JPS62250167A - Method and apparatus for pulse molecular ray vapor deposition - Google Patents

Abstract

PURPOSE:To control vapor-depositing conditions for a thin film of vapor depositing material with high accuracy by injecting a gaseous raw material for vapor deposition in an impulsive state onto a substrate surface at the time of depositing the thin film of a metallic oxide, etc., onto the substrate surface by a vacuum deposition device. CONSTITUTION:The Ti vapors generated by electron ray heating vapor sources 11, 12 using Ti as vapor source are deposited by evaporation onto the quartz substrate 19 by opening shutters 16, 17 at the time of heating the substrate 19 in a vacuum vessel 13 by a heater 18 and forming the thin film of TiO2, etc., onto the surface thereof. The gaseous O2 from a pulse molecular ray generator 1 is then impulsively injected onto the surface of the substrate 19 to oxide the Ti and to form the thin film of TiO2. The generator 1 injects the gas such as O2 introduced from a pipeline 9 under a high pressure impulsively from an ejection port 3 by the impulsive contraction of a high speed ejection gas shutting device 4 consisting of a piezo-electric element using a pulse voltage generator 5. The thickness of the TiO2 film on the substrate 19 can be controlled by adjusting the opening and closing of shutters 16, 17 by rock crystal type film thickness gages 14, 15.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to an improved vacuum evaporation method and apparatus, and more particularly to a vacuum evaporation method and its method for supplying a vapor of a evaporation material to a vacuum evaporation apparatus in a pulsed manner. Regarding equipment.

[Prior art]

Conventionally, in a vapor deposition method called chemical conversion vapor deposition, a vapor deposition material gas having a relatively high pressure of about 10 Torr is introduced into a vapor deposition container in a vapor deposition apparatus, or is evaporated under reduced pressure while being introduced. The evaporation material was deposited on the evaporation material.

However, in such a chemical vapor deposition method, it takes time to introduce and stop the vapor of the vapor deposition material into the vapor deposition container, and it is difficult to precisely control the vapor deposition conditions.

Moreover, since the average degree of vacuum in the vapor deposition container is lowered by introducing the vapor deposition material gas, it has been impossible to analyze the vapor deposited film each time.

[Purpose of the invention]

The present invention solves the above-mentioned conventional drawbacks, can quickly cut off the supply of the vapor deposition material gas flow to the vacuum evaporation apparatus, enables precise control of the evaporation conditions, and also allows the deposition film to be controlled during evaporation. The purpose of the present invention is to provide a vapor deposition method and apparatus that can perform on-site analysis.

[Structure of the invention]

The pulsed molecular beam evaporation method of the present invention achieves the above object,
The method is characterized in that the vapor deposition material is deposited on the material to be deposited by injecting a gas flow of the vapor deposition material in a pulsed manner onto the material to be deposited in the vacuum evaporation apparatus.

Further, the pulsed molecular beam evaporation apparatus of the present invention is composed of a combination of a pulsed molecular beam generation apparatus and a vacuum evaporation apparatus, and the pulsed molecular beam generation apparatus includes a container containing a vapor of a vapor deposition material, and an inner side of the ejection port of the container. The device is characterized in that it comprises a high-speed cutoff means for the ejected gas flow, and a pulse voltage generation source connected to the means.

First, the pulsed molecular beam evaporation apparatus of the present invention will be explained based on the drawings.

FIG. 1 shows an embodiment of a pulsed molecular beam generator that is combined with a vacuum evaporation apparatus in the present invention.

The pulsed molecular beam generator 1 includes a container 2 containing a vapor of a deposition material, a high-speed cutoff means 4 for the ejected gas flow provided inside a gas flow nozzle 3 formed in the container 2, and this high-speed cutoff means 4. The container 2 normally contains a vapor deposition material gas of 10 atmospheres or less, and this gas 2 is introduced through a valve 8 and a pipe 9.

Here, the gas flow in the present invention refers to not only normal gas flow but also all forms of things that can move in the gas phase, such as metal vapor, metal clusters, ultrafine particles, and ions. It also includes flow.

Therefore, in this sense, the present invention is not limited to molecular beams, but is directed to beams in a wide range of gas phases.

The high-speed blocking means 4 for the ejected gas flow includes, for example, a piezoelectric element 6,
Alternatively, it is formed from an electromagnetic solenoid element, or an element having an equivalent function, and a gas flow outlet closing member 7 bonded to the tip of this element 6.

The gas outlet closing member 7 is made of a highly hard material, such as tungsten carbide, or a resin, such as pyton, and the surface thereof in contact with the gas outlet 3 is polished smooth.

This closing member 7 is normally pressed against the spout 3 by the vapor of the vapor deposition material contained in the container 2, and prevents the vapor deposition material gas from leaking from the spout 3.

From the pulse voltage generation source 5, a voltage of 80 to 14 is applied to the piezoelectric element 6.
A pulse voltage of 0 V is applied, the piezoelectric element 6 contracts, and the vapor deposition material gas contained in the container 2 is ejected from the ejection port 3.

When the application of the pulse voltage is stopped, the shape of the piezoelectric element 6 is restored to its original shape, and the closing member 7 comes into contact with the jet nozzle 3 again and closes the jet nozzle 3.
will be closed.

By repeating application and termination of the pulse voltage to the piezoelectric element 6 in this manner, the vapor deposition material gas is ejected from the ejection port 3 in a pulsed manner.

A cooling mechanism, such as a coolant circulation pipe, is attached to the outer wall of the container 2 in order to prevent performance deterioration of the piezoelectric element 6 due to radiant heat from the vapor deposition material.

The vapor deposition material gas ejected in a pulsed manner from the ejection port 3 is transferred to a vacuum vapor deposition device (not shown) combined with a pulsed molecular beam generator.
The vapor is guided to the material to be vapor-deposited and irradiated onto the material to be vapor-deposited, and thereafter the material is vapor-deposited by following the same process as in a normal vapor deposition apparatus.

Here, in the present invention, the vacuum evaporation device combined with the pulsed molecular beam generator is not particularly limited;
For example, in addition to a normal vacuum evaporation apparatus, a cluster ion beam apparatus, a evaporation apparatus using a Knudsen cell, an ionization evaporation apparatus, an ion sputtering apparatus, a magnetron sputtering apparatus, etc. can be mentioned.

The amount of vapor deposition material gas irradiated onto the material to be vaporized by the pulses is determined by the duration Δt of the pulse voltage applied to the piezoelectric element, the pressure of the vapor deposition material gas introduced into the container 2, and the number of pulses. It can be changed.

In addition, in the present invention, although it is possible to form the vr# film of the evaporation material on the material to be evaporated using only the above-mentioned pulsed molecular beam generation device, the evaporation material gas flow formed by the pulsed molecular beam generation device can be It can also be used in combination with a gas flow generated by any deposition material gas generator.

In this case, evaporation is performed by supplying the gas flow generated by the pulsed molecular beam generator to the material to be evaporated, either in combination with the gas flow from other evaporation material gas flow generators, or alternately.

Furthermore, two or more of the pulsed molecular beam generators can be incorporated into the same vapor deposition apparatus at the same time.

In this case, vapor deposition is performed by operating two or more pulsed molecular beam generators simultaneously or alternately.

Furthermore, the pulsed gas flow from the pulsed molecular beam generator can be activated by electrons, ions, or light to promote deposition on the material to be deposited.

Next, the functions of the pulsed molecular beam evaporation apparatus of the present invention will be described in the case where the pulsed molecular beam generation apparatus is combined with a vacuum evaporation apparatus having an electron beam heating evaporation source.

In FIG. 2, a pulsed molecular beam generator 1 is combined with two electron beam heating evaporation sources 11 and 12 to form a vacuum evaporation apparatus 13.

The electron beam heating evaporation sources 11 and 12 can each control the evaporation speed using a crystal film thickness meter 14 and 15, and when a predetermined film thickness is reached, the shutter mechanism 1 is activated.
6.17, it is possible to block the beams from the evaporation sources independently.

In this manner, the beams generated by the electron beam heating evaporation sources 11 and 12 are irradiated onto the material to be evaporated 19, such as the evaporation substrate, which is maintained at a predetermined temperature by the heating device 18, to perform evaporation.

On the other hand, the pulsed evaporation material gas generated in the pulsed molecular beam generating bag W1 is evaporated simultaneously with the beam from the evaporation source 11.12, or after the evaporation is performed with the beam from the evaporation source 11.12, the pulsed molecular beam generator The operation of ejecting the pulsed gas flow from 1 a predetermined number of times is alternately repeated until the total film thickness on the deposition substrate 19 reaches a predetermined value.

The thickness, composition, and structure of the film on the vapor deposition substrate 19 can be determined by momentarily analyzing the analysis pattern from the surface of the vapor deposition film using high-speed electron diffraction devices 20 and 21.

〔Effect of the invention〕

As described above, according to the present invention, a pulsed evaporation material gas flow is formed by the high-speed gas jet cutoff means, and this gas flow is supplied to the vacuum evaporation apparatus, so that the entire vacuum evaporation apparatus has a vacuum atmosphere. By making the pressure thicker (without changing it), only the gas pressure near the material to be evaporated can be controlled at high speed.

Further, the degree of vacuum can be maintained at a degree sufficient to operate a high-speed electron beam diffraction device or a mass spectrometer, and a deposited film can be analyzed on the spot during thin film production.

Therefore, a thin film whose composition and structure are well controlled can be formed on the material to be deposited.

Examples of the present invention will be described below.

〔Example〕

A thin film of titanium oxide was formed on a substrate using the pulsed molecular beam evaporation apparatus shown in FIG.

Titanium vapor generated by the electron beam heating evaporation source 11.12 is evaporated by 2.25 people onto a quartz substrate 19 maintained at 700°C at a deposition rate of 0.5 people/see, and then the pulsed molecular beam generator 1 Oxygen gas was introduced at a back pressure of 0.34 atm, and a pulsed gas flow was injected onto the substrate 19 N times under conditions of a pulse applied voltage of 120 V and a pulse width of 3 m5 ec.

This cycle was repeated 600 times to obtain titanium oxide thin films shown in Table 1 below.

The compositions of the titanium oxides in Table 1 were confirmed to be single-phase by X-ray diffraction.

The pulsed gas flow from the pulsed molecular beam generating bag ffl is injected into the vacuum evaporation device 13 with a half-width of 3 tt+set, and after the injection ends, the degree of vacuum in the container of the vacuum evaporation device returns to the base vacuum within 10 m5 ecl. Ta.

Moreover, the pulsed oxygen flow from the pulsed molecular beam generator is treated as a molecular beam with directionality based on #i! Since the gas is injected onto the substrate 19, it is possible to increase the effective gas partial pressure on the substrate while keeping the average degree of vacuum in the container of the vacuum evaporation apparatus low.

In addition, in FIG. 2, two electron beam heating evaporation sources 11 and 12 are shown.
It is possible to fabricate a multilayer VIt film by using this in combination with a shutter mechanism 16.17, but it is also possible to fabricate a multilayer N film such as TiO/TiN by using two or more pulsed molecular beam generators. can.

In this case, N2 gas can be used as the nitrogen source, but depending on the case, the reaction can also be promoted by ionizing the N2 beam.

With the conventional method of introducing gas into the container of a vapor deposition apparatus using a gas introduction valve, it was difficult to exchange or exhaust the atmospheric gas at high speed. was almost impossible.

[Brief explanation of drawings]

FIG. 1 is a schematic explanatory view showing an aspect of a pulsed molecular beam generator used in the pulsed molecular beam vapor deposition apparatus of the present invention, and FIG. 2 is an explanatory view of the pulsed molecular beam vapor deposition apparatus of the present invention. 1... Pulse molecular beam generator, 2... Evaporation material gas storage device, 3... Jetting port, 4... Jetting gas flow high-speed blocking means, 6... Pulse voltage generating source. Patent applicant: Director of the Agency of Industrial Science and Technology Tatsu Todoroki Figure 1 Figure 2

Claims (1)

[Claims] 1. Pulsed molecular beam evaporation, characterized in that a gas flow of the evaporation material is injected in a pulsed manner onto the material to be evaporated in a vacuum evaporation apparatus to deposit the evaporation material onto the material to be evaporated. Method. 2. Consisting of a combination of a pulsed molecular beam generator and a vacuum evaporation device, the pulsed molecular beam generator includes a container containing the vapor of the evaporation material, and a high-speed interruption of the ejected gas flow provided inside the ejection port of the container. A pulsed molecular beam evaporation apparatus comprising: means; and a pulsed voltage generation source connected to the means.