JPS6313323A - Manufacture of thin film and device therefor - Google Patents

Abstract

PURPOSE:To efficiently form a thin film of good quality at high speed by a method wherein the surface of a substrate only is brought to the thermal decomposition temperature or above at which a compound thin film constituent element is precipitated, and the temperature of the inner wall part and the like of a reaction chamber is controlled in such a manner that it will be maintained within the temperature range between the temperature at which said compound is not condensed and the lower temperature limit or less at which the thin film constituent element is precipitated. CONSTITUTION:Warm air of 45 deg.C is circulated in a heat retaining chamber 9, and raw material containers 1a-1d, the triisobutyle aluminum 2a and 2b contained in said raw material containers, and raw material introducing tubes 10a-10d are maintained at the temperature of 45 deg.C. Also, a part of the inner wall of a reaction chamber 4 is maintained at the temperature of 45 deg.C by circulating the warm water 3a-3h of 45 deg.C. After the reaction chamber 4 has been evacuated to 1-10<-6> Torr using an exhaust system 8, the surfaces of substrates 6a-6h are heated up to 260 deg.C by the heater built-in in a susceptor. The shutting-off valves provided on the raw material introducing tubes 10a-10d are opened, the TIBA 2a-2d which are evaporated at 45 deg.C are introduced into the reaction chamber 4 from raw material introducing holes 11a and 11d, and aluminum is deposited on the substrates 6a-6h. As a result, the speed of deposition of a thin film can be increased, and a flat thin film of good quality and high purity can be manufactured easily.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method and apparatus for producing a thin film using a hydrocarbon-based organic compound or an inorganic compound containing elements constituting the thin film as a raw material, and particularly relates to a method and an apparatus for producing a thin film using a hydrocarbon-based organic compound or an inorganic compound containing elements constituting the thin film.

Using an organic compound in which atoms such as Ga, As, Ti, and Si are bonded to hydrocarbon groups such as alkyl, allyl, and aryl groups, by chemical vapor deposition, low pressure chemical vapor deposition, or molecular beam epitaxy, The present invention relates to a method for efficiently depositing a high-quality thin film containing the above elements at high speed, and an apparatus suitable for carrying out the method.

[Conventional technology]

As a compound containing the constituent elements of the thin film, for example, an organic aluminum compound is used as a raw material, and low pressure chemical vapor deposition (LPC) is used.
According to the method of manufacturing an aluminum thin film using the VD method (VD method), it is possible to form an aluminum thin film with high purity and excellent coverage.

Therefore, research and development of LPCVD methods and devices for application to the formation of wiring aluminum thin films for miniaturized semiconductor devices, etc., is actively progressing. Regarding the LPCVD method and apparatus for forming aluminum thin films using triisobutylaluminum (TIBA), which is a type of conventional organic aluminum compound, as a raw material, see, for example, Japanese Patent Application Laid-open No. 163793/1983 and Solid State Technology December issue (1982). ) pages 62 to 65 (Solid 5tate Techno
logy, December (1982) pp6
2-65]. These LPCVs
In method D and apparatus, aluminum is deposited by heating the reaction vessel from the outside and keeping it above the decomposition temperature of TIBA, so that unnecessary parts such as the inner wall of the aluminum decomposition reaction vessel are This method has disadvantages in that much of the aluminum is precipitated and adheres, and the amount of aluminum deposited on the required substrate is small, the aluminum deposition rate is significantly reduced, and the deposition efficiency is extremely poor.

[Problem that the invention seeks to solve]

In the apparatus described in the December issue of Solid State Technology (1982), which is representative of the conventional LPCVD method described above, the substrate on which aluminum is to be deposited is heated by a heater provided outside the reaction vessel. For this reason,
The temperature of the inner wall of the reaction vessel near the substrate is approximately 22°C, which is the lower limit temperature at which aluminum is precipitated by thermal decomposition of TIBA.
The temperature must be higher than the surface temperature of the substrate, which is set at 0° C. or higher. In an LPGVD device with such a heating structure, most of the vaporized TIBA introduced into the reaction vessel undergoes thermal decomposition on the inner wall of the reaction vessel, where the temperature is higher, and is consumed before reaching the substrate. The problem of putting it away arises. In addition, in conventional LPGVD equipment,
The formed aluminum thin film is said to have excellent coverage and extremely high purity, but the aluminum deposition rate does not depend much on the flow rate of vaporized TIBA introduced into the reaction vessel, and is approximately 30 nm/min at most. It was nothing more than Furthermore, there is a problem in that the surface of the formed aluminum thin film is rough, and when viewed microscopically, considerable unevenness occurs on the thin film surface. The cause of this deterioration in the smoothness of the aluminum thin film is unknown, and the conventional T
In the method of manufacturing an aluminum thin film by the LPCVD method using IBA as a raw material, it was currently considered impossible to obtain an aluminum thin film with a sufficiently smooth surface.

In the conventional LPGVD apparatus, even if the flow rate of vaporized TIBA introduced into the reaction vessel was simply increased, the effect of increasing the flow rate of introduction was hardly realized. This is because, as mentioned above, the inner wall of the reaction vessel is heated to a temperature higher than the surface temperature of the substrate installed in the vessel, and a large amount of TIBA is thermally decomposed on the inner wall of the reaction vessel. This is believed to be because the flow rate of TIBA reaching the surface of the substrate on which the thin film is formed hardly increases. Furthermore, the deposition rate of aluminum on the substrate close to the introduction port of the vaporized TIBA into the reaction vessel differs significantly from that on the substrate far away, resulting in a problem that the thickness of the formed thin film becomes non-uniform.

In this way, in conventional equipment for producing aluminum thin films by the LPCVD method using TIBA as a raw material, little consideration is given to controlling the temperature of the inner wall of the reaction vessel in which the substrate is installed, so the flow rate of the organoaluminum compound is increased. Therefore, it has been extremely difficult to increase the deposition rate of aluminum on the substrate and improve the quality of the aluminum thin film.

As a result of extensive research, the present inventors have found that, for example, when forming an aluminum thin film using the LPCVD method, the organic aluminum compound is prevented from being consumed on the inner wall of the reaction vessel, and more organic aluminum is produced than in the conventional method. We have successfully developed a method for producing aluminum thin films in which the compound reaches the substrate surface, as well as an apparatus for carrying out the method. It has been found that by this method, the aluminum deposition rate can be dramatically increased, and a high-quality aluminum thin film with a substantially smooth surface can be obtained. Furthermore, the organoaluminum compound is not limited to TIBA, but also organoaluminum compounds such as other trialkylaluminiums, alkylaluminum halides, and alkylaluminum hydrides;
Or M, Ga, As, T, which are elements constituting the thin film.
Regarding organic compounds in which atoms such as i, SL, and hydrocarbon groups such as alkyl, allyl, or aryl groups are bonded, or inorganic compounds containing the above elements, an increase in the flow rate of these compounds is caused by the formation of It has been found that there are effects such as increasing the deposition rate of thin films of Ga, As, TL Si, etc., and improving the purity and quality of thin films.

The purpose of the present invention is to produce high-quality materials by chemical vapor deposition (CVD), LPCVD, or molecular beam epitaxy (MBE) using hydrocarbon-based organic or inorganic compounds containing elements constituting thin films as raw materials. An object of the present invention is to provide a method that can form a thin film efficiently at high speed, and an apparatus for implementing the method.

[Means to solve the problem]

The object of the present invention is to use a hydrocarbon-based organic compound or an inorganic compound containing elements constituting a thin film as a raw material.
In a method of forming a thin film on a substrate surface by a VD method, an LPCVD method, or an MRE method, only the temperature of the substrate surface is set to be higher than the thermal decomposition temperature at which the thin film constituent elements of the above compound are precipitated, and the vaporized above compound is introduced and passed through. This is achieved by providing a means for controlling the temperature of the inner wall portion of the reaction vessel, etc., within a temperature range above the temperature at which the above-mentioned compound does not condense (Tv) and below the lower limit temperature (Tp) at which the thin film constituent elements precipitate. Ru. The elements constituting the above thin film are M, Ga, As, Ti, Si, etc., and organic compounds in which these elements are bonded to hydrocarbon groups such as alkyl, allyl, or aryl groups, or inorganic compounds containing the above elements. It is a compound. Hereinafter, for convenience, the case of aluminum will be specifically explained as an example.

For example, using organic aluminum compounds as raw materials.

When forming an aluminum thin film by the LPCVD method, the temperature of the inner wall of the reaction vessel in which the substrate is placed is lower than the surface temperature of the substrate in which aluminum is deposited, and the vaporized organoaluminum compound is transferred from the inlet of the reaction vessel to the substrate. The temperature of part or all of the inner wall of the reaction vessel that may come into contact with it during the process of movement to the surface is set to the temperature at which the organoaluminum compound does not condense (T
v) above, and the lower limit temperature (Tp) at which the thermal decomposition reaction of the organic aluminum compound occurs and aluminum precipitates.
) The object of the present invention is achieved by providing a mechanism for controlling the temperature within a range below ). Here, Tv is 0.05
It is desirable that the temperature is such that a vapor pressure of Torr or higher can be obtained. This is because, at a vapor pressure of less than 0.05 Torr, even if the other conditions for depositing aluminum are optimal, only a fractional nium deposition rate of lonm/min or less can be obtained.

This is because extremely high airtightness is required for the device in order to increase the purity of aluminum. The term "reaction container" as used herein means a container containing a substrate and having a space that is vacuum-blocked by a valve or the like in order to minimize the volume containing the substrate.

When TIBA is used as the raw material organoaluminum compound, the temperature of the part where TIBA contacts the inner wall of the reaction vessel during the process of moving from the inlet to the reaction vessel to the substrate surface is set to be equal to or higher than the Tv temperature of TIBA. 'r
The above object of the present invention is achieved by providing a mechanism for controlling the temperature within a temperature range below the p temperature (approximately 220°C); however, if the temperature of the inner wall of the reaction vessel is above the Tv temperature,
Further favorable effects can be obtained by maintaining the temperature within a temperature range below about 70° C., which is the lower limit temperature at which IBA produces diisobutylaluminum hydride through a thermal decomposition reaction.

In the method of producing an aluminum thin film by the LPCVD method of the present invention, the organic aluminum compounds used as raw materials include organic alkyl aluminum compounds such as trialkyl aluminum, alkyl aluminum halides, and alkylaluminum hydrides. trimethylaluminum, triethylaluminum,
Tri-n-propyl aluminum, triisobutyl aluminum, diethylaluminum chloride, ethyl aluminum dichloride, diethylaluminum hydride.

Examples include diisobutylaluminum hydride. Further, a mixture of these organoaluminum compounds can also be used.

A11-Ti, Al1-8i other than aluminum thin film,
In forming thin films such as Ga-Aa-As and Ga-As, hydrocarbons containing the elements constituting these thin films and having a structure in which these elements are bonded to hydrocarbon groups such as alkyl, allyl, and aryl groups are used. Organic compounds such as organic titanium compounds, organic silicon compounds, organic gallium compounds, and organic arsenic compounds can be used. Furthermore, the constituent elements of the thin film are An, Ga, As,
Inorganic compounds containing Ti, Si, etc. may be used, or the above organic compounds and inorganic compounds may be used in combination.

[Effect]

By the CVD method, LPCVD method, or MBE method of the present invention, for example, the temperature of the inner wall of the reaction vessel in which a thin aluminum film is formed on the substrate surface is kept below the temperature of the substrate surface. Since the organoaluminum compound undergoes a thermal decomposition reaction on the inner wall of the reaction vessel and the amount of aluminum precipitated and consumed can be reduced, the flow rate of the organoaluminum compound introduced to the substrate surface can be substantially increased. The temperature of the inner wall of the reaction container that comes into contact with the organoaluminum compound during the movement of the organoaluminum compound from the inlet of the reaction container to the substrate surface is within a temperature range that is higher than the Tv temperature of the organoaluminum compound and lower than the Tp temperature of the organoaluminum compound. This prevents the vaporized organoaluminum compound from re-liquefying on the inner wall of the reaction vessel, and also prevents the precipitation of aluminum due to unnecessary thermal decomposition reaction of the organoaluminum compound on the inner wall of the reaction vessel, and prevents aluminum from reaching the substrate surface. This makes it possible to substantially increase the flow rate of organoaluminum compounds. in this way.

An increase in the flow rate of the organic aluminum compound that reaches the substrate surface significantly increases the aluminum deposition rate and has the effect of improving the purity of the aluminum thin film and the smoothness of the thin film surface, allowing high-quality aluminum thin films to be obtained at high speed. It has the effect of being

For example, when TIBA is used as the organoaluminum compound, the temperature of the inner wall of the reaction vessel that may come into contact with it during the process of TIBA moving from the inlet of one reaction vessel to the substrate surface is kept at or above the Tv temperature of TIBA. 'rp
T
It is possible to prevent reliquefaction of IBA and to prevent TIBA from being decomposed into diisobutylaluminum hydride and imbutylene, thereby preventing it.

Since the flow rate reaching the substrate surface of TIBA can be further increased, the aluminum deposition rate is further increased, and the purity and smoothness of the thin film are significantly improved.
Compared to the case where the temperature is set below the TP temperature of BA, a higher quality aluminum thin film can be efficiently produced at high speed.

〔Example〕

An example of the present invention will be described below, and further based on the drawings,
Explain in detail. Note that in the figures, the same reference numerals indicate the same parts or parts having the same performance or function.

(Example 1) Figure 1 is a schematic diagram showing the structure of an apparatus for producing an aluminum thin film by low pressure chemical vapor deposition (LPCVD) using triisobutyl aluminum (TIBA) as a raw material, which is an example of the present invention. It is a diagram.

In Fig. 1, the inside of 1 reaction vessel 4 is 5
It is possible to exhaust up to 10'' Torr. Raw material container 1
T I B A 2a to 2d are stored in a to 1d.

The temperature inside the greenhouse 9 is kept at 45℃ by circulating 45℃ warm air.
Therefore, the raw material container 18 installed in the insulating room 9
The temperature of ~1d and the TIBAs 2a~2d housed therein is 45°C, and a vapor pressure of about 0.7 Torr is obtained. 45°C through raw material introduction pipes 10a to 10d equipped with shutoff valves etc. installed in the insulating room 9 and maintained at 45°C.
TIBA2a to 2d vaporized in the raw material introduction ports 11a to 11l
id into the reaction vessel 4.

The substrates 6a to 6h are fixed to a susceptor 5 having a built-in heater, and the surface temperature thereof can be raised up to 350°C. 45°C hot water is circulated inside the susceptor upper body 7, and the surface temperature thereof is maintained at 45°C or more and less than 50°C even when the surface temperature of the substrates 68 to 6h is increased to 350°C. The temperature of the inner wall of the reaction vessel 4 at the portion that can come into contact with the vaporized TIBAs 2a to 2d introduced into the reaction vessel 4 through the raw material introduction ports 11a to lid while moving to the substrates 6a to 6h is 45°C.
Even when the surface temperature of the substrates 68-6h is raised to 350°C by circulating the hot water 38-3h, it is almost completely maintained at 45°C or higher and lower than 50°C. It goes without saying that hot air or other fluids may be used instead of the hot water 38-3 hours.

When the outer wall of the reaction vessel 4 corresponding to this part is directly exposed to 45°C warm air circulating in the insulating chamber 9 without using 38 to 3 hours of hot water, the temperature of the inner wall of the above part becomes 45°C. The temperature is maintained at ℃ or higher and lower than 220℃. According to the aluminum thin film manufacturing apparatus of this embodiment, the vaporized TI introduced into the reaction vessel 4
BA2a-2d can be brought to the surfaces of substrates 68-6h with high efficiency, and an aluminum thin film with a substantially smooth surface can be formed at high speed. Next, a method for manufacturing an aluminum thin film using the aluminum thin film manufacturing apparatus of this embodiment and properties of the manufactured aluminum thin film will be described. Warm air at 45°C is circulated in the insulating room 9, and the raw material containers 18 to 1d and the TIBA 2a contained therein are heated.
~2b, the temperature of the raw material introduction pipes 10a~10d is set to 45°C. In addition, 45°C hot water was circulated for 38 to 3 hours to form the reaction vessel 4.
The temperature of a part of the inner wall of is 45°C. After the inside of the reaction vessel 4 is evacuated to I x 10-' Torr by the exhaust system 8, the substrates 68-
The surface temperature is raised to 260°C for 6 hours. The substrates 68 to 6h used here are silicon substrates on which a thermal oxide film of 0.5-thickness is formed. Other substrates, e.g. Ga-A
An S substrate, a sapphire substrate, etc. may be used, and other films such as a nitride film, a metal film, a resin film, etc. may be formed on the substrate, and if necessary, the substrates 68 to 68 may be formed using Ar ions. A substrate whose surface has been subjected to a substrate surface activation treatment such as sputter etching may be used.Then, the cutoff valves provided in the raw material introduction pipes 10a to 10d are opened, and TIBA2a to 2d vaporized at 45°C are used as raw materials. Introduce the substrate 6 into the reaction vessel 4 through the inlet/lla~lid.
Deposit aluminum on a to 6h. TIBA2a
The total flow rate of ~2d passing through the raw material introduction ports 11a~lid is about 150mQ7 minutes. The pressure inside the reaction vessel 4 during aluminum deposition was adjusted to 0.5 Torr by a conductance adjustment valve provided in the exhaust system 8.

The aluminum deposition rate was 200 nm/min, the resistivity of the film was 2.8 μΩ·cm, and impurity analysis by Auger electron spectroscopy showed that the amount of carbon in the aluminum film was 0.3 atomic percent or less. With conventional manufacturing equipment, the deposition rate is at most 30 stops/min, and the resistivity of the thin film is 3.1 μΩ・am.
Therefore, even if the flow rate of TIBA introduced into the reaction vessel was increased, the deposition rate hardly increased and the resistivity of the film did not decrease. Furthermore, the problem of microscopic irregularities on the surface of the aluminum thin film, which was a problem when using conventional manufacturing equipment, was also significantly improved by using the equipment of this embodiment. When the thickness of the aluminum thin film was 600 nm, the local thickness distribution was approximately ±25n+a. This value was 175, compared to about ±125 nm in conventional manufacturing equipment, and an aluminum thin film with a substantially smooth surface could be formed. Note that when a part of the outer wall of one reaction vessel 4 is directly exposed to 45°C warm air circulating in the insulating chamber 9 without using hot water 3a to 3h, the aluminum deposition rate is 1100 n/min, and the film is Resistivity is 2.9μΩ
・It was cra. In addition, the thickness of the aluminum thin film is 6
00 nm, the local film thickness distribution was approximately ±50 nm.

Note that there was no significant difference in the film quality or deposition rate of the aluminum thin films deposited on the plurality of substrates 68 to 6h. This is considered to be the result of effectively making the distances from the raw material introduction ports 11a to 11lid to the plurality of substrates 68 to 6h substantially equal in the apparatus of this embodiment.

(Example 2) FIG. 2 is a schematic diagram showing the structure of an apparatus for producing an aluminum thin film by the LPCSVD method using trimethylaluminum (TMA) as a raw material, which is another example of the present invention. is 5 x 10- by exhaust system 8
' It is possible to exhaust up to Torr.

TMA 2 e in the raw material container le is maintained at 35°C by circulating hot water 3a at 35°C. The resulting vapor pressure is approximately 15T orr. When the shutoff valve 8a is opened, vaporized TMA 2 e is introduced into the reaction vessel 4 through the raw material introduction ports 11a and llb. The raw material introduction pipe 10a, lob, and cutoff valve 8a leading from the raw material container 1e to the reaction container 4 are maintained at 35° C. by circulating 35° C. hot water 3b, 3c.

Substrates 6a and 6b are placed on a susceptor 5 in the reaction vessel 4, and the surface temperature of the substrates 6a and 6b can be raised to 450° C. by the heater 12. Susceptor 5° substrate 6a,
The temperature of the inner wall of the reaction vessel 4 except for 6b is 35°C hot water 3d.
The surface temperature of the substrates 6a and 6b is increased to 450℃ by circulating ~3g of water.
Even when the temperature rises to 35°C, it is maintained at 35°C or higher and 150°C or lower.

The exhaust system is equipped with traps 14a and 14b cooled by liquid nitrogen 13a and 13b. These traps 14a and 14b are used for undecomposed T discharged from the reaction vessel 4.
While adsorbing M A 2 e, T M A 2
It has the function of adsorbing hydrocarbons generated by the thermal decomposition of e and improving exhaust efficiency during aluminum deposition.

According to the aluminum thin film manufacturing apparatus of this embodiment, it is possible to reach the surfaces of the substrates 6a and 6b at a high rate of the vaporized TMA2e introduced into the reaction vessel 4, and a high purity aluminum thin film can be formed at high speed. be able to.

Hereinafter, using the apparatus of this embodiment, the raw material inlets 11a, ll
TMA2e vaporized from b was introduced at a flow rate of about 100 m and Q 7 minutes, the surface temperature of 6a and 6b was 350°C, and the reaction vessel 4 was heated.
The properties of an aluminum thin film deposited at a pressure of 0.3 Torr will be described below. The shutoff valves 8b and 8c that adjust the conductance are opened equally, and the pressure inside the reaction vessel 4 is reduced to 0.
．． At 3 Torr, the aluminum deposition rate is 5
0 n+a/min, the resistivity of the thin film was 3.5 μΩ·cm, and the thin film contained about 2 atomic % of carbon. When the circulation of hot water 3d to 3g, which is circulated to maintain the temperature of the inner wall of the reaction vessel 4, is stopped and aluminum is deposited under the same conditions as in the conventional manufacturing equipment, the deposition rate is 30 rv/min, and the resistivity of the thin film is 5 μΩ·can, and carbon was contained in the thin film at about 5 atomic %. Note that when 3d to 3g of hot water at 35°C is circulated, the conductance adjustment shutoff valve 8C is completely closed, and the pressure inside the reaction vessel 4 is set to 0.3 Torr using only the conductance adjustment shutoff valve 8b, aluminum The deposition rate is 40 nm/min, and the resistivity of the thin film is 4 μΩ・
The carbon content in the thin film was approximately 3 JM%. The exhaust efficiency is higher when the pressure inside the reaction vessel 4 is adjusted by opening the conductance adjustment shutoff valves 8b and 8c equally. was able to form a higher quality aluminum film at a faster rate.

(Example 3) Figure 3 shows G by the LPCVD method, which is another example of the present invention.
FIG. 1 is a schematic diagram showing the structure of an apparatus for manufacturing an a-An-As thin film. In the figure, a substrate 6 is fixed to a susceptor 5 and can be heated to 1000° C. by a heater 12. The interior of the reaction vessel 4 in which the substrate 6 is installed is provided with an I
It is possible to exhaust up to 10-' Torr. TIBA2
A is housed in a raw material container 1a, and placed in a heat insulating room 9 in which warm air at 45° C. is circulated. Steam 0.7 Tor
The raw material introduction pipe 10a leading to the reaction vessel 4 for the vaporized TIBA2a of r is placed in the insulating chamber 9, and the vaporized TIBA2a in the reaction vessel 4 is maintained at 45°C from the raw material introduction port 11a to the substrate 6. There are 4 parts that come into contact during movement.
By circulating hot water 3a and 3b at 5°C, Ga-Al1”As
During the deposition, the temperature is maintained almost completely above 45°C and below 50°C. Raw materials of Ga and As are introduced from the raw material inlet 11b. As raw materials for Ga and As, triethyl gallium and trimethyl arsine are each supplied at a rate of 2.5 m/r from the raw material inlet 11b.
The pressure inside the six reaction vessels 4 in which Ga-Jing-As was deposited was 0.2 To.
rr, and the surface temperature of the substrate 6a was 600°C.

When hot water 3a, 3b at 45°C is circulated, the amount of carbon contained in the formed Ga-Al1-As thin film is reduced to about 115 compared to when no hot water is used, and the defect density on the thin film surface is about 1/2. It became.

In this example, trimethylarsine was used as the arsenic compound that is a constituent element of the Ga-An-As thin film, but the hydrogen of the inorganic compound arsenic hydride (AsH) or As H3 could be replaced with a hydrocarbon group. It has been confirmed that the same effect can be obtained using arsine, which is In addition, although the LPCVD method was described in the above embodiments of the present invention, M
The BE method is a thin film forming method based on essentially the same principle as the LPCVD method, and it goes without saying that the method and apparatus for manufacturing a thin film using the MBE method described above are included in the present invention.

In addition, in the above example, the Ga-M-
Although the method for producing an As thin film has been described above, it goes without saying that thin films other than aluminum can be formed using other organometallic compounds or inorganic compounds such as trimethyl gallium.
The method of the present invention is also effective in forming metal or semiconductor thin films such as -3i and Ga-As. but,
Particularly favorable results are obtained when applied to the deposition of aluminum using TIBA.

Furthermore, in the above examples, the case of LPCVD method was given as an example, but CVD method performed at normal pressure or MB
The method of the present invention can also be applied to method E.

〔Effect of the invention〕

As explained in detail above, the thin film manufacturing method according to the present invention can also be applied to hydrocarbon-based organic compounds containing thin film constituent elements.
It is possible to prevent inorganic compounds from being consumed on the inner wall of the reaction vessel.

Since most of it can reach the substrate surface, the deposition rate of the thin film is fast, and a very high quality thin film with high purity and a flat surface can be easily produced. especially,
When forming an aluminum thin film using an organic aluminum compound, or an organic gallium compound,
Ga
The effects of the present invention are extremely significant when forming a -Aa-As thin film or the like.

[Brief explanation of drawings]

Figure 1 is a schematic diagram showing the structure of a reduced pressure chemical vapor deposition bag (LPGVD apparatus) used in Example 1 of the present invention, and Figure 2 is a schematic diagram showing the structure of the LPGVD apparatus used in Example 2 of the present invention. A schematic diagram and FIG. 3 are schematic diagrams showing the structure of an LPGVD apparatus used in Example 3 of the present invention. 1a, 1b, 1c, 1d... Raw material container for triisobutyl aluminum (TIBA) 1e... Raw material container for trimethyl aluminum (TMA) 2a, 2b, 2c, 2d-T I B A2e...
TMA 3a, 3b, 3c, 3d, 3e, 3f, 3g, 3h-
...Hot water 4...Reaction container 5...Susceptor 6a, 6b, 6c, 6d, 6e, 6f, 6g, 6h-
... Substrate 7 ... Susceptor upper body 8 ... Exhaust system 8a, 8b, 8c ... Shutoff valve 9 ... Insulation chamber 10a, 10b, 10c, 10d - Raw material introduction pipe 11
a, llb, llc, lld...raw material inlet 12.
...Heaters 13a, 13b...Liquid nitrogen 14a, 14b...Trap

Claims (1)

[Claims] 1. Using a hydrocarbon-based organic compound or inorganic compound containing the constituent elements of the thin film as a raw material, by chemical vapor deposition method, low pressure chemical vapor deposition method, or molecular beam epitaxy method,
In the method of forming a thin film on the surface of a substrate, the temperature of the surface of the substrate placed in the reaction vessel in which the thin film is formed is as follows:
The above compound is maintained at a temperature at which it thermally decomposes and the thin film constituent elements are precipitated, and the temperature of the raw material supply system for the above compound and the inner wall of the reaction vessel is maintained at a temperature higher than that at which the above compound does not condense, and the thin film constituent elements of the above compound are maintained at a temperature above which the above compound does not condense. A method for producing a thin film, comprising forming a thin film on the surface of the substrate by controlling the temperature to be within a temperature range below the lower limit temperature for precipitation. 2. The method for producing a thin film according to claim 1, wherein the hydrocarbon-based organic compound containing the constituent elements of the thin film is an organoaluminium compound, and an aluminum thin film is formed. 3. The method for producing a thin film according to claim 1 or 2, wherein the organoaluminum compound is triisobutylaluminum, and the aluminum thin film is formed by low-pressure chemical vapor deposition. 4. When the organoaluminum compound is triisobutylaluminum and a thin aluminum film is formed on the substrate surface by low-pressure chemical vapor deposition, the triisobutylaluminum raw material supply system and the inner wall of the reaction vessel in which the substrate is placed. The temperature is controlled within a temperature range above a temperature at which the triisobutylaluminum does not condense and below 70°C, which is the lower limit temperature at which the triisobutylaluminum thermally decomposes to produce diisobutylaluminum halide. A method for producing a thin film according to any one of claims 1 to 3. 5. Claim 1, characterized in that the hydrocarbon-based organic compound or inorganic compound containing the constituent elements of the thin film is a gallium compound, an aluminum compound, and an arsenic compound, and a gallium-aluminum-arsenic thin film is formed. The method for producing a thin film described in . 6. The gallium compound is triethylgallium, the aluminum compound is triisobutylaluminum,
Claim 1, wherein the arsenic compound is arsenic hydride or arsine in which the hydrogen of arsenic hydride is replaced with a hydrocarbon group, and the gallium-aluminum-arsenic thin film is formed by low-pressure chemical vapor deposition. The method for producing a thin film according to item 5. 7. Using a hydrocarbon-based organic compound or an inorganic compound containing the constituent elements of the thin film as a raw material, a thin film is formed on the surface of a substrate placed in a reaction vessel by chemical vapor deposition, reduced pressure chemical vapor deposition, or molecular beam epitaxy. In the apparatus for forming a thin film, a heating control means for maintaining the surface temperature of the substrate in the reaction vessel in which the thin film is formed at a temperature at which the compound thermally decomposes and the thin film constituent elements are precipitated, and a raw material supply system for the compound. and an apparatus for producing a thin film, comprising means for controlling the temperature of the inner wall of the reaction vessel to a temperature range above a temperature at which the compound does not condense and below a lower limit temperature at which thin film constituent elements of the compound precipitate. . 8. The heating control means for the substrate is a heating device using an electric heater or a high-frequency coil, and the temperature control means for the compound raw material supply system and the inner wall of the reaction vessel is a constant temperature device using hot water or hot air. A thin film manufacturing apparatus according to claim 7.