JPH09249973A - Production of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a tin-contg. metal oxide dielectric thin film with good step covering property and to obtain a semiconductor device having excellent performance by using an org. tin compd. as one source material for a chemical vapor growth method to form the dielectric thin film. SOLUTION: In the production of a semiconductor device having an oxide dielectric thin film containing tin as the structural element, the dielectric thin film is formed by a chemical vapor growth method using an org. tin compd. as one source material. As for the org. tin compd., a compd. of tin having at least one THD (2,2,6,6-tetramethyl-3,5-heptanedione) group coordinated is preferably used. For example, Sn(THD)2 , SnO(THD)2 can be used. A liquid source material prepared by dissolving the org. tin compd. in a solvent is preferably used. The preferable aspect of the oxide dielectric thin film containing tin is BaTix Sn1-x O3 film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device having an oxide-based dielectric thin film as a constituent element, for example, a DRA using such an oxide-based dielectric thin film as a capacitor dielectric film.
A method of manufacturing a dielectric memory such as M.

[0002]

2. Description of the Related Art With the miniaturization of electronic devices, the function of the electronic device is achieved not only by the circuit configuration but by utilizing the characteristics of the material (particularly the functional thin film) itself. Is becoming more advantageous.

For example, an SRAM (Static Random Access read) that performs an operation of storing information by a combination of transistors.
write Memory), EEPROM (Electrically Erasab
leaned programmable read only memory), or DRAM (Dynamic Random Access Memory) that stores information by combining a transistor and a capacitor,
FRAM (Ferroelectric Random Access read write M
In the case of an integrated circuit such as an emory), it has become very difficult to realize desired characteristics with conventional MOS transistors and MOS capacitors as the cell area of these elements is reduced. In particular, in these integrated circuits, it is necessary not to reduce the S / N of the capacitor element even if the minimum processing dimension of the integrated circuit is reduced, and for that purpose, a certain capacitor capacity is secured even if the element dimension is reduced. Must. In order to meet such requirements, as a capacitor dielectric film of a capacitor element,
The adoption of functional materials that exhibit a higher dielectric constant than conventional silicon oxide films and silicon nitride film / silicon oxide film laminated films (NO films), that is, ferroelectric thin films, has been studied. Is coming.

Ba _x S having a perovskite crystal structure
r _1-x TiO ₃ and PbZr _x Ti _1-x O ₃ etc.
Since it has a dielectric constant of several hundreds or more at room temperature, it is promising as a capacitor dielectric film. However, as these materials also become thinner, the dielectric constant decreases. Therefore, even if such a high dielectric constant thin film is used, when it is applied to a gigabit class memory, a simple three-dimensional structure such as a groove is adopted to obtain sufficient capacitor capacity. It is necessary to increase the area.

Assuming that such a three-dimensional structure is adopted, when a ferroelectric film is used to form a capacitor element of a semiconductor integrated circuit having a high degree of integration, a chemical technique is used as a ferroelectric film forming technique. It is considered necessary to use a vapor phase growth method (CVD method). This is because the CVD method is superior to the precise controllability of the composition and the reproducibility of the process in comparison with other film forming techniques such as sputtering, and further, the excellent step coverage which is indispensable for adopting a three-dimensional structure is obtained. Therefore, there is an advantage that the reliability of the electronic device is significantly improved.

On the other hand, according to recent research, Ba _x Sr
_{Even 1-x} TiO ₃ and PbZr _x Ti _1-x O ₃ do not have a large relative permittivity enough to realize a planar capacitor, and therefore, in order to realize a gigabit-class memory, the aspect ratio is It has been found necessary to employ two or more relatively deep trench capacitors. In addition, Ba _x Sr _1-x TiO ₃ film and PbZr _x Ti _1-x O
It has been found that the _three films have to be thinned to 75 nm or less in the case of 1G DRAM, and are extremely difficult to form the upper electrode.

Therefore, in recent years, BaTi _x Sn _{1 -x} O ₃ (also referred to as B for the sake of simplicity hereinafter) having a perovskite crystal structure is also used.
(Abbreviated as TS) has attracted attention as a dielectric thin film for semiconductor devices. See the following references for this.

・ NTTLSI Lab, Mitsuo Tsukada, Masashi Mukata,
Shintaro Miyazawa; “Preparation of Ba (Ti _1-x Sn _x ) O ₃ thin film and its dielectric properties”; Proceedings of the 56th Annual Meeting of the Society of Applied Physics, Autumn 1995 p351 The above BTS contains tin as a component. Since it has a Curie point near room temperature, it can exhibit an extremely high dielectric constant. The BTS film actually formed by the laser ablation method using the excimer laser is
A sample having a film thickness of 80 nm has a dielectric constant of 1,000 or more, and even in a gigabit class memory, there is an advantage that a three-dimensional capacitor having an aspect ratio of 1 or less can obtain a sufficient charge storage capacity.

However, as described above, a film forming method excellent in step coverage, that is, a CVD method is indispensable for manufacturing a three-dimensional structure capacitor, but for BTS, an appropriate CVD method (especially tin) is used. No CVD source material) has been found. Therefore, there is a problem that the BTS film cannot be effectively used as a capacitor dielectric film of a three-dimensional structure capacitor.

[0010]

The present invention has been made in view of the above circumstances, and its object is to provide a multi-element metal oxide dielectric thin film containing tin as a constituent element with good step coverage. An object of the present invention is to manufacture a semiconductor device having excellent performance by providing a chemical vapor deposition method capable of forming a film.

[0011]

The present invention relates to a method of manufacturing a semiconductor device comprising an oxide-based dielectric thin film containing tin as a constituent element, wherein the dielectric thin film is used as one of raw materials for an organotin compound. A method of manufacturing a semiconductor device is characterized in that it is formed by a chemical vapor deposition method using.

The object of manufacture in the present invention is mainly a semiconductor device, such as a DRAM, which uses the above-mentioned oxide-based dielectric thin film containing tin as a charge storage film such as a capacitor dielectric film.
It is. In the present invention, since the oxide-based dielectric thin film containing tin is formed by CVD, good step coverage can be realized even when a three-dimensional structure such as a groove type capacitor is adopted.

In one preferred embodiment of the invention,
At least one THD is added to tin as the organotin compound that is a raw material for chemical vapor deposition (hereinafter referred to as CVD).
An organotin compound in which a (2,2,6,6-tetramethyl-3,5-heptanedione) group is coordinated is used. Examples of such an organic tin compound include Sn (THD) ₂ , Sn (THD) ₃ ,
SnO (THD) ₂ , Sn (THD) ₂ (OR) (O
R ′), Sn (THD) ₂ RR ′ and Sn _m (TH
D) _{2 m} . However, R and R'are alkyl groups and m is an integer of 2-8.

In another preferred embodiment of the present invention, the tin-containing oxide-based dielectric thin film described above is BaTi _x Sn.
_{It is a 1-x} O ₃ film (hereinafter abbreviated as BTS film). When the above BTS film is used as the oxide-based dielectric thin film, it is preferable to use an organic barium compound in which THD is coordinated with barium as a raw material for CVD as well as a tin component. Examples of such an organic barium compound include Ba (THD) ₂ , Ba ₄ (THD) ₈ and Ba (THD).
HD) ₂ THF, Ba (THD) ₂ triglyme, Ba (T
HD) ₂ tetraglyme and the like.
More preferably, as for the Ti component, it is preferable to use an organic titanium compound having THD coordinated as a raw material. As such an organic titanium compound, for example, TiO (TH
D) ₂ , Ti (THD) ₂ , TiO (THD) ₂ , Ti
(THD) ₂ RR 'and Ti (THD) ₂ OROR'
Is mentioned. However, R and R ′ are CH ₃ , C ₂ H
₅ , alkyl groups such as n-C ₃ H ₇ and i-C ₃ H ₇ .

In the present invention, the CV is controlled so that all the decomposition of the organometallic raw material used for CVD is reaction-controlled.
It is preferable to select the condition D. This makes it possible to realize perfect step coverage, and as a result, it is possible to easily manufacture a semiconductor device incorporating a metal oxide-based dielectric thin film having good step coverage.

Furthermore, in another preferred embodiment of the present invention, an organotin compound in which at least one THD group is coordinated with tin is preferably used as a liquid raw material obtained by dissolving the compound in a solvent. Furthermore, it is preferable to use a liquid raw material obtained by dissolving another organic metal raw material in a solvent.

The greatest feature of the present invention resides in that the oxide dielectric thin film containing tin is formed by the CVD method. Heretofore, as the oxide-based dielectric thin film containing tin, only the one formed by the laser ablation method has been known, and this constitutes a novel feature of the present invention.

Conventionally, the reason why the oxide-based dielectric thin film containing tin could not be formed by the CVD method seems to be that the raw material which enables it was not found. The inventor has found that an organotin compound in which at least one THD group is coordinated to tin has an appropriate vapor pressure as a raw material for CVD and also performs a suitable film formation reaction.

According to the results of earnest studies by the present inventors,
An organometallic compound having a THD group has a property that it is relatively stable in a gas phase and hardly causes film formation when it is a single substance, but it is relatively easily bonded to a THD complex of a different metal to form an intermediate, It has the property of causing film formation. By paying attention to this property, the inventors have succeeded in forming an oxide-based dielectric containing tin by the CVD method. For example, when forming a BTS film, at least one T is added to tin such as Sn (THD) _2.
When an organotin compound in which HD groups are coordinated is used as a CVD raw material, a strong interaction works with a Ba raw material such as Ba (THD) ₂ , and a reaction intermediate containing Ba and tin is formed. Since this intermediate body actively migrates on the substrate surface, good step coverage is realized.

Hereinafter, a BaTi _x Sn _1-x O ₃ film (BTS
The present invention will be described in more detail with respect to the case of forming a film), focusing on its action. As described above, an organometallic compound having a THD group has a property that it is relatively stable in a gas phase and hardly causes film formation, while it is easily bonded to a THD complex of a different metal to form an intermediate. It forms the body and causes film formation. An example thereof is a THD complex of Ba which is a main constituent element of BTS.

With respect to Ba, there is a problem that almost no organic compound having a high vapor pressure suitable for a CVD source gas is present. Therefore, a β-diketone complex having a relatively high vapor pressure is used as an MOCVD raw material for Ba, and particularly Ba (THD) ₂ having a THD group coordinated,
Ba ₄ (THD) ₈ , Ba (THD) ₂ THF, Ba
(THD) ₂ Triglyme, Ba (THD)
₂ Tetraglyme is used. Therefore, it was examined to use an organic metal raw material having a THD group also for tin. As a result, when an organotin compound coordinated with at least one THD group is used as a CVD raw material, a strong interaction between the organotin compound and the organic barium compound is exerted, and an adduct of a Ba compound and a Sn compound is formed. It was confirmed that a reaction intermediate was formed, and the intermediate actively migrated on the surface of the substrate to realize good step coverage.

FIG. 5 shows, as an example of the above intermediate, a heterodimer obtained by reacting Ba (THD) ₂ with SnO (THD) ₂ , that is, Ba (THD) ₂ —O—Sn (T
HD) ₂ shows possible structures. As is clear from the figure, in this dimer molecule, the metal ions Ba and Sn are surrounded by large THD molecules.
The charges of metal ions are shielded by the molecules. The active migration of the intermediate on the surface of the substrate is probably due to such structural characteristics. According to the result of examination by the present inventors, this is
Not only (THD) ₂ but also Sn (THD) ₂ and SnO
(THD) ₂ , Sn (THD) ₂ RR ′, Sn (TH
It was confirmed that the same applies to other THD complexes such as D) ₂ OROR ′. In addition, Sn (i-OC ₃ H
₇ ) ₄ , Sn (CH ₃ ) ₄ and the like, similar effects were obtained with complexes using ligands other than THD, but it was confirmed that the effects were not as great as with THD complexes.

In order to produce the above dimer as an intermediate, the Sn and Ti raw materials are supplied in excess of the stoichiometric ratio to Ba (Ba / (Sn + Ti) = 1). It is important to. The conditions therefor depend on the film forming conditions such as the film forming temperature and the film forming pressure, the configuration of the film forming apparatus, and the like. However, according to what the present inventors have diligently studied, it is necessary that the ratio of the Sn and Ti raw material partial pressure to the Ba raw material partial pressure is at least 2 or more.

Next, a more specific manufacturing process and its effect will be compared and described with reference to the drawings. FIG.
Is Sn (i-OC ₃ H ₇ ) ₄ , TiO (THD) ₂ , B
a (THD) ₂ is used to deposit BaTi _x Sn _1-x O by CVD at a temperature of 600 ° C. where the film formation rate is the rate-determining condition.
_The film formation state when _three films are formed is shown. The step coverage in this case was about 40%.

FIG. 6b shows the result when the same raw material system as in the case of FIG. 6a is used and the film formation temperature is lowered to 400 ° C. to perform CVD. Under this temperature condition, the reaction rate of the raw material is lower than the supply rate, so that the film formation is performed under the reaction rate-determining condition. Generally, in the present invention, the reaction-controlled condition is preferable, but in this case, unevenness is considered to be caused by interference between the raw materials, and the step coverage is hardly improved as compared with FIG. 6a. It was

FIG. 6c shows that the raw materials for Ti and Ba are:
As in FIGS. 6a and 6b, TiO (THD) ₂ , Ba
(THD) ₂ is used, while Sn is used as a raw material.
It shows the result when a film is formed by using (THD) ₂ at 600 ° C. under the supply rate controlling condition. Under the supply rate-determining condition, active migration of the intermediate on the substrate surface cannot be expected, so 100% step coverage cannot be obtained. However, as compared with FIG. 6a, a good 60% step coverage was obtained.

On the other hand, in the same raw material system as in FIG. 6c, when the film forming temperature was lowered to 400 ° C. where the deposition of all raw materials was a reaction rate-determining condition, 100% step coverage was obtained as shown in FIG. 6d. Was obtained.

As can be seen from these results, by using the organic tin compound as one of the raw materials, the oxide-based dielectric thin film containing tin can be formed by the CVD method. In that case, it is preferable to use a compound containing at least one THD as the organic tin compound. Further, in order to form BTS with good step coverage, Ba,
It is preferable to use a compound having a THD group for all Ti and Sn. Further, in the above example, TiO (THD) ₂ is used as a raw material of Ti, but Ti (THD) 2
₂ , TiO (THD) ₂ , Ti (THD) ₂ RR ', T
i (THD) ₂ OROR '[however, R and R'are CH ₃ and C ₂
H ₅ , n-C ₃ H ₇ , alkyl groups such as i-C ₃ H ₇ ] and the like can be used.

Thus, the most preferred embodiment of the present invention,
That is, CVD satisfying all of the following conditions (a) to (c)
Using the method, it is possible to achieve perfect step coverage.

(A) Use of an organotin compound in which at least one THD group is coordinated to tin as a CVD raw material for tin. (B) As a raw material of Ba and Ti, use of an organometallic compound in which at least one THD group is coordinated with these metallic elements.

(C) The film formation of BTS is selected so that the decomposition of all the organometallic raw materials used for CVD is reaction-controlled. The film-forming temperature at the boundary between the reaction-controlled condition and the supply-controlled condition is determined by examining the film-forming temperature dependence of the deposition amount of each metal constituent element and finding the temperature at which the deposition amount shows a sharp decrease. it can. In addition, the temperature dependence of the step coverage of the metal oxide film is investigated to find a good step coverage, for example, a film formation temperature at which the ratio of the film thickness between the flat portion and the bottom of the step is 1.3 or less. It is also possible to decide by

Further, according to the confirmation by the present inventors, by using an intermediate formed between the organometallic compound having a THD group as a precursor of the reaction, it is incorporated into the film during film formation. It was confirmed that impurities or residual defects in the film were significantly suppressed, and as a result, the formed BTS film exhibited extremely good dielectric properties. For example,
In a BaTix Sn _1-x O ₃ film having a film thickness of 40 nm,
A high relative dielectric constant as shown in FIG. 7 was obtained in a wide composition range of 0.4 ≦ x ≦ 1.

[0033]

Embodiments of the present invention will be described below. Example 1 Using a normal cold wall type CVD apparatus, solid Ba (THD) ₂ , solid TiO (THD) ₂ and liquid Sn (THD) ₂ are used as raw materials for Ba, Ti and Sn, respectively. I was there. Each of these raw materials is stored as a solid or liquid in an independent raw material container and is stored in an independent oven.
It was kept at 170 ° C. Argon gas controlled by a flow rate controller was used as a carrier gas, and each raw material was carried along with the carrier gas and transported to a reaction tube. A CVD reaction is performed in a reaction tube, and a B film having a thickness of 50 nm is formed on the substrate kept at 420 ° C.
An a (Ti, Sn) O ₃ film was formed. The ratio of Ti and Sn is 85:15. Since this film was amorphous at the time of film formation, it was crystallized by annealing. As a result of crystallization in oxygen at normal pressure for 2 hours, it was confirmed by XRD (X-ray diffraction) that a perovskite crystal phase of the Ba (Ti, Sn) O ₃ film was formed. Also, Sn (CH ₃ ) ₄ is used as a raw material of Sn, and BT of 50 nm at 600 ° C.
An S film was formed. The results of evaluating the electrical characteristics of these samples are shown in the table.

[0034]

[Table 1]

The converted film thickness in the table is the thickness of the SiO ₂ film required to obtain the same relative dielectric constant using the SiO ₂ film, and is expressed by the following equation. Converted film thickness = 3.9 × BTS film thickness / dielectric constant of BTS Here, 3.9 is the dielectric constant of SiO ₂ .

As is clear from the above results, when the CVD raw material of the present invention is used, Ba (Ti, S) having an excellent permittivity that can be used as a capacitor dielectric film of DRAM.
n) The O ₃ film can be formed by the CVD method.
In particular, when Sn (THD) ₂ was used as a source of Sn and CVD was performed at a temperature at which the film formation rate became the reaction rate, the characteristics of the obtained BTS film were remarkably excellent.

Second Embodiment: A second embodiment of the present invention will be described. Cold wall type CVD similar to that of Example 1
Using the apparatus, a liquid raw material container, a liquid flow rate control device for transporting the liquid raw material, and a vaporizer for vaporizing the liquid raw material and supplying the liquid raw material into the reaction vessel were attached to this CVD apparatus.

As raw materials, Ba (THD) ₂ tetraglyme, Ti (THD) ₂ (i-OC ₃ H ₇ ) ₂ and Sn were used.
A liquid raw material was used in which each of (THD) ₂ (CH ₃ ) ₂ was dissolved in THF. The molar concentration of each raw material is
It is 0.1 mol / L, 1 mol / L, 0.7 mol / L.

The liquid raw material was supplied to a vaporizer maintained at 250 ° C. at a flow rate of 0.05 sccm by a liquid flow rate controller, and vaporized to be a reaction gas. Using this reaction gas, a Ba (Ti, Sn) O ₃ film having a film thickness of 100 nm was formed on a stepped substrate kept at 600 ° C. and 420 ° C. The ratio of Ti and Sn is 85:15. Since this film was amorphous at the time of film formation, it was crystallized by annealing. As a result of crystallization in oxygen at normal pressure for 2 hours, it was confirmed by XRD that a perovskite crystal phase of the Ba (Ti, Sn) O ₃ film was formed.

The raw materials for Ba and Ti are the same as above, while Sn (CH ₃ ) ₄ is used as the raw material for Sn.
A BTS film having a thickness of 100 nm was formed at 600 ° C. and 420 ° C.

The results of evaluating the step coverage of the BTS film thus obtained are shown in the table. However, A. R. Is an abbreviation for aspect ratio, which is the ratio of the depth to the width of the groove provided in the substrate.

[0042]

[Table 2]

As is clear from the results shown in the table, the BTS film obtained according to the present invention has step coverage so that it can be used as a capacitor dielectric film of a groove type capacitor. Is the reaction-controlled condition at 420 ° C
In the film formation of, excellent step coverage was obtained.

Example 3 In this example, a method of manufacturing a DRAM according to the present invention will be described with reference to FIGS.

An element isolation region 102 is formed on a single crystal silicon substrate 101. Then, the single crystal silicon substrate 10
A thermal oxide film and a polycrystalline silicon film are sequentially formed on 1 and processed by using a normal photolithography technique and a reactive ion etching technique to form a gate electrode 103. Subsequently, the n-type regions 104 and 105 separated from each other are formed by the ion implantation method (FIG. 1).

Next, a CVD oxide film 106 to be an interlayer insulating film.
Is formed, and a contact hole communicating with the n-type region 104 is opened. Then, a polycrystalline silicon film 107 is formed in the contact hole and phosphorus is doped. Next, a tungsten silicide film is formed and patterned by a normal photoetching method to form the bit line 108. Next, the CVD oxide film 10 is formed on the entire surface of the substrate.
9 is deposited. Subsequently, the CVD oxide film 109 and the CVD oxide film 106 are patterned by a normal photolithography technique and a reactive ion etching method to form a contact hole communicating with the n-type region 105. Next, an arsenic-doped polycrystalline silicon film 110 is formed by the CVD method and etched back to fill the contact holes with the arsenic-doped polycrystalline silicon film 110 (FIG. 2).

Next, a ruthenium film 111 is formed on the entire surface of the substrate by the sputtering method. Next, the ruthenium film 111 is processed by a normal photoetching technique to form a lower electrode of the capacitor element (FIG. 3).

Next, B was used as a raw material at a film forming temperature of 430 ° C.
a (THD) ₂ , TiO (THD) ₂ , SnO (TH
D) Amorphous BTS film 112 of 30 nm is formed by the CVD method using ₂ and O ₂ . Depending on the above film forming conditions, BT
The S film 112 grows with extremely high step coverage. Next, the BTS film 112 and the ruthenium film 111 are subjected to RTA treatment at 700 ° C. for 1 minute in an argon atmosphere. B by RTA treatment at 700 ° C for 1 minute in argon atmosphere
The TS film was crystallized, and a relative dielectric constant of 900 and an oxide film equivalent film thickness of 0.13 nm were obtained. Next, a ruthenium film 113 to be an upper electrode of the capacitor was formed by a sputtering method to form a DRAM memory cell portion (FIG. 4).

Thereafter, a passivation film is formed and wiring is formed according to a normal LSI manufacturing process to form an integrated circuit, but description of these steps is omitted.

Although the embodiment for forming the BTS film has been described above, the present invention is not limited to this.
If it is a metal oxide thin film containing Sn as a component, BTS
By forming a thin film of a metal oxide such as a ferroelectric thin film and a superconducting oxide thin film other than the film, according to the present invention, good step coverage and good insulation by suppressing the incorporation of impurities can be obtained. The same excellent results as those described in the above embodiment can be obtained.

[0051]

As described above, according to the present invention,
It is possible to realize a capacitor with a high accumulated charge density by using a high dielectric film having a perovskite crystal structure with a high dielectric constant, and realize a method for manufacturing a semiconductor integrated circuit memory element with high performance and low manufacturing cost. it can.

[Brief description of drawings]

FIG. 1 is a process sectional view showing an embodiment of a method of manufacturing a semiconductor device according to the present invention.

FIG. 2 is a process sectional view showing an embodiment of a method of manufacturing a semiconductor device according to the present invention.

FIG. 3 is a process sectional view showing an embodiment of a method for manufacturing a semiconductor device according to the present invention.

FIG. 4 is a process sectional view showing an embodiment of a method of manufacturing a semiconductor device according to the present invention.

FIG. 5 is a schematic diagram of a reaction intermediate according to the present invention.

FIG. 6 is a process sectional view showing a step film property of a dielectric film according to the present invention.

FIG. 7 is a process cross-sectional view showing the composition dependence of the relative dielectric constant of the dielectric film according to the present invention.

[Explanation of symbols]

101 ... Single crystal silicon substrate, 102 ... Element isolation region,
103 ... Gate electrode, 104, 105 ... N-type region, 10
6, 109 ... CVD oxide film, 107 ... Polycrystalline silicon film, 108 ... Bit line, 110 ... Arsenic-doped polycrystalline silicon film, 111, 113 ... Ruthenium film, 112 ... Ba
Ti0.85Sn0.15O3 film.

Claims (4)

[Claims] 1. A method for manufacturing a semiconductor device having an oxide-based dielectric thin film containing tin as a constituent element, comprising: chemical vapor deposition using an organic tin compound as one of the raw materials for the dielectric thin film. A method of manufacturing a semiconductor device, characterized in that the semiconductor device is formed by a method. 2. The method of manufacturing a semiconductor device according to claim 1, wherein an organotin compound in which at least one THD group is coordinated with tin is used as the organotin compound. 3. An organotin compound in which at least one THD group is coordinated with tin, Sn (THD) ₂ , Sn
(THD) ₃ , SnO (THD) ₂ , Sn (THD) ₂
(OR) (OR '), Sn (THD) ₂ RR' and S
3. At least one selected from the group consisting of n _m (THD) _2m [wherein R and R ′ are alkyl groups and m is an integer of 2 to 8] is used. Manufacturing method of semiconductor device. 4. The method of manufacturing a semiconductor device according to claim 2, wherein an organotin compound in which at least one THD group is coordinated with the tin is used as a liquid raw material obtained by dissolving the compound in a solvent. .