JP2000336481A - Method of forming metal compound thin film - Google Patents

Abstract

(57) [Summary] Sr (THD) used as a raw material for a metal compound thin film
₂ can be supplied efficiently, and a high-quality metal compound thin film can be formed. SOLUTION: This is a method for forming a metal compound thin film containing at least strontium as one of the constituent elements by a chemical vapor deposition method.
A method for forming a metal compound thin film using r (THD) ₂ , wherein the metal compound thin film is formed using Sr (THD)
_The sublimation of the solid raw material of No. ₂ makes the film formation atmosphere S
supplying r (THD) _2, and the ratio of monomer converted for Sr (THD) ₂ whole contained in a solid material in Sr (THD) ₂ trimers following multimers contained in the solid material To 80% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a metal compound thin film, and more particularly to a method for forming a metal compound thin film containing strontium by a CVD method.

[0002]

2. Description of the Related Art As the size of an electronic device becomes smaller, it is advantageous not only to achieve the function of the electronic device only by a circuit configuration but also to utilize the characteristics of the material itself by using a functional thin film. It is becoming.

For example, an integrated circuit such as an SRAM or an EEPROM that stores information by a combination of transistors or a DRAM that stores information by a combination of a transistor and a capacitor is realized by a conventional MOS transistor and a MOS capacitor. Has become very difficult as the cell area of these devices has been reduced.

In particular, it is necessary for the capacitor element to keep a constant capacitor capacity so that the S / N ratio does not decrease even if the minimum processing size of the integrated circuit is reduced. Therefore, as a capacitor dielectric film of the capacitor element, a material exhibiting a higher dielectric constant than a silicon oxide film or a silicon nitride film / silicon oxide film laminate film (NO _{film), Ba x Sr 1-x} TiO 3 (BST) And SrBi
_{The use of a} thin film of a functional material such as ₂ Ta ₂ O ₉ (SBT) has been studied. In addition, as a material having high conductivity, which is a metal oxide, SrRuO
_{The use} of functional material thin films such as ₃ (SRO) has also been considered. By adopting such a functional material thin film, FRAM (Ferroelectric R)
andomAccess read write Me
devices with a new principle of operation, such as memory.

The above-mentioned BST, SBT, etc. exhibit a dielectric constant of several hundred or more at room temperature, so that it is difficult to secure a sufficient capacitor area as the degree of integration increases. Promising as a dielectric film. Also, the above-mentioned SRO is a BST or SB
Since it has the same perovskite crystal structure as T and can form a good electrode / dielectric interface with few crystal defects and the like, it is suitable as an electrode for BST or SBT.

[0006] When a capacitor element of a highly integrated semiconductor integrated circuit is formed by using BST or SRO, a chemical vapor deposition method (a chemical vapor deposition method) is used as a dielectric (high dielectric, ferroelectric) and electrode film forming technique. CVD method) is suitable. That is,
The CVD method has the advantages that the precision of composition can be controlled, the reproducibility of the process, and the excellent step coverage can be obtained, so that the reliability of the electronic device is greatly improved.

[0007] In order to form a multi-component metal oxide thin film as described above, film formation is generally performed under a supply rate-controlling condition in which composition control is easy. Of BST, the reaction rate is limited by CVD.
(Japanese Patent Application No. Hei 7-0510)
4).

However, when performing CVD of a metal compound, there is a problem that alkaline earth metals such as Sr do not have a compound having a high vapor pressure. That is, the conventionally used THD complex (THD = C ₁₁ H ₁₉ O ₂ ) is a solid at room temperature, and requires a high temperature of 200 ° C. or higher to start vaporizing. Further, there is also a problem that the THD complex is decomposed when kept at a high temperature for a long time. Therefore, there is a problem that it is very difficult to control the supply of the raw material.

The thermal instability as such a raw material is
Sr (THD) _TwoSolid at room temperature
The raw material is dissolved in an organic solvent and the solution
It is stored, weighed and transported in the state, and the vaporizer
Those who raise the temperature and vaporize at a stretch in a high temperature part called
A law has been proposed.

However, in the case of Sr (THD) ₂ ,
In particular, when a highly concentrated solution (a solution having a concentration of 0.2 mol / liter or more) is used, it is difficult to completely vaporize the solution.
Residues form in the vaporizer. For this reason, there has been a problem that frequent maintenance of the vaporizer is inevitable or supply controllability is deteriorated.

When a THD complex is used, since 22 carbon atoms are supplied to the substrate for each metal atom, there is a problem that carbon is easily incorporated into the film as an impurity.

[0012]

As described above, B
Metal compound thin films such as ST, SBT, and SRO are promising as functional material thin films used for integrated circuits. When these are to be formed by the CVD method, since Sr does not have a compound having a high vapor pressure, Sr (THD) is used as a raw material of Sr.
A method for evaporating ₂ has been proposed.

However, it is difficult to completely vaporize Sr (THD) ₂ , and residues are generated in the vaporizer, so that maintenance of the vaporizer becomes complicated and controllability of the supply of raw materials is reduced. Was. In addition, Sr (THD) ₂
Has 22 carbon atoms with respect to one Sr atom, and therefore has a problem that carbon is easily taken in as an impurity in the formed metal compound thin film.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems.
When forming by the VD method, Sr (THD) _{2 as} a raw material
It is an object of the present invention to provide a method capable of efficiently supplying, and also capable of forming a high-quality metal compound thin film by reducing the amount of carbon taken into the metal compound thin film.

[0015]

The present invention is a method for forming a metal compound thin film containing at least strontium as one of the constituent elements by a chemical vapor deposition method, and uses Sr (THD) ₂ as a raw material of strontium. A method of forming a metal compound thin film, comprising: supplying Sr (THD) ₂ to a film formation atmosphere by sublimating a solid material of Sr (THD) ₂ when forming the metal compound thin film; Sr (THD) ₂ contained in the above-mentioned solid raw material as a multimer of trimer or less of Sr (THD) ₂ contained in the raw material
D) The ratio in terms of monomer to the whole ₂ is 80% or more.

Further, the present invention is a method for forming a metal compound thin film containing at least strontium as one of the constituent elements by a chemical vapor deposition method, and using Sr (THD) ₂ as a raw material of strontium. A method of forming a thin film, wherein, when forming a metal compound thin film,
By vaporizing a solution in which Sr (THD) ₂ is dissolved in an organic solvent, Sr (THD) ₂ is supplied to the film-forming atmosphere, and a Sr (THD) ₂ trimer or less contained in the solution is used. Sr (TH contained in the solution of the multimer
D) The ratio in terms of monomer to the whole ₂ is 80% or more.

Note that the Sr (THD) ₂ is a Sr (CHD)
₁₁ H ₁₉ O ₂ ) ₂ . The term "monomer conversion ratio" as used herein means a ratio when a Sr (THD) ₂ multimer is converted to a Sr (THD) ₂ monomer, and is included in a multimer of trimer or less. This is equivalent to the ratio of the total number of Sr contained in the multimers smaller than the trimer to the sum of the total number of Sr contained in the multimers larger than the tetramer.

As a result of investigations by the inventors of the present invention, it has been found that the above-mentioned problem in the prior art arises because the mixing ratio of each Sr (THD) ₂ multimer is not properly controlled. found. The ratio of the Sr (THD) ₂ trimer or less multimer (dimer and trimer) contained in the solid raw material or the solution is 80% or more (the ratio of the trimer or less multimer is 100%, that is, including only the multimer of trimer or less), it was found that the problems of the prior art can be effectively prevented as described below.

First, the ratio of the multimer equal to or less than the trimer is reduced to 80%.
With the above, carbon can be prevented from being taken into the metal compound thin film as an impurity. In particular, when crystallization is performed by heat treatment after forming a metal compound thin film in an amorphous state, much of the impurity carbon contained in the amorphous metal compound thin film is released outside the film by the heat treatment during crystallization. , Membrane shrinkage occurs. The amount of film shrinkage increases as the amount of carbon impurities increases, causing film cracking during crystallization, increasing the leakage current and peeling the film. Therefore, by setting the proportion of the multimer equal to or less than trimer to 80% or more, the amount of impurity carbon in the film can be significantly reduced, so that such a problem can be prevented.

Further, since a multimer of Sr (THD) ₂ or less than a trimer has a higher vapor pressure than a multimer of more than a tetramer (at 250 ° C., 0.3 Torr for a trimer,
By increasing the proportion of multimers less than trimers, the ratio of multimers less than trimers is lower than that in the case where the proportion of multimers less than trimers is small. A large amount of raw material can be supplied to the film forming apparatus.

In addition, since the Sr (THD) ₂ multimer of less than trimer melts at a lower temperature than the multimer of more than tetramer (the melting point of the dimer is 130 ° C. and the melting point of the trimer is 130 ° C.) Is 210
C. and the melting point of the tetramer is 260 ° C., and when these are mixed, the melting point differs depending on the mixing ratio. In addition, it is possible to prevent the powder from being wound up during sublimation and to be a factor of dust generation, and it is possible to obtain stable vaporization characteristics.

Further, since the Sr (THD) ₂ multimer of less than trimer is melted at a lower temperature than the multimer of tetramer or more, Sr (THD) ₂ in the solution is vaporized by the vaporizer. At this time, it can be once liquefied in the heat medium of the vaporization section. Therefore, Sr (THD) ₂ can be uniformly permeated and diffused into the heat medium, so that Sr (THD) ₂ can be supplied to the film forming apparatus at a high supply rate.

In addition, when 20% or more of the Sr (THD) ₂ tetramer or higher multimer is contained, even when liquefied at the time of heating, the viscosity is high and the heat medium of the vaporizer is easily blocked. Therefore, the vaporization amount with respect to the solution supply amount is likely to become unstable, the controllability of the raw material supply is deteriorated, and frequent maintenance of the vaporizer is required. Such a problem can be prevented by setting the ratio of the Sr (THD) ₂ trimer or less multimer to 80% or more.

[0024]

Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1) First, a first embodiment of the present invention will be described with reference to FIG.

In the present embodiment, in order to confirm the effect of the present invention, the following control experiment was performed on the BST film formation using the apparatus shown in FIG.

The BST film-forming CVD apparatus shown in FIG. 1 comprises a raw material supply apparatus 110 using a sublimation method, a hot wall batch type reaction vessel 120, and an exhaust system 130.

The raw material supply device 110 is independently temperature controlled.
Raw material oven 111a (Ba oven), 11
1b (oven for Sr) and 111c (oven for Ti)
Bun). Each oven 111a, 111b and
Ba (THD)_Two, Sr (THD)
_Two, Ti (THD)_Two(I-OC_ThreeH₇)_TwoThe pellet
Raw material containers 112a and 11 each containing a solid raw material formed into a shape.
2b and 112c are attached respectively. material
The pellets are formed into pellets, making it easy to exchange raw materials.
Can have different mixing ratios of trimer and tetramer.
Sr (THD) _TwoProcesses should be made so that comparison of raw materials can be performed easily.
My husband has been.

Ba, Sr, Ti raw material oven 111
The temperatures of a, 111b and 111c are 230 ° C., respectively.
The temperature was 220 ° C. and 160 ° C., and the flow rate of Ar as a carrier gas was controlled independently by the gas flow controllers 113a, 113b and 113c, and supplied to each raw material container. The pressure in each of the raw material containers 112a, 112b and 112c is
Using the needle valves 114a, 114b and 114c at the raw material container outlet, respectively, 100 Torr, 100
Controlled at Torr and 60 Torr.

The solid raw material of Sr (THD) ₂ includes S
Ratio of r (THD) ₂ trimer to Sr (THD) ₂ total monomer (trimer + tetramer) in terms of monomer (trimer / (trimer + tetramer): hereinafter, trimer 100%, 90%, 80%, 65% and 50% of pellets, respectively.

Each material of Ba, Sr and Ti is supplied to a valve 115.
a, 115b and 115c, and the O ₂ is supplied to the reaction vessel 120 by the gas flow control device 116.
Is controlled by the gas flow controller 117 to supply the gas into the reaction vessel 120.

The BST film is a sample (semiconductor substrate, etc.) held in a hot wall batch type reaction vessel 120.
121 was formed. During film formation, the pressure in the reaction tube was adjusted by heating the sample 121 to a constant temperature by the heater 122 and evacuating the sample 121 by the exhaust pump 131 via the automatic pressure control device 132.

Using the above-described apparatus, a BST film was formed under the following conditions.

The film forming temperature is 400 ° C. and the reaction tube pressure is 100
Pa, the total gas flow rate was 2 slm, and the container 112 for Ba was
The flow rates of the carrier gas flowing into the container 112c for a and Ti were 300 sccm and 80 sccm, respectively.

The flow rate of the carrier gas flowing into the Sr container 112b is different from that of the raw material having a different trimer ratio because the vapor pressure is different as a result of the experiment. And 250 to obtain the film composition.
It was set in the range from sccm to 420 sccm.

FIG. 2 shows the relationship between the obtained carrier gas flow rate and the trimer ratio. If the trimer ratio decreases, the same BST will be required unless the carrier gas flow rate is increased.
It can be seen that the film thickness and film composition cannot be obtained.

Generally, there is a relation f∝Fp / (P-p) ≒ Fp / P among the raw material container pressure P, the carrier gas flow rate F, the raw material vapor pressure p and the raw material supply amount f. From the above experimental results, the raw material container pressure P
It has been found that in order to keep f constant under certain conditions, F must be changed for each pellet. That is,
This is because the raw material vapor pressure p is different between pellets having different trimer ratios. The trend shows that a higher vapor pressure can be obtained as the trimer ratio is increased. High vapor pressure is extremely important in practical use.

Under the conditions described above, Ba _0.5 Sr _0.5
A Ti _1.04 O ₃ film could be formed at a film formation rate of 0.3 nm / min.

FIG. 3 shows a BST film formed by the above method.
Carbon concentration in the sample by Auger electron spectroscopy and SIMS analysis
It shows the result of the evaluation. From FIG. 3, the BST film
There is a correlation between medium carbon concentration and trimer ratio,
When the trimer ratio in the medium is 80% or more, the carbon impurity concentration is 0.0
As low as 1 (atomic%), the trimer ratio
Carbon impurity concentration increases sharply as
You can see that it gets bigger. Therefore, the carbon in the BST film
In order to suppress elemental impurities, Sr (THD) _TwoThree quantities of
It is important to increase body ratio to 80% or more
You.

At present, it is difficult to obtain a dimer of Sr (THD) ₂ stably, but in order to obtain a desired effect such as lowering the concentration of carbon impurities, the ratio of the dimer must be increased. You may do so. Generally speaking, an Sr (THD) ₂ trimer or less multimer (S) contained in the solid raw material
Ratio of monomer (r (THD) ₂ dimer and trimer) to the total amount of Sr (THD) ₂ contained in the solid material ((multimer less than trimer) / (trimer) In other words, the total number of Sr contained in the trimer or less multimer in the solid raw material and the Sr contained in the tetramer or more multimer in the solid raw material (The ratio of the total number of Sr contained in the multimers equal to or smaller than the trimer in the solid raw material to the total number of Sr) may be 80% or more.

(Embodiment 2) Next, a second embodiment of the present invention will be described with reference to FIG.

In the present embodiment, in order to confirm the effects of the present invention, the following control experiment was performed on the BST film formation using the apparatus shown in FIG.

The BST film-forming CVD apparatus shown in FIG. 4 includes a raw material supply apparatus 210 using a liquid phase supply method, a hot wall batch type reaction vessel 220, and an exhaust system 230.

The raw material supply device 210 has independently provided liquid raw material supply systems for Ba, Ti, and Sr. Each raw material supply system includes raw material containers 211a, 211b, 2
11c and 211d, liquid flow control devices 212a and 21
2b and 212c, vaporizers 213a, 213b and 21
3c and the like.

In particular, regarding the Sr raw material supply system, Sr
(THD) and a _second trimer solution and Sr (THD) ₂ tetramer solution so that it can be delivered by mixing in any ratio, containers Sr (THD) ₂ trimer The mixing solution is devised so that the mixed solution can be sent to the liquid flow control device 212c from the 211c and the tetramer container 211d through the mixing manifold 214 at an arbitrary ratio. As a result, the monomer-converted ratio of the Sr (THD) ₂ trimer contained in the mixed solution to the entire Sr (THD) ₂ contained in the mixed solution (trimer + tetramer) (trimer / ( Trimer +
Tetramer): trimer ratio) can be adjusted.

As a raw material solution, THF was used as an organic solvent.
(C ₄ H ₈ O), to which Ba (THD) ₂ , Sr
(THD) ₂ , Ti (THD) ₂ (i-OC ₃ H ₇ ) ₂
Were dissolved at a rate of 0.3 mol / liter. Ba, Sr, Ti vaporizers 213a, 213
13b and 213c, a gas flow control device 215a,
Ar is supplied via 215b and 215c,
The temperatures of the vaporizers 213a, 213b, and 213c were 250 ° C., 250 ° C., and 180 ° C., respectively.

The organic solvent includes, in addition to the above-mentioned THF, methyl THF (C ₅ H ₁₀ O), n-butyl acetic acid,
It is also possible to use pyridine, benzene and the like.

The raw materials of Ba, Ti and Sr vaporized by the vaporizers 213a, 213b and 213c are supplied to a valve 216.
a, fed to the reaction vessel 220 through the 216b and 216c, also the O ₂ in the gas flow control device 217, Ar
Is controlled by the gas flow controller 218 to supply it into the reaction vessel 220.

The BST film is a sample (semiconductor substrate, etc.) held inside a hot wall batch type reaction vessel 220.
221 was formed. At the time of film formation, the pressure in the reaction tube was adjusted by heating the sample 221 to a constant temperature by the heater 222 and evacuating by the exhaust pump 231 via the automatic pressure control device 232.

Using the above-described apparatus, a BST film was formed under the following conditions. The film forming temperature was 400 ° C., the reaction tube pressure was 100 Pa, the total gas flow rate was 2 slm, and Ba, Sr,
The supply rate of each Ti material is 0.25 sccm,
0.35 sccm and 0.55 sccm were set.

Under the conditions described above, Ba _0.5 Sr _0.5
A Ti _1.04 O ₃ film could be formed at a film formation rate of 0.5 nm / min.

FIG. 5 shows the result of evaluating the carbon concentration in the BST film formed by the above-described method by Auger electron spectroscopy and SIMS analysis. From FIG. 5, there is the same correlation between the carbon concentration in the BST film and the trimer ratio in the liquid source as in the case of Embodiment 1. When the trimer ratio is 80% or more, the carbon impurity concentration becomes 0. It can be seen that the carbon impurity concentration sharply increases as the trimer ratio decreases, whereas it is as low as about 0.011 (atomic%) (indicated by black circles in the figure).

FIG. 5 also shows the results of an experiment conducted using a raw material in which Sr (THD) _{2 in} which a trimer and a tetramer were mixed was dissolved in THF from the beginning (shown by white circles in the figure). T). As is clear from the figure, there is no difference between the two experimental results. Therefore, based on the results of this experiment,
It can be seen that there is no problem even if an appropriate trimer ratio in the raw material solution is estimated.

When the trimer ratio is 30% or less, the Sr sharply increases.
The vaporizer 213c of the raw material supply system was clogged, and it was difficult to perform an experiment. When the vaporizer was disassembled, it was found that a large amount of brownish tar-like residue had adhered. When this residue is analyzed, mainly Sr, C
And O, which was presumed to be a decomposition product of Sr (THD) ₂ tetramer.

The BST films obtained as described above were all amorphous, but could be crystallized by heat treatment in a nitrogen atmosphere at 650 ° C. FIG. 6 shows the relationship between the amount of contraction of the film thickness and the trimer ratio at that time. As shown in FIG. 6, when the amorphous BST is crystallized, the essential thickness shrinkage due to the change in the crystal structure is about 15%.
Exists.

As can be seen from FIG. 6, the trimer ratio is 80%
In the above films, the shrinkage of the film thickness is slightly less than 20%, but as the trimer ratio is reduced, the shrinkage of the film thickness sharply increases, and the shrinkage reaches 40% or more. SEM observation of a sample having a film thickness shrinkage of about 40% (trimer ratio 50%) revealed that cracks had occurred on the BST film surface. This crack is considered to be caused by a large film shrinkage due to crystallization.

FIG. 7 shows the BST films obtained when a solution containing only trimers was used as a raw material and when a solution containing trimers of 80%, 70% and 50% was used as raw materials. It shows the electrical characteristics.

The sample used for the evaluation of the electric characteristics is the above-mentioned B
In this structure, the ST film is sandwiched between a lower electrode and an upper electrode. As the lower electrode, a 100-nm-thick Pt film formed by a sputtering method on a 400-nm-thick thermal oxide film was used. After forming an amorphous BST to a thickness of 30 nm on the BST film,
A material that was crystallized by performing a heat treatment for 30 minutes in a nitrogen atmosphere at 0 ° C. was used. The upper electrode has a thickness of 50 n formed by sputtering in an argon atmosphere containing 10% oxygen.
m Pt was used. The processing of the upper electrode was performed using a shadow mask.

When the leak current density was measured by applying voltages of +1 V and -1 V to the sample, the leak current density was low in the sample containing only trimer and in the sample containing 80% trimer, It was found that the leak current density was significantly increased in the sample having a body ratio of 70% or less. Trimer ratio of 8
TEM evaluation was performed on the 0% and 70% BST films. As a result, no defect was observed in the 80% film, whereas a void having a diameter of about several nm was observed in the 70% film. . It is considered that this void was generated due to a large film shrinkage due to carbon desorption.

From the results of FIGS. 5 to 7 described above, in order to suppress carbon impurities in the BST film, it is necessary to use Sr (THD) ₂
It is understood that it is important to increase the trimer ratio to 80% or more.

At present, it is difficult to obtain a dimer of Sr (THD) ₂ stably, but in order to obtain a desired effect such as lowering the concentration of carbon impurities, the ratio of the dimer should be increased. You may do so. Generally speaking, a multimer (Sr (THD) ₂ or less) of Sr (THD) ₂ contained in the solution
Ratio of (THD) ₂ dimer and trimer) to the total amount of Sr (THD) ₂ contained in the solution in terms of monomer ((multimer less than trimer) / (multimer less than trimer) Multimer + multimer of tetramer or more): In other words, the sum of the total number of Sr contained in the multimer of less than trimer in the solution and the total number of Sr contained in the multimer of more than tetramer in the solution (The ratio of the total number of Sr contained in the multimer of the trimer or less in the solution to the total number of Sr) may be 80% or more.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and can be variously modified and implemented without departing from the gist thereof.

[0063]

According to the present invention, by setting the ratio of the Sr (THD) ₂ trimer or lower multimer to 80% or more, the amount of impurity carbon taken into the metal compound thin film can be reduced. A high-quality metal compound thin film can be formed, and Sr (TH
D) ₂ can be supplied. Further, Sr (T
HD) ₂ , the method of vaporizing the solution in which the solution is dissolved facilitates the maintenance of the vaporizer.

[Brief description of the drawings]

FIG. 1 is a diagram showing a configuration example of a film forming apparatus according to a first embodiment of the present invention.

FIG. 2 shows the trimer ratio and S in the first embodiment of the present invention.
The figure which showed the relationship of the carrier gas flow rate of r (THD) ₂ .

FIG. 3 shows the trimer ratio and B in the first embodiment of the present invention.
The figure which showed the relationship of the carbon concentration in ST film.

FIG. 4 is a diagram showing a configuration example of a film forming apparatus according to a second embodiment of the present invention.

FIG. 5 shows the trimer ratio and B in the second embodiment of the present invention.
The figure which showed the relationship of the carbon concentration in ST film.

FIG. 6 shows the trimer ratio and B in the second embodiment of the present invention.
The figure which showed the relationship of the film thickness shrinkage rate at the time of crystallization of an ST film.

FIG. 7 is a view showing electric characteristics of a BST film when a trimer ratio is changed in a second embodiment of the present invention.

[Explanation of symbols]

110: raw material supply device 111a, 111b, 111c: raw material oven 112a, 112b, 112c: raw material container 113a, 113b, 113c, 116, 117: gas flow control device 114a, 114b, 114c: needle valve 115a, 115b, 115c: valve 120, 220: hot wall batch type reaction vessel 121, 221 ... sample 122, 222 ... heater 130, 230 ... exhaust system 131, 231 ... exhaust pump 132, 231 ... automatic pressure control device 210 ... raw material supply device 211a, 211b, 211c, 211d: raw material containers 212a, 212b, 212c: liquid flow control device 213a, 213b, 213c: vaporizer 214: mixing manifold 215a, 215b, 215c, 217, 218: gas flow control device 16a, 216b, 216c ... valve

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/8242 (72) Inventor Soichi Yamazaki 8 Shinsugitacho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture Toshiba Yokohama Business Co., Ltd. In-house (72) Inventor Kazuhiro Eguchi 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 4K030 AA11 BA01 BA18 BA42 BA54 BB01 FA10 HA15 JA05 LA02 5F045 AA06 AB31 AB40 AD08 AE19 AF10 BB13 CB05 DP19 EE02 HA11 5F058 BA04 BA11 BC01 BC03 BF01 BF02 BF04 BF21 BF22 BF27 BF29 BH01 BH04 BJ04 5F083 AD11 FR01 GA27 GA30 JA14 JA17 JA31 JA38 JA45 PR21 PR33

Claims (2)

[Claims] 1. A method of forming a metal compound thin film containing at least strontium as one of the constituent elements by a chemical vapor deposition method, and using Sr as a raw material of strontium.
A method of forming a metal compound thin film using (THD) ₂ , wherein a Sr (THD) ₂ is formed into a film forming atmosphere by sublimating a solid material of Sr (THD) ₂ when forming the metal compound thin film.
HD) ₂ and S contained in the solid raw material.
forming a thin film of a metal compound, wherein a ratio of a monomer of r (THD) ₂ or less to a total of Sr (THD) ₂ contained in the solid material is 80% or more in terms of monomer. Method. 2. A method for forming a metal compound thin film containing at least strontium as one of the constituent elements by a chemical vapor deposition method, and using Sr as a raw material of strontium.
A method for forming a metal compound thin film using (THD) ₂ , wherein a solution in which Sr (THD) ₂ is dissolved in an organic solvent is vaporized to form Sr (THD) ₂ supplies, and the Sr contained in the solution (THD) Sr contained in the solution of ₂ trimers following multimers (THD) ₂ ratio of the monomer conversion for the entire 80% or more A method for forming a metal compound thin film, characterized in that: