual halogen to modify the color. Solar heat control film. 10. Improved abrasion resistance comparable to silicon- and chromium-based solar control films 8. The solar heat regulating film according to claim 7, characterized in that: