JPS59128234A - Formation of multilayered film on surface of substrate - Google Patents

Abstract

PURPOSE:To form plural ceramic layers on a glass substrate by evaporating a metal in a vacuum vessel contg. the substrate while introducing different gases each forming ceramics by combination with the metal with the lapse of time. CONSTITUTION:A glass substrate 8 is suspended in a vessel 1 for reactive vacuum deposition by heating with electron beams, the vessel 1 is evacuated to a high degree of vacuum, and a metal 5 in a water-cooled copper hearth 4 is evaporated by heating with electrons emitted from a filament 3. At this time, a gas forming ceramic by combination with the metal 5 is introduced through a valve 6a and reacted with vapor of the metal, and the resulting ceramics is deposited on the substrate 8. The gas is then changed over to other gas, and other ceramics formed by the reaction of the gas with vapor of the metal is deposited on a layer of said ceramics. A multilayered transparent ceramic film is formed by using O2 and F as gases when the metal is Mg or Ce; O2, F, NH3 and N2 as gases when the metal is Al; O2, N2 and C2H2 as gases when the metal is Ti or Ta; and N2 and C2H2 as gases when the metal is Si.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of forming a multilayer film on the surface of a substrate such as a glass by a physical method.

Conventionally, physical vacuum evaporation, sputtering, and ion plate ink methods are known as methods for forming a helical multilayer film on the surface of a substrate such as glass. Forming multilayer films by such physical methods requires the separate evaporation of multiple raw materials. Therefore, in forming a multilayer film using this method, it is necessary to set individual evaporation conditions suitable for each raw material, J.
5 and its operation is complicated.

Furthermore, multilayer films formed by conventional physical methods have a tH point in the adhesion between the multilayer films. Therefore, the multilayer film (
It has the disadvantage that it is weak against mechanical abrasion and easily peels off (and also easily generates fine racks).

The present invention is based on the conventionally known method for forming a reactive physical film, and forms a multilayer film composed of at least two types of compounds on the surface of a substrate by changing the reaction gas without changing the evaporation substance. This invention provides a new physical multilayer film formation method.

The method of forming a multilayer film on the surface of a substrate according to the present invention involves evaporating metal in a high vacuum atmosphere, causing the evaporated metal to react with a gas in the atmosphere, and causing Ml to react on the substrate surface. In a method of forming a compound film, a reactive gas in the atmosphere is changed over time, and a multilayer film consisting of at least two different compounds/ζ layers is formed on the surface of a substrate. What are the characteristics?

d3 Steam destination here Outside means evaporation in a broad sense, and spatter.

Substrates used in the method of the present invention include glass plates, glass optical components, transparent plastic plates, transparent glass optical components, and the like. This substrate is not particularly limited to a transparent substrate, but its selection is limited depending on the purpose of the multilayer film coating, thin film formation conditions, etc. For example, when forming a multilayer film at a relatively high temperature for the purpose of preventing reflection of visible light or increasing reflection of heat rays, glass plates or glass optical components are used.

The metals that are evaporated substances used in the method of the present invention include magnesium, cerium, titanium, tankle, aluminum, and silicon (which is originally a metalloid but is included in the metals herein). <'c d3 The above metals include alloys consisting of two or more metals.The reactive gas used in the method of the present invention may be one that becomes a gas under the reaction conditions, including oxygen, These include fluorine, nitrogen, ammonia, nortylene, ethylene, etc. In the method of the present invention, by changing the reactive gas over time, the reactive gas is reacted with the evaporated metal to form a multilayer film, so that the metal teeth,
It is specified in relation to the reactive gas used. That is, it is necessary for the metal to react with the reactive gas used (to form a stable solid compound). Therefore, when the reactive gas is fluorine, metals such as titanium, silicon, In addition, only one type of metal is used in the method of the present invention, and since the reactive gas used is one on two pairs, it reacts with the reactive gas on two pairs, and the reactive gas on =0 is used. It must be a metal that forms stable compounds.The metal must also react with a reactive gas to form a transparent multilayer film (although this is not specified, When the purpose is to form an optical interference film using a multilayer film, it is desirable that the multilayer material is transparent.For example, when the metal is magnesium and the gases are oxygen and fluorine.

From the above, the combination of metal and reactive gas used is
For magnesium and cerium, it is oxygen, fluorine, etc. For aluminum, it is oxygen, fluorine, ammonia or nitrogen, etc. For titanium and tantalum, it is oxygen, nitrogen, aleburene, etc. For silicon, it is nitrogen. , aretylene, etc., and other metals can also be combined with specific reactive gases.

(1) When changing the reactive gas orally in the method of the present invention, the decrease in one gas can be inversely proportional to the increase in the other gas. In this method, two types of gases coexist in the boundary region forming opening N between the multilayer crotches. Each of these two types of gas and one type of metal react, and a boundary region 461 is formed by the two types of metal compounds.

In the method of the present invention, it is extremely easy to introduce two types of reactive gases into the same reactor over time, and it is also easy and simple to stack J5 membranes alternately by reacting them with metal alternately. It is. Moreover, since it is sufficient to use one type of metal and there is no need to evaporate a plurality of metals or metal compounds under individual conditions suitable for each, the operation for forming a multilayer film becomes extremely easy. Therefore, according to the method of the present invention, a multilayer film can be formed more easily and conveniently than conventional physical methods.

Further, according to the present invention, it is possible to mix the hooking compound produced by the reaction of both gases in the boundary area between the multilayer crotches. In such a case, the multilayer film has extremely good adhesion because the - compound changes from the other compound without showing a boundary line. Therefore, the multilayer film is resistant to mechanical abrasion and is not easily peeled off. Moreover, it becomes possible to laminate more multilayer films, and the function as a thin film is greatly improved.

The present invention will be explained below with reference to Examples.

Example 1 Figure 1 is a schematic cross-sectional view of a reactive vacuum deposition apparatus using electron beam heating (Fig. 2 shows an enlarged cross-section). ))
Here's an explanation.

First, the inside of the vacuum reaction tank 1 is passed through the valve 2 to 1Q -
A high vacuum of 51-o'rr or less is used. The electrons ejected from the filament 3 heat the magnesium 5 in the water-cooled copper hearth 4 and evaporate the magnesium. Next, the reactive gas oxygen is introduced into the barrier pull leak valve 6a, and at the same time, the shutter 7 is turned on to react magnesium and oxygen in a high vacuum. 1 layer) Avoid forming 9.

Immediately before the formation of a predetermined film thickness is completed, the barrier pull leak valve 6a is slowly turned down by 11 ft, and at the same time, another same valve 6b is slowly turned on, and another reactive gas, fluorine, is simultaneously cut off and vacuumed. Introduce it into the reaction tank. During this time, fluorine and oxygen are introduced at the same time, so two types of compounds, magnesium oxide and magnesium fluoride, coexist within the layer. After forming the predetermined mixed layer 10, the barrier pull leak valve 6a is completely closed. After that, a thin layer (second layer) 11 of only magnesium fluoride is formed. 21st
Immediately before the thin film i;
I? ? 4. Forming the magnesium fluoride layer 15. By this method, a 4-layer multi-layer structure is formed in which 9.13 layers of magnesium oxide and 1 ml of magnesium fluoride and 1 ml of magnesium fluoride are alternately stacked.

"The enlarged cross-sectional view of the four-layer film formed by the above method is shown in the second figure.
Accept the illustration.

The thickness of the four layers formed by the above method is 1510.1900.1510111 in order from the first layer to the fourth layer.
111, 95071 ngs 1 - one step wrong. As a result, the relationship between the reflectance for each wavelength as shown in Fig. 3 is shown, and the average visible light reflectance is less than 1%, so it has very high utility value as an antireflection film.
``Due to the presence of a mixed layer at the boundary between membranes, the adhesion between the membranes is excellent.

Example 2 Similar to Example 1, this example is a method of forming a multilayer film of cerium oxide and cerium fluoride on the surface of a glass substrate using the reactive chemical vapor deposition method using electron beam heating.

However, in this embodiment, in order to make the boundary surface of the multilayer film smooth, other gases are introduced after removing as much of the remaining gas as possible.

Using hylium as the metal and using oxygen and fluorine as the reactive gas, oxide AVi (first layer) was formed on the Nocolas substrate in the same manner as in Example 1, and then fluoride was used to form the lithium layer < a12 layer. ) are roughly alternately formed with layers of each compound to form a 6-layer film. .

- A 6@ film can be easily formed on a glass base plate by the opening method. And the thickness of those six layer films is 1140.1600.1140 respectively from the first layer to Figure 6.
．． 1600.1140.800 Angus 1-mouth-11
[7. Example 1.2 is a reactive vacuum F/TA'Z
Although the method was explained using the method, the well-known reaction 1
The above multilayer film can also be easily formed by the C sputtering method.

[Brief explanation of the drawing]

Fig. 1 is a schematic cross-sectional view of a reactive vacuum evaporation apparatus for forming a multilayer film, Fig. 2 is an enlarged cross-sectional view of the multilayer film obtained in Example 1, and Fig. 3 is a multilayer film of Fig. 2 (Example 1). It is a '9' diagram showing the characteristics of the film and showing the relationship between the wavelength of incident light and the reflectance. 1... Vacuum reaction tank 2... Vacuum adjustment valve 3
...Filament 4...Water-cooled copper hearth 5...
Gold h7JX 6a, (31)...Barrier pull leak valve 7...
Shi17 Tsuta 8... Crow board 9.13...
Magnesium oxide layer 11.15... Magnesium fluoride layer 10.12.1
/'I...Mixed layer of magnesium oxide and magnesium fluoride Figure 1 Figure 3

Claims (1)

[Claims] (1) A metal is vaporized in a high vacuum atmosphere, the evaporated metal is reacted with a gas in the atmosphere, and the reaction occurs on the substrate surface. A method for forming a film of a compound containing at least two different compounds (11z) is formed on the surface of a substrate by changing the reactive gas in the atmosphere over time. A method for forming a multilayer film on the surface of a substrate, characterized in that the metal is magnesium or relium, and reaction 1
11. The method according to claim 11, wherein the one gas is oxygen and fluorine. (3) The method according to claim 1, wherein the substrate is a glass plate. (4) The method according to claim 1, wherein when changing the reactive gas in the atmosphere, the decrease in one gas is inversely proportional to the increase in the other gas.