JP2000109971A - Method and device for producing thin film by raman shift pulse laser beam vapor deposition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and device for producing a thin film having smoothness of a nanometer dimension by raman shift pulse laser beam vapor deposition. SOLUTION: In this method, a thin film of a substance is formed on a substrate by irradiating a substance having a high reference molecular frequency with an ultraviolet ray pulse laser beam, making the laser beam a short wave length, generating the pulse laser beam, which is subjected to laman shift, contains a vacuum ultraviolet ray and has the output energy enough for vapor deposition and stability, and evaporating a target substance pulse with pulse laser beam vapor deposition including a laman shift vacuum ultraviolet ray. This laser beam deposition method is independent of a kind of a thin film material/substance to be produced. When a target is produced, independently of an inorganic material or an organic material, even in the case any of a metal oxide group, metal group, compound group of a semiconductor and dielectric inductive, super conductive, magnetic, conductive, insulation substances, etc., is objective substance, its crystal thin film can be produced, further, a high quality multilayer laminated layer thin film can be produced by only changing a target position sequentially.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for producing high-quality crystalline thin films and laminated thin films having nanometer-dimensional smoothness by suppressing the generation of surface particles by Raman shift pulse laser deposition. Yes, more specifically, thin films of various materials such as semiconductors, dielectrics, superconductors, magnetic materials, conductors, metal oxides such as insulators, metals, and inorganic and organic compounds, for example, The present invention relates to a method and an apparatus for producing an epitaxial (single-crystal) thin film, a crystalline thin film, an amorphous thin film, a laminated thin film thereof, an artificial lattice, and a thin film for an electronic / magnetic element of a magnetic material.

[0002]

2. Description of the Related Art As methods for producing thin films of various materials, there are a pulse laser deposition method, a sputtering method, a heating deposition method using a K cell or an electron beam, a plasma CVD method, and the like. Of which
The pulse laser vapor deposition method has features such as being applicable to both inorganic and organic materials, being capable of forming a film even under an oxygen pressure, and being easy to precisely control the composition ratio of constituent elements in the film. For that purpose, pulsed laser deposition is used for the production of devices such as metal oxides and compounds such as copper oxide-based high-temperature superconductors and manganese-based oxide giant magnetoresistive materials with complex element composition ratios. Suitable as a film forming method. However, the laser vapor deposition method has a disadvantage that surface particles are easily generated, and this is the biggest problem to be solved.

In order to develop next-generation electronic and magnetic thin-film devices such as a superconductor three-terminal device, a Josephson coupling device, a magnetic head made of a giant magnetoresistive material, and a tunnel transistor, a nanometer-dimensional smoothness is required. It is necessary to achieve the production of a high-quality crystal thin film having a high thickness and the lamination of thin films. However, none of the conventional methods has produced such a high-quality crystal thin film and a laminated thin film due to precipitation of surface particles or the like, and none of the conventional methods has been used in industry.

In the pulse laser deposition method, it is expected that a higher quality film can be produced by using a laser beam having a shorter wavelength. Therefore, argon fluoride (ArF) having a wavelength of 193 nm or 24
Ultraviolet excimer gas lasers such as 9 nm krypton fluoride (KrF) have been mainly used and studied, but they have not yet completely suppressed surface particles. N
d: A solid-state laser such as YAG has a fundamental wave (1064n
m), the second harmonic (532 nm), and the third harmonic (355 nm).
nm), the fourth harmonic (266 nm) and a harmonic generation crystal can be used to change the wavelength. When using up to the conventional third harmonic, a high-quality crystal thin film having many surface particles has not been produced.

[0005]

Under these circumstances, the present inventors have developed a Ba ₂ Cu ₃ O _y (YBCO) high-temperature superconductor by a laser deposition method using the fourth harmonic of Nd: YAG. Research on the preparation of thin films has succeeded in significantly suppressing the generation of surface particles. This is because the laser light was changed to short-wavelength light from the third to the fourth harmonic, and the pulse width of the YAG solid-state laser was narrower than that of the excimer gas laser (1/1).
3-1 / 5) is advantageous, and the surface particles can be reduced. From this, it can be seen that generation of surface particles can be further reduced by shortening the wavelength. Came to be certified.

[0006] In order to suppress the generation of surface particles and to produce a high-quality crystal thin film and laminated thin film having nanometer-order smoothness for the development of electronic and magnetic elements, a vacuum ultraviolet region with a wavelength as short as possible is required. Laser light is required. Also,
In order to form a thin film by evaporating an inorganic material by a pulse laser method, continuous and stable oscillation of pulse laser light with an output energy of several tens mJ / pulse is required. However, since there is no light source having a wavelength shorter than the 193 nm oscillation frequency of the ArF excimer laser, and having high output and stable oscillation, a pulsed laser light source in the vacuum ultraviolet region having a sufficient output and stability and a laser using the same. It is necessary to develop a method and an apparatus for producing a thin film or a laminated thin film by vapor deposition.

SUMMARY OF THE INVENTION The present invention has been made to solve such a problem, and it is intended to reduce the wavelength of a laser beam by using the Raman effect and to provide sufficient output energy and stability for vacuum deposition including vacuum ultraviolet rays. Provided are a method for producing a high-quality crystal thin film and a laminated thin film in which a Raman-shifted pulsed laser beam having the following characteristics is generated and generation of surface particles is suppressed by pulsed laser deposition using the laser beam, and an apparatus capable of embodying the method. With the goal. The present invention also provides a method and apparatus for producing a thin film by Raman shift pulsed laser deposition that suppresses generation of surface particles and enables production of a high-quality crystal thin film and a laminated thin film having nanometer-dimensional smoothness. The purpose is to:

[0008]

SUMMARY OF THE INVENTION The present invention for solving the above problems is to irradiate a substance having a high reference molecular frequency with an ultraviolet pulse laser beam to shorten the wavelength of the laser beam,
Raman-shifted pulsed laser light having sufficient output energy and stability for vapor deposition including vacuum ultraviolet rays is generated, and the target material is vaporized by pulsed laser deposition including the Raman-shifted vacuum ultraviolet rays to deposit the substance on a substrate. This is a method for producing a thin film. Further, the present invention provides the following stroke; advance (1) gas having a higher standard molecular vibration frequency [nu _f such as hydrogen and deuterium molecules in the high-pressure gas-filled tube having at both ends an optical window that can transmit light A predetermined pressure of several atmospheres to several tens of atmospheres is sealed, and an ultraviolet pulse laser beam having a frequency of ν ₀ is condensed into a sealed gas using a lens or the like from one of the windows to irradiate ν ₀ ± n a first step of efficiently generating Raman shift light having a frequency of ν _f (n is an integer) and including vacuum ultraviolet rays toward the other window; (2) setting a substrate such as an inorganic single crystal substrate or a glass substrate; The target is previously set in a vacuum chamber having a substrate holder with a heater capable of controlling the temperature and a target holder capable of setting a target of an inorganic or organic material for forming a thin film and capable of evacuating to a low pressure or vacuum. ; Then condenses irradiated with light spectrally pulsed laser beam or it was Raman shift on use lens target,
A second step of decomposing and evaporating the target material in a pulsed manner and evaporating the same to collide with the substrate is performed a predetermined number of times, and
This is a method for producing a crystalline or amorphous thin film of the substance.

Further, according to the present invention, a plurality of targets are set in advance in a vacuum chamber provided with a target holder on which a plurality of targets can be set and a substrate holder. , The second step are performed for each target sequentially for a predetermined number of pulses, and thin films (laminated thin films) of these materials are sequentially stacked on a substrate to produce a thin film (laminated thin film).

[0010] The present invention is also an apparatus for producing the above thin film, wherein a Raman shift pulse laser beam containing vacuum ultraviolet rays having a shorter wavelength is generated by filling a high pressure gas and irradiating the pulse laser beam. Laser light generating means,
Raman-shifted laser beam or a light beam obtained by splitting the laser beam is radiated to a target by changing the degree of focusing with a lens or the like that can also transmit vacuum ultraviolet rays. Vapor deposition means using a vacuum chamber having a substrate holder with a heater capable of controlling the temperature thereof and a target uniform evaporation mechanism such as a target rotation mechanism capable of setting a target and uniformly evaporating the target; It is a device which has.

Further, the present invention relates to an apparatus for producing the above-mentioned laminated thin film, wherein the means for generating the Raman shift pulse laser light, the variable irradiation means for focusing the Raman shift pulse laser light, the substrate holder and the target A vacuum chamber having a uniform evaporation mechanism and a target position moving mechanism capable of setting a plurality of targets of various substances and materials and sequentially moving each target to a laser beam condensing irradiation position is used. And a vapor deposition unit.

[0012]

Next, the present invention will be described in more detail. As described above, the present invention irradiates a substance having a high reference molecular frequency with an ultraviolet pulse laser beam to shorten the wavelength of the laser beam, including vacuum ultraviolet rays, and having sufficient output energy and stability for vapor deposition. The method is characterized in that a Raman-shifted pulse laser beam having the following characteristics is generated, and a target material is evaporated by pulse laser deposition including the Raman-shifted vacuum ultraviolet light to form a thin film of the material on a substrate. Note that the Raman effect, a substance having a reference molecule frequency of vibration frequency [nu _f, is irradiated with light such as pulsed laser light having high power the frequency of _{ν 0, ν 0 + n ν} f (n is an integer ) Frequency (anti-Stokes line) and ν ₀ −
This is a phenomenon in which light having a frequency of n ν _f (Stokes line) is generated. In order to efficiently generate short-wavelength pulsed vacuum ultraviolet light, a high-frequency and high-output ultraviolet pulsed laser light such as the fourth harmonic of an Nd: YAG laser or an ArF excimer gas laser is used as incident light. As a substance for Raman shift, it is necessary to use a molecular gas such as hydrogen or deuterium having a point symmetric molecular structure, which is a necessary condition for the Raman effect to occur, and having the highest possible reference frequency. In the present invention, as incident light,
The fourth harmonic of a Nd: YAG laser, the third and fourth harmonics of a Ti: sapphire laser, and an ArF excimer gas laser, and hydrogen, deuterium, methane, deuterated methane, Ethane, deuterated ethane and the like are preferably used, but these are not limited.

The film formation by the pulsed laser deposition method based on the Raman shift does not depend on the material or substance of the thin film to be formed. However, in describing the present invention, a pulse laser including the Raman shift vacuum ultraviolet light will be described. The facts that the present inventors have learned during the study of the preparation of a thin film of YBCO superconductor and LaPbMnO-based magnetic material and a laminated thin film of YBCO and CeO ₂ (cerium oxide) by vapor deposition,
In addition, the method of the present invention will be described in detail below by taking as an example that it has been demonstrated that a crystal thin film and a laminated thin film with higher quality than conventional methods can be produced.

In order to increase the efficiency of conversion into vacuum ultraviolet rays and produce a good quality crystal thin film, it is necessary to set the gas pressure of hydrogen gas and the like in the high-pressure gas sealing tube within the range of about 4-20 atm. There is. When a crystal thin film is formed by laser evaporation using the fourth harmonic of a conventional YAG laser, 25-4
A laser energy of about 0 mJ / pulse is required. On the other hand, in the case of film formation by the pulsed laser deposition method using the Raman shift, there is an energy loss due to light absorption and scattering by the gas in the sealed tube and absorption by a lens or the like. The fourth harmonic required about twice the energy of about 50-70 mJ / pulse. Therefore, the laser for incidence needs to be high power and variable, and in order to increase the conversion efficiency to vacuum ultraviolet rays, a variable focusing function for focusing and irradiating into the gas sealed tube is required. .

At the time of film formation, a chemical bond of a target material is cut by irradiation with a pulse laser beam, and particles such as atoms, ions, and various clusters of constituent elements are instantaneously generated and are called an ablation plume. A flame in the plasma state is generated, which strikes the substrate and forms a thin film. In this evaporating flame, the particles collide with oxygen and an oxidation reaction occurs. The quality and electromagnetic properties of the thin film greatly depend on the energy and the degree of oxidation of the particles in the evaporating flame at the time of film formation and, therefore, the shape, size and color of the evaporating flame. In addition, in the Raman shift pulse laser deposition method, light of various wavelengths is mixed, and all of these lights have different focal lengths, so that the lens mainly emits light of which wavelength and to what extent on the target. The evaporation flame changes greatly depending on whether the target is decomposed and evaporated by condensing and irradiating.
For this purpose, it is necessary to use a lens that also transmits short-wavelength vacuum ultraviolet rays and change its position under vacuum or the like to make the light collection variable. Further, for example, in order to produce a crystal laminated thin film of a plurality of materials such as YBCO and CeO ₂ , both targets are placed in a vacuum chamber from the beginning, and the targets are sequentially changed without breaking the vacuum and vapor deposition is performed. There is a need.

Based on these facts, the Raman shift pulse laser vapor deposition method needs to construct and optimize the number of manufacturing means and optimization of the conditions as much as the Raman effect as compared with the conventional method. If constructed and optimized, the Raman shift pulsed laser deposition will demonstrate that it is possible to produce thin films and multilayer thin films with reduced surface particles with good reproducibility, and this can be a technology that can be used in industry. It became clear.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, an embodiment of a method for producing a thin film and a laminated thin film and an apparatus for producing a thin film and a laminated thin film according to the present invention will be described with reference to the accompanying drawings. 1 shows an embodiment, and the present invention is not limited to the embodiment.

FIG. 1 is a schematic view showing an example of the configuration of a thin film / laminated thin film manufacturing apparatus 1 embodying the method for manufacturing a thin film and a laminated thin film according to the present invention. In this embodiment, the thin-film and laminated thin-film manufacturing apparatus 1 includes a short-wavelength ultraviolet pulse laser generation unit 2 and a high-pressure gas sealing capable of sealing a gas such as hydrogen to a high pressure and generating vacuum ultraviolet rays by a Raman shift effect. A tube 3, a condensing variable lens 4 for condensing and irradiating the light from the ultraviolet pulse laser generation unit 2 into the high-pressure gas sealed tube 3, and a pulse laser beam containing vacuum ultraviolet light generated by the Raman effect Includes variable condensing irradiation means 5 for changing the degree of light condensing on the target in the vacuum chamber by changing the position, etc., and a heater that can set a substrate such as a crystal or glass substrate and control the temperature of the substrate to a high temperature A vacuum chamber 9 having a substrate holder 6 and a target holder 7 in which a target can be set, and which can be evacuated to a low pressure or vacuum by a vacuum pump 8. It was the thing.

Since the ultraviolet pulse laser generator 2 needs to have as high an output as possible and oscillate the laser light stably, the pulsed ultraviolet laser light having the highest possible frequency and the highest output, for example, Nd: YAG A fourth harmonic pulse laser or an excimer gas laser such as ArF or KrF is used. The high-pressure gas sealing tube 3 preferably has a pressure adjusting function so that the pressure of the sealing gas can be changed from several atmospheres to several tens of atmospheres to optimize the Raman shift vacuum ultraviolet ray generation efficiency and the effect on laser deposition. Equipped with a hydrogen gas cylinder 3a and a pressure gauge 3b. The high-pressure gas sealing tube 3 has a laser incident optical window 3c and an optical window for outputting Raman shift light. The incident optical window is used for irradiating an ultraviolet pulse laser beam from the laser generating unit 2. An optical window for output is made of magnesium fluoride, calcium fluoride, or lithium fluoride so that it can transmit vacuum ultraviolet rays generated by the Raman effect. Alternatively, these lenses 5a for condensing irradiation can also be used for condensing light on the target.

Since the substrate holder 6 optimizes the distance between the target and the substrate as one of the conditions when optimizing the film forming conditions, the substrate holder 6 has a linear introduction mechanism (terminal) 10 for changing the distance. To do. In addition, the target holder 7 is not only for producing one thin film, but also for setting a plurality of targets (for example, three A, B, C, etc.) and applying Raman shift vacuum ultraviolet rays so that the thin films can be sequentially laminated. A target position moving mechanism 11 such as a step motor drive for sequentially moving the target to a position where the pulsed laser light is condensed and irradiated, and a method for preventing the laser light from concentrating on one point and causing damage to the target. A target uniform evaporation mechanism such as a target rotation mechanism 12 driven by a motor is provided. In the case where a thin film of a metal oxide-based electronic or magnetic material is formed by laser deposition, the vacuum pump 8 needs to change the oxygen pressure while changing the pressure to optimize the conditions. A pressure control system 8a was provided.
The configuration of each of the above mechanisms is not limited as long as they have similar functions.

Next, the method of the present invention will be specifically described based on an example in which a crystal thin film of a YBCO superconductor is manufactured using the laser-evaporated thin film manufacturing apparatus configured as described above.

1) Method A disk-shaped target such as a YBCO superconductor is set on a target holder 7 in a vacuum chamber 9. The target is rotated by a target rotation mechanism 12 for preventing the laser beam from concentrating on one point and causing damage to the target. Washed SrTiO
₃ (STO) Substrate holder 6 with heater
, And the vacuum chamber is once evacuated to a high vacuum. After cleaning the substrate surface by raising the substrate temperature to a predetermined temperature (about 650-800 ° C.), a small amount of ultra-high purity oxygen is introduced into the vacuum chamber, and the pressure control system 8 a connected to the vacuum pump 8 is adjusted. To a predetermined oxygen pressure (0.1-
(About 1.0 Torr). A predetermined pressure (approximately 4 to 20 atm) of hydrogen is introduced into the high-pressure gas sealing tube 3 for Raman shift.
To introduce.

After performing the above operation in advance, the fourth harmonic of the YAG pulse laser is condensed into the high-pressure gas sealing tube 3 by using the converging lens 4, and is irradiated with the vacuum ultraviolet pulse by the Raman effect. Generates laser light. The pulsed laser light including the vacuum ultraviolet light is condensed and irradiated on the target by the converging variable irradiation means 5, and the target material is ablated toward the substrate in a pulsed manner, and the YB is irradiated on the substrate.
A crystal thin film of CO is prepared. At the time of film formation, in addition to the conditions in a normal laser vapor deposition method, that is, various conditions such as a substrate temperature, an oxygen pressure, and a laser frequency, the conditions accompanying the Raman shift laser vapor deposition method, that is, hydrogen gas in a high-pressure gas sealed tube The pressure, the output of the fourth harmonic of the YAG laser, the focusing distance in the high-pressure gas sealing tube, and the focusing density of the Raman shift pulse laser light including vacuum ultraviolet rays on the target were optimized as follows. Substrate temperature: 740 ° C, oxygen pressure: 50P
a, laser frequency: 1 Hz, hydrogen gas pressure: 5 atm, Y
The output of the fourth harmonic of the AG laser: 70 mJ / pulse, the focusing distance in the high-pressure gas sealed tube: 45 cm, the focusing density of the Raman shift pulse laser beam: about ² J / cm ² / pulse. Through the above process, a crystal thin film of the YBCO superconductor was produced.

2) Results a) The characteristics of the crystal thin film of the YBCO superconductor produced by the experiment of the Raman shift pulse laser deposition method described above,
b) Comparison with the characteristics of a thin film produced by a conventional laser vapor deposition method using the fourth harmonic of YAG is shown in FIGS. 2, 3, 4 and 5.
Shown in FIG. 2 shows the temperature dependence of the electric resistance. The superconducting transition temperature of both thin films is about 89K, which is comparable to each other. However, looking at the electrical resistance in the temperature range above the transition temperature, the sample prepared by the Raman shift pulse laser vapor deposition method of a) shows a value less than one third of the sample of b). It can be seen that the thin film has better quality.

As shown in the X-ray diffraction spectrum of the thin film in FIG. 3, the films prepared by both the laser deposition methods a) and b) are both (h00); h = 1-3 of the STO crystal used for the substrate.
Other than the X-ray diffraction line of
l); only consists of the diffraction spectrum of l = 1-11, but the intensity of the diffraction line is generally stronger in the thin film of a).
This indicates that although a single-crystal thin film having both c-axis orientations was prepared, a) is a better quality crystal film.

Further, scanning electron microscope (SEM) photographs of the thin films of FIGS. 4 and 5 (upper figure: 1 μm, lower figure: 10 μm)
As shown in FIG. 4A, the film produced by the Raman shift pulse laser deposition method shown in FIG. 4A has a more impurity surface particle than the thin film produced using the conventional YAG fourth harmonic shown in FIG. Have been greatly reduced and their size has become extremely small. From the above, it can be seen that the film produced by the Raman shift pulse laser vapor deposition method of a) has improved surface quality by suppressing generation of surface particles.

FIG. 6 is an X-ray diffraction spectrum of a two-layer sample in which YBCO and CeO ₂ are sequentially formed by the Raman shift pulse laser deposition method. In addition to the (h00) of the STO crystal used for the substrate;
(001) of CO superconducting crystal; l = 1-11 and CeO ₂
Since only the diffraction spectrum of (h00); h = 2, 4 of the crystal is obtained, it indicates that a high-quality crystal layered thin film of YBCO / CeO ₂ has been produced.

[0028]

As described above, the method and apparatus for producing a thin film and a laminated thin film according to the present invention include a system for generating a Raman shift pulsed laser beam including vacuum ultraviolet rays by the Raman effect and a method for condensing the laser beam on a target. The variable condensing irradiation system that irradiates with varying degrees of irradiation and the vacuum chamber system are organically combined to suppress the generation of impurity surface particles that could not be produced with the conventional YAG fourth harmonic. As a result, it is possible to produce a crystalline thin film of a high quality material such as YBCO.

Moreover, the laser deposition method of the present invention does not depend on the type of material or substance of the thin film to be formed. In other words, as long as the target can be produced, it does not depend on whether it is an inorganic material or an organic material, and also a metal oxide, a metal or a compound such as a semiconductor, a dielectric, a superconductor, a magnetic, a conductor, or an insulator. The crystalline thin film can be manufactured for any of the above, and a high-quality multilayer laminated thin film can be manufactured only by sequentially changing the target position.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus 1 for producing a thin film and a laminated thin film by a Raman shift pulse laser deposition method.

FIGS. 2A and 2B are respectively a Raman shift pulse laser deposition method and a YBC produced by a pulse laser deposition method using a fourth harmonic of a Nd: YAG pulse laser.
It is a characteristic curve figure which shows the temperature dependence of the electric resistance of O superconducting crystal thin film.

FIGS. 3A and 3B respectively show a Raman shift pulse laser deposition method and a YBC produced by a pulse laser deposition method using the fourth harmonic of a Nd: YAG pulse laser.
3 is an X-ray diffraction spectrum of an O superconducting crystal thin film.

FIG. 4 is a scanning electron microscope (SEM) photograph of the surface of a YBCO superconducting crystal thin film produced by a Raman shift pulse laser deposition method.

FIG. 5 is a scanning electron microscope (SEM) photograph of the surface of a YBCO superconducting crystal thin film produced by a pulsed laser deposition method using the fourth harmonic of a Nd: YAG pulsed laser.

FIG. 6 is an X-ray diffraction spectrum of a YBCO / CeO ₂ two-layer laminated thin film produced by the Raman shift pulse laser deposition method.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 thin film and laminated thin film manufacturing apparatus 2 ultraviolet pulse laser generating unit 3 high pressure gas sealed tube for generating Raman shift pulse laser light 4 variable focusing lens 5 variable focusing irradiation means 6 substrate holder with heater 7 target holder 8 vacuum Pump 9 Vacuum chamber 10 Linear introduction mechanism (terminal) 11 Target position moving mechanism 12 Uniform evaporation mechanism such as target rotation mechanism

Claims (5)

[Claims] 1. A material having a high reference molecular frequency is irradiated with an ultraviolet pulse laser beam to shorten the wavelength of the laser beam, and contains Raman shift having sufficient output energy and stability for vapor deposition including vacuum ultraviolet rays. A method of generating a pulsed laser beam, and evaporating a target material by pulsed laser deposition including the Raman-shifted vacuum ultraviolet light to form a thin film of the material on a substrate. Wherein following step: (1) the number previously gases with high standards molecular vibration frequency [nu _f such as hydrogen and deuterium molecules in the high-pressure gas-filled tube having at both ends an optical window that can transmit light A predetermined pressure of from atmospheric pressure to several tens of atmospheric pressure is sealed, and an ultraviolet pulse laser beam having a frequency of ν ₀ is condensed into a sealed gas using a lens or the like from one of the windows to irradiate ν ₀ ± n ν a first step of efficiently generating Raman shift light having a frequency of _f (n is an integer) and including vacuum ultraviolet rays toward the other window; (2) setting a substrate such as an inorganic single crystal substrate or a glass substrate, In a vacuum chamber that has a substrate holder with a heater that can control the temperature and a target holder that can set a target (target substance) made of an inorganic or organic material for forming a thin film and that can evacuate to a low pressure or vacuum. Beforehand A target is set, and Raman-shifted pulsed laser light or light obtained by dispersing the Raman-shifted light is focused and irradiated on a target using a lens to decompose and evaporate the target material in a pulsed manner and collide with a substrate. 2. A method for producing a thin film by laser vapor deposition, wherein the two steps are performed a predetermined number of times to produce a crystalline or amorphous thin film of the substance. 3. A plurality of targets are set in advance in a vacuum chamber having a target holder on which a plurality of targets can be set and a substrate holder, and a first step and a second step are performed. 3. The method for producing a thin film according to claim 2, wherein the step of performing the predetermined number of pulses is sequentially performed for each target, and the thin films of those substances are sequentially laminated on the substrate. 4. An apparatus for producing a thin film according to claim 2, wherein said high-pressure gas filling tube for Raman shift is capable of generating a Raman shift pulse laser beam containing vacuum ultraviolet light having a short wavelength by irradiating a pulse laser beam. Means for irradiating a target with Raman-shifted pulsed laser light or light obtained by dispersing the pulsed laser light by changing the degree of light collection by a lens or the like that can also transmit vacuum ultraviolet light, and an inorganic unit. A substrate holder with a heater capable of setting a substrate such as a crystal substrate or a glass substrate and controlling the temperature to a high temperature; a target uniform evaporating means such as a target rotating mechanism for setting a target and uniformly evaporating the target; And a vacuum chamber comprising: a thin film production apparatus by vapor deposition. 5. An apparatus for producing a thin film according to claim 3, wherein said high-pressure gas filling tube for Raman shift is capable of generating a Raman shift pulse laser beam containing vacuum ultraviolet light having a short wavelength by irradiating a pulse laser beam. Means for irradiating Raman-shifted pulsed laser light or a light obtained by dispersing the same with a lens or the like capable of transmitting vacuum ultraviolet rays with a different degree of light collection and irradiating the target with Raman-shifted pulsed light; A target uniform evaporation mechanism such as a target rotation mechanism for uniformly setting and evaporating a target, and a plurality of targets of various substances and materials can be set and each target can be set. And a target position moving mechanism capable of sequentially moving to a laser beam condensing irradiation position, and a vacuum chamber having a Thin film production equipment.