JP2003264185A - Vaporization supply method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vaporization supply method capable of efficiently vaporizing a raw material obtained by dissolving a solid CVD raw material in an organic solvent, and supplying an obtained vaporized gas to a semiconductor manufacturing apparatus with extremely high purity. SOLUTION: After a raw material obtained by dissolving a solid CVD raw material in an organic solvent is supplied to a vaporizer and vaporized, a vaporized gas containing the CVD raw material is filtered by a filter to remove particles contained in the vaporized gas, Supply to semiconductor manufacturing equipment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for supplying a gaseous CVD raw material to a semiconductor manufacturing apparatus (CVD apparatus). More specifically, it relates to a method of efficiently vaporizing a raw material obtained by dissolving a solid CVD raw material in a solvent and supplying the obtained vaporized gas to a semiconductor manufacturing apparatus with extremely high purity.

[0002]

2. Description of the Related Art In insulating thin films for semiconductor devices,
SiO _{2 is used} as a gate insulating film, Si ₃ N _{4 is used as} a capacitor insulating film, and PSG (phosphorus silicon.
Glass) and BPSG (boron phosphorus silicon glass). Conventionally, SiH ₄ , NH ₃ , PH ₃ , and B ₂ H have been used as materials for manufacturing these with a CVD apparatus.
_Although gas raw materials such as ₆ have been used, the demand for planarization of the insulating film is increasing as the device becomes three-dimensional and the wiring becomes multi-layered. Liquid raw materials capable of forming thin films are also used. For example, tetraethoxysilicon (Si (OC ₂ H ₅ ) ₄ ) is used as the raw material for the SiO ₂ film, and trimethoxyboron (B (OCH ₃ ) ₃ ) and trimethoxyphosphorus (P (OCH ₃ ) are used as the raw materials for the BPSG film. ) ₃ ) etc. are used.

[0003] several times higher dielectric constant the Ta ₂ O ₅ film showing the SiO ₂ in this addition, Al ₂ O ₃ and new types of thin film or the like have been developed, of the Ta ₂ O ₅ film As a raw material,
Liquid pentaethoxy tantalum (Ta (OC ₂ H ₅ ))
₅ ) is used as a raw material for the Al ₂ O ₃ film, and liquid triisopropoxyaluminum (Al (OCH (C
H ₃ ) ₂ ) ₃ ) or trimethylaluminum (Al
(CH ₃ ) ₃ ) is used.

In recent years, lead zirconate titanate (PZT) has a higher dielectric constant and a higher step coverage as an oxide-based dielectric thin film for semiconductor memory.
A film, a barium strontium titanate (BST) film, or the like is used. Examples of raw materials for these thin films include Pb (DPM) ₂ (solid raw material) as a Pb source, Zr (OC (CH ₃ ) ₃ ) ₄ (liquid raw material) as a Zr source, and Zr (D
PM) ₄ (solid material), Ti (OCH (C
H ₃ ) ₂ ) ₄ (liquid raw material), Ti (OCH (CH ₃ ) ₂ )
₂ (DPM) ₂ (solid raw material), Ba (DP
M) ₂ (solid raw material) and Sr (DPM) ₂ (solid raw material) are used as the Sr source.

When a liquid raw material is used as a CVD raw material, the liquid raw material is usually supplied to a vaporizer together with a carrier gas, made into a gas state in the vaporizer, and then supplied to a CVD apparatus. However, since liquid raw materials generally have low vapor pressure, high viscosity, and vaporization temperature and decomposition temperature are close to each other, they can be efficiently vaporized at a desired concentration and flow rate without deteriorating their quality. Was difficult. Further, the solid raw material, it is possible to obtain a high-purity raw material by holding at a high temperature and sublimating to vaporize and supply, but it is extremely difficult to ensure a sufficient supply amount industrially, Usually, it is dissolved in a solvent such as tetrahydrofuran and used as a liquid raw material to be vaporized and used. However, the vaporization temperature of the solid raw material is largely different from that of the solvent, and only the solvent is vaporized by heating to easily precipitate the solid raw material, which is more difficult than the vaporization of the liquid raw material.

As described above, the production of a semiconductor thin film using a liquid raw material or a solid raw material requires high technology,
Since higher quality and higher purity can be expected from semiconductor thin films using gas raw materials, various vaporizers or vaporization supply devices have been developed for the purpose of efficiently vaporizing these raw materials without causing deterioration or precipitation. It was As such a vaporizer, for example, a vaporizer in which the contact portion of the CVD raw material supply portion with the CVD raw material is made of a corrosion-resistant synthetic resin such as a fluorine resin or a polyimide resin, or a vaporization supply device Examples of the vaporization supply device include the vaporizer as described above, and the metal constituent part of the CVD raw material supply part that receives heat conduction from the heating means when the vaporization chamber is heated can be cooled by a cooler. (Japanese Patent Application No. 2001-349840).

[0007]

The vaporizer is a CVD device.
In addition to heat resistance, the constituent material of the contact part with the raw material is a corrosion-resistant synthetic resin that has heat insulating properties and does not easily adhere to the CVD raw material. The solid CVD raw material was dissolved in an organic solvent. Even when a raw material is used, rapid heating of the raw material can be prevented, so that only the solvent is vaporized and the CVD raw material is extremely unlikely to deposit, and a vaporizer having a high vaporization efficiency of 99.9% or more can be obtained. The vaporization supply device has the vaporizer and is configured to cool the CVD raw material supply part of the vaporizer when the vaporization chamber is heated.
It is a vaporization and supply device in which the VD raw material precipitation preventing effect is further improved.

However, even if such a vaporizer and vaporization supply device having excellent vaporization efficiency are used, when a raw material prepared by dissolving a solid CVD raw material in an organic solvent is used, a trace amount of impurities are mixed in the semiconductor thin film. However, the quality of the semiconductor thin film may be adversely affected. Therefore, the problem to be solved by the present invention is to provide a vaporization and supply method capable of efficiently vaporizing even when a solid raw material is used as a CVD raw material and supplying the obtained vaporized gas to a semiconductor manufacturing apparatus with extremely high purity. It is to be.

[0009]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that the vaporized gas has pp
m-level unvaporized solid CVD raw material or precipitated solid CVD raw material is included, and many trace impurities in the semiconductor thin film are derived from the solid CVD raw material,
Further, they have found that particles of these solid CVD raw materials and the like can be easily removed by a filter and reached the present invention. That is, the present invention, after the solid CVD raw material is dissolved in an organic solvent, the raw material is supplied to a vaporizer and vaporized,
The vaporized supply method is characterized in that the vaporized gas containing the CVD raw material is filtered by a filter to remove particles contained in the vaporized gas and supplied to a semiconductor manufacturing apparatus.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is applied to a vaporizing and supplying method of vaporizing a raw material obtained by dissolving a solid CVD raw material in an organic solvent and supplying the vaporized raw material to a semiconductor manufacturing apparatus. The vaporization supply method of the present invention is a method in which a raw material obtained by dissolving a solid CVD raw material in an organic solvent is supplied to a vaporizer to be vaporized, and then the vaporized gas is filtered by a filter to obtain an unvaporized solid CVD contained in the vaporized gas.
This is a method of removing particles such as raw materials and precipitated solid CVD raw materials and supplying them to a semiconductor manufacturing apparatus.

CVD applied to the vaporization supply method of the present invention
The raw material is not particularly limited as long as it is a solid at room temperature and atmospheric pressure, and is appropriately selected and used according to the application. For example, hexacarbonyl molybdenum (Mo (CO) ₆ ), dimethyl pentoxy gold (Au (CH ₃ ) ₂ (OC ₅ H ₇ )), bismuth (III) tertiary butoxide (Bi (OtB)
u) ₃ ), bismuth (III) tertiary pentoxide (Bi (OtAm) ₃ ), triphenylbismuth (Bi
Ph ₃ ), bis (ethylcyclopentadienyl) ruthenium (Ru (EtCp) ₂ ), (ethylcyclopentadienyl) (trimethyl) platinum (Pt (EtCp) M
e ₃ ), 1,5-cyclooctadiene (ethylcyclopentadienyl) iridium (Ir (EtCp) (co
d)), bis (hexaethoxytantalum) strontium (St [Ta (OEt) ₆ ] ₂ ), bis (hexaisopropoxytantal) strontium (St [Ta (Oi
Pr) ₆ ] ₂ ), tris (2,2,6,6, -tetramethyl-3,5 heptanedionite) lanthanum (La (DPM) ₃ ), tris (2,2,6,6, -tetramethyl -3,5 heptane dionite) yttrium (Y (DPM) ₃ ), tris (2,2,6,
6, -Tetramethyl-3,5 heptanedionite) Ruthenium (Ru (DPM) ₃ ), bis (2,2,6,6, -tetramethyl-
3,5 heptane dionite) barium (Ba (DP
M) ₂ ), bis (2,2,6,6, -tetramethyl-3,5 heptanedionite) strontium (Sr (DPM) ₂ ), tetra (2,2,6,6, -tetramethyl-3 , 5 heptane dionite)
Titanium (Ti (DPM) ₄ ), tetra (2,2,6,6, -tetramethyl-3,5 heptanedionite) zirconium (Z
r (DPM) ₄ ), tetra (2,6, -dimethyl-3,5 heptanedionite) zirconium (Zr (DMHD) ₄ ), bis (2,2,6,6, -tetramethyl-3,5 heptane Gionite)
Lead (Pb (DPM) ₂ ), (di-tertiary butoxy)
Bis (2,2,6,6, -tetramethyl-3.5.heptanedionite) titanium (Ti (OtBu) ₂ (DPM) ₂ ),
(Di-isopropoxy) bis (2,2,6,6, -tetramethyl-
3,5, -heptanedionite) titanium (Ti (OiP
r) ₂ (DPM) ₂ ), (isopropoxy) tris (2,2,
Examples of CVD raw materials include 6,6, -tetramethyl-3,5, -heptanedionite) zirconium (Zr (OiPr) (DPM) ₃ ) or tetrakis (isobutyryl pivaloyl methanate) zirconium. it can. However,
It is usually necessary to dissolve these in an organic solvent at a concentration of about 0.1 to 1.0 mol / L before use.

The organic solvent used as a solvent for the solid CVD raw material usually has a boiling point of 40 ° C to 140 ° C.
Is an organic solvent. As those organic solvents, for example,
Ethers such as propyl ether, methyl butyl ether, ethyl propyl ether, ethyl butyl ether, trimethylene oxide, tetrahydrofuran, tetrahydropyran, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, acetone, ethyl methyl ketone, iso-propyl methyl ketone ,
ketones such as iso-butyl methyl ketone, propylamine,
Examples thereof include amines such as butylamine, diethylamine, dipropylamine and triethylamine, esters such as ethyl acetate, propyl acetate and butyl acetate, and hydrocarbons such as hexane, heptane and octane.

Next, the vaporization supply method of the present invention will be described in detail with reference to FIG. 1, but the present invention is not limited to this. FIG. 1 is a configuration diagram showing an example of a vaporization supply system to which the vaporization supply method of the present invention is applied. The vaporization supply system of FIG. 1 includes a CVD raw material container 2, a degasser 3, a liquid mass flow controller 4, a vaporizer 5, and a carrier gas supply line 7 in which a raw material 1 in which the solid CVD raw material is dissolved in an organic solvent is enclosed. , A filter 10 having a heater 9, an inert gas supply line 12 and the like. Although FIG. 1 shows a vaporization supply system having one system (one type of raw material) of vaporization supply lines, the vaporization supply method of the present invention can also be applied to a vaporization supply system having a plurality of systems of vaporization supply lines.

In the vaporization supply system as shown in FIG. 1, by applying an inert gas pressure in the CVD source container, the source is introduced into the liquid mass flow controller via the degasser, and the flow rate in the liquid state is reached. Is weighed and then fed to the vaporizer. In a vaporizer with excellent vaporization efficiency, the solid CVD raw material can be vaporized with a high vaporization efficiency of 99.9% or more. However, even if such a vaporizer is used, pp
It is presumed that the unvaporized solid CVD raw material remains at the m level and the solid CVD raw material is deposited at the ppm level from the vaporized gas. It is considered that these solid CVD raw materials usually exist as aggregate particles. The size of particles derived from such a solid CVD raw material varies depending on the type of vaporizer, the type of raw material, vaporization conditions, etc. and cannot be unconditionally limited, but is usually 0.00
It is about 1 to 0.1 μm. These particles adversely affect the quality of the semiconductor thin film and must be removed. The vaporized gas is presumed to contain a small amount of fine particles derived from impurities contained in the raw material and fine particles derived from the elution of the piping material by the solvent.

The filter in the vaporization supply method of the present invention can filter the particles as described above contained in the vaporized gas before the CVD raw material in the vaporized gas is used as the raw material for the vapor phase growth reaction in the semiconductor manufacturing apparatus. It may be installed at a position, and is usually installed at the outlet of the vaporizer, the inlet of the semiconductor manufacturing apparatus, or between the vaporizer and the semiconductor manufacturing apparatus.
For example, a vaporizer having a filter element (filter material) installed at the vaporized gas outlet, or a semiconductor manufacturing apparatus having a filter element (filter material) installed at the vaporized gas inlet can be used. However, it is preferable to install the filter between the vaporizer and the semiconductor manufacturing apparatus as shown in FIG. 1 in terms of easy maintenance.

Further, in the vaporizing and supplying method of the present invention,
Particles can be captured by the filter by installing the filter as described above, but the particles are once captured by maintaining the temperature at the time of filtering at or near the vaporization temperature of the CVD raw material. It is also possible to vaporize the solid CVD raw material and supply it to the semiconductor manufacturing apparatus. For this reason, it is preferable that the temperature of the vaporized gas or the temperature of the filter element at the time of filtering with a filter is within a range of 100 ° C. lower to 100 ° C. higher than the vaporized gas temperature in the vaporizer, and further 50 ° C. More preferably, it is in the range of low temperature to 50 ° C. higher.

The temperature of the vaporized gas or the temperature of the filter element at the time of filtering with a filter is 1 from the vaporization temperature.
If it is lower than 00 ℃, solid-state CVD in the filter
There is an inconvenience that the trapped amount of the raw material increases and the pressure loss increases, and when the vaporization temperature is 100 ° C. or higher, the CVD raw material may be decomposed. As a method for maintaining the temperature of the filter as described above, a method in which the distance between the vaporizer and the filter is shortened to perform filtration at a temperature close to the vaporization temperature, a heating means such as a heater is provided in the filter to keep the temperature at a predetermined level. A method of filtering while maintaining can be exemplified.

The filter used in the vaporization supply method of the present invention is not particularly limited as long as it has heat resistance and corrosion resistance above the vaporization temperature of the CVD raw material, but is usually a sintered metal. Filters, ceramic filters, fluororesin filters, etc. are used. However, the ceramic filter is usually limited to about 200 ° C. or lower, and the fluororesin filter is usually limited to about 230 ° C. or lower. Further, the filter is preferably one capable of removing particles corresponding to a diameter of 0.01 μm with a removal rate of 99.99% or more, and further capable of removing particles corresponding to a diameter of 0.001 μm with a removal rate of 99.99% or more. The thing is more preferable. Examples of commercially available filters include stainless steel filters (manufactured by Nippon Pionics Co., Ltd., SLF-E, L, M, X), Teflon (registered trademark) membrane filters (Japan Pionics Co., Ltd.).
Manufactured by XLF-D, E, L, M) can be used.

The vaporizer used in the vaporization and supply method of the present invention is not particularly limited, but preferably a CVD raw material whose flow rate is controlled with high accuracy by a liquid flow rate controller such as a liquid mass flow controller. What is capable of supplying the semiconductor manufacturing apparatus at a desired concentration and flow rate with extremely high vaporization efficiency is used. As such a vaporizer, for example, the shape of the vaporization container is spherical, ellipsoidal,
A vaporizer having a barrel shape, or a cylindrical shape having rounded ends, a conical shape, a truncated cone shape, or a hemispherical shape, and the carrier gas is set so as to form a swirl flow in the vaporization vessel (Japanese Patent Laid-Open No. 11-3
No. 42328), a vaporizer (Japanese Patent Application No. 2001-34) in which the contact portion of the CVD raw material supply portion with the CVD raw material is composed of a corrosion-resistant synthetic resin such as a fluorine-based resin or a polyimide-based resin.
9840) and the like.

[0020]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these.

Example 1 (Production of vaporization supply system) A vaporizer as shown in FIG. 2 was produced. The inside of the CVD raw material supply unit and the surface on the vaporization chamber side are made of a fluororesin (PFA), and the contact portion with the outside of the vaporizer is made of stainless steel (SUS316). The fluorinated resin component has an outer diameter of 16 mm and a height of 3
It has a cylindrical shape of 4.2 mm, and the thickness of the stainless steel outside thereof is 2.0 mm. Further, the vaporizer is the CV described above.
In addition to the D raw material supply section, it has a vapor gas discharge port, a heating means for the vaporization chamber, and a protrusion in which a heater is incorporated. The vaporization chamber has a cylindrical shape with an inner diameter of 65 mm and a height of 92.5 mm.
The height of the protrusion on the bottom is 27.5 mm, and 1 from the bottom.
A vaporized gas discharge port is provided at a height of 5 mm.

Next, solid-state CVD raw material (di-isopropoxy) bis (2,2,6,6, -tetramethyl-3,5, -heptanedionite) titanium (Ti (OiPr) ₂ (DP
M) ₂ ) is dissolved in THF, and a liquid CVD raw material container in which a raw material (concentration of solid CVD raw material: 0.3 mol / l) is sealed, a degasser, a liquid mass flow controller, a carrier gas supply line, a vaporizer, Stainless filter (manufactured by Nippon Pionics Co., Ltd., SLF-M, diameter 0.0)
1 μm uniform particle removal rate: 99.999999
9%), a vaporization supply system as shown in FIG. 1 was manufactured by connecting to a semiconductor manufacturing apparatus or the like on which a Si substrate was set.

(Evaporation supply test) Using the evaporation supply system as described above, an evaporation supply test is carried out as follows,
A TiO ₂ thin film was deposited on a Si substrate. The inside of the vaporizer is 1.6 kPa (12 torr), the temperature is 230 ° C., the inside of the semiconductor manufacturing apparatus is 0.93 kPa (7.1 torr), 5
The temperature of 50 ° C and the temperature of the filter element were maintained at 230 ° C. Next, Ti (OiPr) ₂ (DPM) ₂ / THF
0.2 g / mi using liquid mass flow controller
Argon gas heated to 230 ° C. from the carrier gas supply line while being supplied to the vaporizer at a flow rate of n,
The CVD raw material was vaporized in the vaporizer by supplying the vaporizer at a flow rate of 0.1 L / min. Further, argon gas and oxygen gas heated to 230 ° C. immediately before the semiconductor manufacturing apparatus were added at a flow rate of 0.1 L / min and 1.0 L / min, respectively, and vaporized gas was supplied to the semiconductor manufacturing apparatus for 2 hours.

After completion of the vaporization and supply, the substrate was taken out from the semiconductor manufacturing apparatus, and the surface of the TiO ₂ thin film was observed with an electron microscope to measure the adhered state of particles. Diameter 0.01μ
Table 1 shows the number of particles corresponding to a size of m or more per unit area. Further, it was confirmed that the weight of the filter increased due to the adhesion of particles. Table 1 shows the amount of particles attached.

Example 2 and Example 3 The temperature of the filter element in Example 1 was set to 200 each.
The vaporization supply test was performed in the same manner as in Example 1 except that the temperature was changed to 260 ° C., and a TiO ₂ thin film was deposited on the Si substrate. Table 1 shows the number of particles having a diameter of 0.01 μm or more per unit area and the amount of particles attached to the filter.

Example 4 Using the same vaporization supply system as in Example 1, tetra (2,6, -dimethyl-3,5 heptanedionite) zirconium (Zr (DPM) ₄ ) which is a solid CVD raw material was used as a raw material. Raw material dissolved in THF (concentration of solid CVD raw material: 0.
(3 mol / l) was used to perform a vaporization supply test as described below to deposit a ZrO ₂ thin film on a Si substrate.

The inside of the vaporizer is 1.6 kPa (12 torr).
r), the temperature of 230 ℃, 0.93k in the semiconductor manufacturing equipment
The temperature of Pa (7.1 torr), 550 ° C, and the temperature of the filter element were maintained at 230 ° C. Next Zr (DPM)
_While supplying ₄ / THF to the vaporizer at a flow rate of 0.2 g / min using a liquid mass flow controller,
Argon gas heated to 230 ° C. was supplied from the carrier gas supply line to the vaporizer at a flow rate of 0.1 L / min to vaporize the CVD raw material in the vaporizer. Further, argon gas and oxygen gas heated to 230 ° C. immediately before the semiconductor manufacturing apparatus are used at 0.1 L / min and 1.0 L / min, respectively.
And the vaporized gas was supplied to the semiconductor manufacturing apparatus for 2 hours.

After the vaporization and supply was completed, the substrate was taken out from the semiconductor manufacturing apparatus, and the surface of the ZrO ₂ thin film was observed with an electron microscope to measure the adhered state of particles. Diameter 0.01μ
Table 1 shows the number of particles corresponding to a size of m or more per unit area. Further, it was confirmed that the weight of the filter increased due to the adhesion of particles. Table 1 shows the amount of particles attached.

Example 5 and Example 6 The temperature of the filter element in Example 4 was set to 200 each.
A ZrO ₂ thin film was deposited on a Si substrate by performing a vaporization supply test in the same manner as in Example 4 except that the temperature was changed to 260 ° C. Table 1 shows the number of particles having a diameter of 0.01 μm or more per unit area and the amount of particles attached to the filter.

Example 7 Using the same vaporization and supply system as in Example 1, the raw material was solid CVD raw material bis (2,2,6,6, -tetramethyl-3,3).
5 Heptane dionite) lead (Pb (DPM) ₂ ) in THF
Raw material dissolved in (concentration of solid CVD raw material: 0.3 mo
1 / l) was used to carry out a vaporization supply test as described below to deposit a PbO thin film on a Si substrate.

The inside of the vaporizer is 1.6 kPa (12 torr).
r), 210 ° C temperature, 0.93k inside semiconductor manufacturing equipment
The temperature of Pa (7.1 torr), 550 ° C, and the temperature of the filter element were maintained at 230 ° C. Then Pb (DPM)
₂ / THF was supplied to the vaporizer at a flow rate of 0.36 g / min using a liquid mass flow controller, and the argon gas heated to 210 ° C from the carrier gas supply line was vaporized at a flow rate of 0.1 L / min. Then, the CVD raw material was vaporized in the vaporizer. Further, the argon gas and the oxygen gas heated to 210 ° C. just before the semiconductor manufacturing equipment are 0.1 L / min and 1.0 L / m, respectively.
The vaporized gas was supplied to the semiconductor manufacturing apparatus for 2 hours after the addition at a flow rate of in.

After completion of the vaporization and supply, the substrate was taken out from the semiconductor manufacturing apparatus, and the surface of the PbO thin film was observed with an electron microscope to measure the adhered state of particles. 0.01 μm diameter
Table 1 shows the number of particles corresponding to the above size per unit area. Further, it was confirmed that the weight of the filter increased due to the adhesion of particles. Table 1 shows the amount of particles attached.

Example 8 and Example 9 The temperature of the filter element in Example 7 was set to 200 each.
The vaporization supply test was performed in the same manner as in Example 7 except that the temperature was changed to 260 ° C., and a PbO thin film was deposited on the Si substrate. Table 1 shows the number of particles having a diameter of 0.01 μm or more per unit area and the amount of particles attached to the filter.

Comparative Example 1 A vaporization supply system similar to that of Example 1 was manufactured except that no filter was used. Using this vaporization supply system, a vaporization supply test was conducted in the same manner as in Example 1, and TiO 2 was used.
_Two thin films were deposited on a Si substrate. After completion of vaporization and supply, the substrate was taken out from the semiconductor manufacturing apparatus, and the surface of the TiO ₂ thin film was observed with an electron microscope to measure the adhered state of particles. Table 1 shows the number of particles having a diameter of 0.01 μm or more per unit area.

Comparative Example 2 Using the same vaporization supply system as in Comparative Example 1, a vaporization supply test was conducted in the same manner as in Example 4 except that no filter was used, and a ZrO ₂ thin film was deposited on a Si substrate. After vaporization and supply, take out the substrate from the semiconductor manufacturing equipment and
The surface of the rO ₂ thin film was observed with an electron microscope to measure the adhesion state of particles. Table 1 shows the number of particles having a diameter of 0.01 μm or more per unit area.
Shown in.

Comparative Example 3 Using the same vaporization supply system as in Comparative Example 1, a vaporization supply test was conducted in the same manner as in Example 7 except that no filter was used, and a PbO thin film was deposited on the Si substrate. After the vaporization and supply is completed, the substrate is taken out from the semiconductor manufacturing apparatus, and Pb
The surface of the O thin film was observed with an electron microscope to measure the adhered state of particles. Table 1 shows the number of particles having a diameter of 0.01 μm or more per unit area.

[0037]

[Table 1]

[0038]

According to the vaporization and supply method of the present invention, even when a solid raw material is used as a CVD raw material, it is possible to supply a vaporized gas of extremely high purity to a semiconductor manufacturing apparatus, which has been heretofore unknown. It has become possible to prevent deterioration of the quality of the semiconductor thin film due to the mixing of particles after vaporization of the raw material.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of a vaporization supply system to which a vaporization supply method of the present invention is applied.

FIG. 2 is a vertical sectional view showing an example of a vaporizer that can be used in the present invention.

[Explanation of symbols]

1 Raw material obtained by dissolving solid CVD raw material in organic solvent 2 CVD raw material container 3 degasser 4 Liquid mass flow controller 5 vaporizer 6 Gas mass flow controller 7 Carrier gas supply line 8 gas preheater 9 heater 10 filters 11 Semiconductor manufacturing equipment 12 Inert gas supply line 13 Insulation 14 CVD raw material inlet 15 Vaporization chamber 16 Vaporized gas outlet 17 Carrier gas inlet 18 Fluorine resin component 19 heater 20 protrusions

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Mitsuhiro Iwata             5181 Tamura, Hiratsuka, Kanagawa Japan Pio             Nix Corporation Hiratsuka Research Center F-term (reference) 4K030 AA11 BA01 BA18 BA22 BA42                       BA46 CA04 EA01 EA03 FA10                       JA10                 5F045 AA04 BB14 EE10

Claims (7)

[Claims] 1. A raw material obtained by dissolving a solid CVD raw material in an organic solvent is supplied to a vaporizer to be vaporized, and the vaporized gas containing the CVD raw material is filtered by a filter to remove particles contained in the vaporized gas. A vaporization and supply method, which comprises removing and supplying to a semiconductor manufacturing apparatus. 2. The vaporization supply method according to claim 1, wherein the filter is installed at the outlet of the vaporizer, the inlet of the semiconductor manufacturing apparatus, or between the vaporizer and the semiconductor manufacturing apparatus. 3. The vaporization and supply method according to claim 1, wherein the filter is a sintered metal filter, a ceramic filter, or a fluororesin filter. 4. The vaporization and supply method according to claim 1, wherein the filter is a filter capable of removing uniform particles having a diameter of 0.01 μm at a removal rate of 99.99% or more. 5. The particles are unvaporized solid CVD raw material and / or precipitated solid CVD raw material.
The vaporization and supply method described in. 6. The vaporization and supply method according to claim 1, wherein the temperature of the vaporized gas at the time of filtering with a filter is in the range of 100 ° C. lower to 100 ° C. higher than the vaporized gas temperature in the vaporizer. 7. The temperature of the filter element when filtering the vaporized gas is set by the heating means within a range of 100 ° C. lower to 100 ° C. higher than the vaporizing temperature.
The vaporization and supply method described in.