JPH0253508B2 - - Google Patents

Description

Detailed Description of the Invention The present invention creates an excess state of electrons around a metal electrode, and when many types of ions that form a compound arrive at this metal electrode, the probability of covalent bonding of many types of ions is increased. This relates to a supersaturated electron type ion plating method that takes advantage of the high density.

In general, compounds such as intermetallic compounds and ceramics are considered to have two or more types of atoms in close contact with each other, and their outer electrons are covalently bonded. Since there are many electrons in the molten metal, it is easy to form compounds, but in a vacuum,
Because atoms and electrons exist separately,
Even if atoms are in close contact with each other in an ionic state, the probability of forming a compound is low if there is a lack of electrons.
In addition, metals are neutral because they have just the right amount of electrons, and even when a negative voltage is applied to the metal electrode to collect ions, there are no electrons on the surface of the electrode. It is thought that there is just the right amount of excess and deficiency, and when ions reach that electrode, electrons are supplied from the electrode to which a negative voltage is applied, and these electrons form covalent bonds, forming an alloy. being judged.

Therefore, in the conventional ion plating method,
Research and development has been carried out on the shape of the electrode, the temperature of the evaporated metal, the evaporation method, how to create ions, the excitation method (high frequency method) to increase the temperature of atoms, etc., but the conditions for ions to bond are not yet detailed. No experimental research had been conducted on it, and it remained unknown.

In consideration of the above points, the present invention connects a diode to the electrode substrate to prevent electrons from flowing from the electrode substrate, irradiates the water-cooled crucible with electrons generated by the first electron gun, and irradiates the water-cooled crucible with the electrons generated by the first electron gun. By irradiating the electrode substrate with electrons generated by a gun and creating a state of excess electrons around the electrode substrate, many types of ions that form compounds arrive there.
It is characterized by increasing the probability of covalent bonding, and its purpose is to provide a supersaturated electron type ion plating method that can easily form compounds such as intermetallic compounds or ceramics even in a vacuum. Embodiments of the present invention will be described in detail below with reference to the drawings.

First, the inventor discovered that in the general ion plating method, the areas where very good ion plating is applied are areas with an excess of electrons, and there are more electrons than in the electrode substrate on which the compound is made. It was confirmed through experiments that very good ion plating was achieved in the areas where the ions gathered. For example, even in a magnetically deflected electron beam reactor, in which the electron stream emitted from an electron gun is deflected by a magnetic field and irradiated onto the evaporated metal placed in a water-cooled crucible, very good ionization occurs in the part where the restrained electrons gather. It was confirmed that plating was possible.
Therefore, the present invention is characterized in that a good product can be manufactured by creating a condition in which good ion plating can be performed around the substrate electrode, which is a workpiece in a vacuum chamber.

FIG. 1 shows a block diagram for carrying out the method of the present invention, in which 1 is a water-cooled crucible, a metal 2 to be alloyed is placed on top of this water-cooled crucible 1, and this water-cooled crucible 1 is It is connected to the positive side of the DC power supply 3. 4 is a first electron gun consisting of a magnetic field type electron gun, and the electrons generated by this first electron gun 4 are deflected by an external magnetic field 5 provided obliquely above the irradiation port of the first electron gun 4. and irradiates the metal 2.
6 is an electrode substrate, a workpiece 7 is attached to this electrode substrate 6, an anode of a diode 8 is connected to the electrode substrate 6, and a cathode of this diode 8 is connected to the negative side of the DC power source 3. . 9
is a second electron gun consisting of an electrostatic electron gun, and the workpiece 7 is irradiated with electrons generated by this second electron gun 9. In addition, the DC power supply 3 and the diode 8
The rest are provided inside the vacuum chamber 10.

Next, the operation of this embodiment will be explained. First, the first
When the electrons generated from the electron gun 4 are deflected by the magnetic field 5 and irradiated onto the metal 2 on the water-cooled crucible 1, the metal 2 is melted, evaporated, and ionized. Here, secondary electrons are generated when the metal 2 evaporates, but these secondary electrons are deflected by the external magnetic field 5 and do not reach the workpiece 7 of the electrode substrate 6. Therefore, the metal 2 evaporates and reaches the workpiece 7, and the gas that forms a compound with the metal 2 in the vacuum chamber is ionized by the electrons from the first electron gun 4 and reaches the workpiece 7. However, the disadvantage is that it is difficult to form compounds.

Therefore, in the present invention, a second electron gun 9 is provided,
The electrons generated by this second electron gun 9 are transferred to the workpiece 7.
irradiate. Here, since the electrons irradiated onto the workpiece 7 of the electrode substrate 6 do not flow to the DC power supply 3 due to the diode 8, the area around the electrode substrate 6 and the workpiece 7 becomes oversaturated with electrons. When the workpiece 7 is irradiated with electrons in this way, the workpiece 7 is heated to near the annealing temperature, so the surface of the workpiece 7 is cleaned in vacuum and the surface is activated. Therefore, in a supersaturated state of electrons, the evaporated metal or metal ions react with the reactive gas ions, giving the surface of the workpiece 7 a very hard surface without changing the overall structure of the workpiece 7. Compounds, ceramics, or alloys with high ion plating properties can be made to provide highly adhesive ion plating. Further, since good ion plating is performed on the part irradiated with electrons from the second electron gun 9, ion plating can also be performed on a desired part of the workpiece.

Note that the electrons irradiated from the second electron gun 9 to the workpiece 7 are accelerated to the voltage (5000v) between the filament and the anode of this second electron gun 9, but the electrode substrate 6 is at a negative voltage. (2000v), the electrons below this negative voltage are at the electrode substrate 6.
However, this does not pose any problem; the unreached electrons are useful for ionizing the reactant gas and vaporized metal.

FIG. 2 shows a block diagram for carrying out the method of the present invention, in which 1 is a water-cooled crucible, 2 is a metal to be combined, 3 is a DC power supply, 4 is a first electron gun, 6 is a water-cooled crucible;
is an electrode substrate, 7 is a workpiece, 8 is a diode, 1
0 is a vacuum chamber, and since the configuration thereof is the same as in the previous embodiment, a description thereof will be omitted. 11 is a control device, 12 is a measurement electrode, 13 is a current detector, 14
is a plasma generator, 15 is a plasma electron gun, 1
6 is a plasma power supply, 17 is a reaction gas supply port, 1
8 is a plasma extraction electrode, and 19 is a coil electrode.

Next, the operation of this embodiment will be explained. First, in order to generate a reactive gas plasma (a state in which the same number of + ions and - ions are floating) from the plasma generator 14, a reactive gas that combines with the metal 2 is supplied from the reactive gas supply port 17. The plasma electron gun 15 enters a plasma state, is extracted by a plasma extraction electrode 18, focused by a coil electrode 19, and irradiated onto the workpiece 7. Irradiating the workpiece 7 with this plasma results in the same state as irradiating the workpiece 7 with electrons from the second electron gun 9 in the embodiment described above.

On the other hand, the first electron gun 4 is an electrostatic electron gun,
When the metal 2 is irradiated with electrons generated by the first electron gun 4, the metal 2 is evaporated and ionized. This ionization rate is detected by the measurement electrode 12, the current flowing through the measurement electrode 12 is detected by the current detector 13, and the control device 11 controls the current supplied to the first electron gun 4 based on the detection signal. .

Also in this embodiment configured in this way, similarly to the second electron gun 9 of the above-described embodiment, the electrode substrate 6 is irradiated with plasma generated by the plasma generator 14 onto the workpiece 7. and workpiece 7
A state of supersaturation of electrons is created around the surface of the workpiece 7, and the ions of the metal 2 generated from the water-cooled crucible 1 and the reaction gas ions generated in the plasma generator 14 are covalently bonded, and a very hard compound is formed on the surface of the workpiece 7. A membrane can be created.

In addition, in the explanation of the above embodiment, it was explained that reactive gas ions and metal ions are sent to a place where there are supersaturated electrons around the substrate electrode 6 and the workpiece 7 to form a compound on the surface of the workpiece 7. Not only this, but if the workpiece is a metal, if many electrons are sent to the surface of the metal, the surface of the workpiece will be heated by the electron beam and become high temperature.
Therefore, some of the gas adsorbed on the surface of the workpiece reacts with the metal to form a compound (and evaporates when heated to a higher temperature), but at that time, a small amount of a metal that easily forms compounds, such as titanium, is deposited. However, if the aforementioned ion plating is then performed, an even harder film will be formed on the surface of the workpiece. Furthermore, in the above embodiment,
Although an example in which an electromagnetic type electron gun is used as the first electron gun 4 has been described, it goes without saying that an electrostatic type electron gun can also be used in the same manner. Furthermore, the ion plating device proposed by the present inventor (patent application 1983-
151892), it goes without saying that a second electron gun for irradiating the workpiece can be provided as in the method of the present invention.

As explained above, according to the present invention, by creating a supersaturated state of electrons around the workpiece using the second electron gun and the plasma generator, and sending metal ions and reactive gas ions in this state, Very good ion plating can be performed on the surface of the workpiece.

[Brief explanation of drawings]

FIG. 1 is a block diagram for implementing the method of the present invention, and FIG. 2 is a block diagram for implementing another method of the present invention. DESCRIPTION OF SYMBOLS 1... Water-cooled crucible, 2... Metal, 3... DC power supply, 4... First electrode gun, 5... External magnetic field, 6...
... Substrate electrode, 7 ... Workpiece, 8 ... Diode, 9 ... Second electron gun, 10 ... Vacuum chamber, 11
...Control device, 12...Measurement electrode, 13...Current detector, 14...Plasma generator, 15...Plasma electron gun, 16...Plasma power supply, 17...
... Reaction gas supply port, 18 ... Plasma extraction electrode, 19 ... Coil electrode.

Claims (1)

[Claims] 1 In the ion plating method, in which two or more types of atoms are combined in a vacuum to form a compound such as a ceramic or an intermetallic compound on a workpiece of an electrode substrate, the electrode substrate and a water-cooled crucible are placed in a vacuum chamber with a space between them. The electrode substrate is connected to the anode of the diode, the diode is connected to the negative side of the power source through a resistor, the water-cooled crucible is connected to the positive side of the power source, and the parts other than the electrode substrate are connected to the anode of the diode. The metal of the water-cooled crucible is irradiated with electrons generated from a first electron gun provided in the water-cooled crucible to generate ionic atoms of the metal, and the electrons generated from the second electron gun or ion generator are irradiated with the metal of the water-cooled crucible. In a state in which the workpiece of the electrode substrate is irradiated, electrons are prevented from flowing from the electrode substrate by a diode connected to the electrode substrate, and a large amount of electrons are suspended around the electrode substrate. A compound of the reactive gas ionized by the electrons and the metal is formed on the electrode substrate by feeding ionic atoms of the metal, or a compound of the metal and the electrons is formed on the electrode substrate. Supersaturated electrons characterized by forming a compound of the reactive gas and the metal on the electrode plate by making the number of electrons larger than the amount of ions in a plasma state where approximately the same number of ions exist. type ion plating method.