JPH09213664A - Method of processing substrate and processing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method of processing a substrate, in which organic compound removed from the substrate does not re-attach it, water molecules are effectively removed form it without increasing processing steps, the steps of drying process are not necessary before forming a thin film on the processed substrate, the deterioration of the roughness or the flatness of the substrate by the processing is little and the processing is not dependent on the material of the substrate and to provide the processing device. SOLUTION: In the processing method of the substrate, the substrate arranged in a gas tight chamber provided with exhaust means is exposed to ozone gas or/and heated gas. The density of the impurity included in the ozone gas or the heated gas is desirable to be 10ppb or less. Further, the temperature of the heated gas is 80 deg.C or more is desirable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate processing method and processing apparatus. More specifically, the present invention relates to a method and apparatus for treating a substrate for removing organic impurities or / and water molecules attached to the surface of the substrate.

[0002]

2. Description of the Related Art In recent years, in the fields of display devices and semiconductors, higher capacity and higher density are desired. At this time, in these fields, it is necessary to realize fine display technology and fine circuit technology.

To achieve the above technique,
Various film forming steps, etching steps, and cleaning steps are performed in a reduced pressure (vacuum) atmosphere, and various assembly steps, cleaning steps, and etching steps are performed in the air atmosphere.

In any process, when the substrate is subjected to any treatment, it is necessary to keep the surface of the substrate clean before the treatment. That is, it is important to remove organic impurities and water molecules existing on the surface of the substrate as much as possible. If the cleanliness is lowered or unstable, the characteristics of the substrate after the treatment in each step are greatly varied. As a result, there has been a problem that the yield of various products manufactured through each process is reduced.

Conventionally, as a method for dealing with the above problem,
The following techniques are known. A method of performing various kinds of drying treatment after wet-cleaning a substrate with pure water, various alcohols, or various solvents in the air, and before forming a thin film on the substrate. A method of performing various dry treatments after wet etching a substrate with various etching solutions in the air and before forming a thin film on the substrate. A method of dry etching a substrate using various plasmas in a vacuum. In the air, ozone is generated by decomposing oxygen contained in the atmosphere with a light source of ultraviolet rays having a non-single spectrum (a wavelength of 184 nm and a wavelength of 200 nm or more) such as a low-pressure mercury lamp. A method of exposing the substrate to A method of depositing one or more thin films on a substrate in a vacuum to form a new clean surface on the substrate.

However, the above conventional technique has the following problems. (1) In the above techniques and, various drying treatment steps are indispensable before forming a thin film on a substrate, resulting in high manufacturing cost. In addition, since it is exposed to the atmosphere after the treatment, organic substances and water molecules are redeposited on the surface of the substrate. (2) In the above techniques and, the roughness of the surface of the substrate increases due to etching, and the flatness of the substrate also decreases, so that disorder occurs in the thin film or structure formed on the substrate. (3) In the above technique, the polymerization of the organic substance removed from the substrate occurs, and it reattaches to the substrate.
Further, the ozone generation efficiency is low under reduced pressure. (4) The above-mentioned technique has many restrictions because the number of processes under vacuum increases, the manufacturing cost becomes high, and the material of the substrate depends.

[0007]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a method for treating a substrate and an apparatus for treating the substrate, in which organic substances removed from the substrate do not redeposit.

A second object of the present invention is to provide a substrate processing method and a processing apparatus capable of efficiently removing water molecules without increasing the number of processing steps.

Further, according to the present invention, various drying treatment steps are not required before forming a thin film on the treated substrate, and the treatment does not increase the roughness or flatness of the substrate surface, and
A third object of the present invention is to provide a substrate processing method and a substrate processing apparatus which are less dependent on the material of the substrate.

[0010]

The present invention is a method for treating a substrate, characterized in that the substrate disposed in an airtight chamber provided with at least exhaust means is exposed to ozone gas and / or heated gas. There is a summary in.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The operation of each claim according to the present invention will be described below.

According to the first aspect of the present invention, since the substrate disposed in the airtight chamber provided with at least the exhaust means is exposed to the ozone gas, the residual amount of the organic impurities existing on the substrate can be reduced.

According to the second aspect of the present invention, since at least the substrate arranged in the airtight chamber provided with the exhaust means is exposed to the heated gas, the amount of water molecules remaining on the substrate can be reduced.

According to the third aspect of the invention, since the substrate disposed in the airtight chamber having at least the exhaust means is exposed to the ozone gas and the heated gas, the residual amount of the organic impurities existing on the substrate and The residual amount of water molecules can be reduced at the same time.

In the invention according to claim 4, since the concentration of impurities contained in the ozone gas is 10 ppb or less,
The remaining amount of organic impurities existing on the substrate can be further reduced.

In the invention according to claim 5, since the impurity concentration contained in the heated gas is 10 ppb or less, the residual amount of water molecules existing on the substrate can be further reduced.

In the invention according to claim 6, since the temperature of the heated gas is 80 ° C. or higher, the effect of reducing the residual amount of water molecules existing on the substrate is significantly enhanced. As a result, the processing time of the substrate can be shortened.

In the invention according to claim 7, since the heated gas is one gas selected from rare gas, nitrogen gas, ozone gas or hydrogen gas, the action of removing water molecules existing on the substrate is achieved. A high substrate processing method is obtained.

According to the invention of claim 8, claims 1 to 7
Since the method for treating a substrate according to any one of 1 above is used,
It is possible to obtain a substrate treating apparatus capable of reducing the residual amount of organic impurities and / or the residual amount of water molecules existing on a substrate.

According to a ninth aspect of the present invention, there is provided an apparatus for treating a substrate having an airtight chamber having at least an exhaust means and a treatment chamber, wherein the treatment of the substrate according to any one of the first to seventh aspects is performed in the airtight chamber. A thin film having a stable structure is obtained because the thin film is formed in the processing chamber on the substrate subjected to the method.

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

(Airtight chamber equipped with at least exhaust means) The airtight chamber according to the present invention can eliminate ozone gas or heated gas introduced into the airtight chamber as shown in FIG. 2, FIG. 3 or FIG. It has an exhaust means. Various general-purpose pumps may be used as the exhaust means. When reducing the pressure in the airtight chamber, various vacuum pumps are appropriately used.
In particular, when the flow rate of the introduced gas is large, a plurality of pumps are connected in multiple stages and used. For example, a combination of a molecular drug pump (manufactured by Daikin, DMS600ACR) + mechanical booster pump (manufactured by Edwards, QMB500) + dry pump (manufactured by Edwards, QDP80) can be mentioned. With this combination, the gas flow rate is 50 SLM
Allows continuous use.

Examples of the material forming the inner wall of the hermetic chamber include SUS (316L, 304L, etc.), Al, Ni alloy (Hastelloy, etc.). In particular, when introducing ozone gas into the airtight chamber, the inner wall of the airtight chamber must be made of a material having high ozone gas resistance. Examples of such a material include Fe ₂ O ₃ / SUS-316L (Fe on the surface is
SUS-316L) in which a ₂ O ₃ film is formed with a thickness of several tens of nm is preferable. This is advantageous because the material is not modified by O ₃ and O ₃ is not deactivated as compared with Al.

When a heated gas other than O ₃ is introduced, the material forming the inner wall of the hermetic chamber is, for example, (Cr ₂ O ₃ , Fe ₂ O ₃ ) / SUS-316L (electrolytic polishing or composite C on the surface of electrolytically polished SUS-316L
r ₂ O ₃ film and Fe ₂ O ₃ film which was provided), Al to the surface roughness Ra is polished to about 0.1μm is preferably used.
It is excellent in that the emission of the impurity gas from the material itself constituting the surface is small.

The position where the gas introduction system is connected to the airtight chamber is
It is preferable that the exhaust means is provided substantially opposite to the position where it is connected to the airtight chamber, and that the gas introduced into the airtight chamber becomes a turbulent flow. When this arrangement is adopted, the gas is not retained and the effect of the present invention is not impaired, which is advantageous. For example, the arrangement as shown in FIG. 2 or FIG.

The above-mentioned airtight chamber is connected to the T through a gate valve.
A DS (Thermal Desorption Spectroscopy) analysis room was provided. In the TDS analysis room, heat was applied to the substrate to release organic impurities and water molecules adhering to the substrate surface, and the released gas was quantitatively evaluated by an analyzer described later.

The TDS analysis chamber is equipped with an evacuation means, and the evacuation means is appropriately selected in the same manner as the airtight chamber depending on the atmospheric pressure for evaluating and analyzing organic impurities and water molecules adhering to the surface of the substrate.

When the pressure in the TDS analysis chamber is measured near atmospheric pressure, a TDS device (UG-21) manufactured by Hitachi Tokyo Electronics was attached to the analysis chamber (FIG. 2). The evaluation of organic impurities and water molecules desorbed from the substrate surface is performed by TD
APIMS (Atmospheric Pressure I
onization Mass Spectrometer, atmospheric pressure ionization mass spectrometer). Further, during the analysis, Ar, N _2, etc. were appropriately introduced as a carrier gas.

On the other hand, in the case of measurement under reduced pressure, a TDS device (EMD-WA1000K) manufactured by Electronic Science was attached to the analysis room (FIG. 3). Evaluation of organic impurities and water molecules desorbed from the surface of the substrate is performed by QMS attached to the TDS device.
(Quadrupole Mass Analyzer).

(Substrate) Examples of the substrate include a glass substrate (alkali-free borosilicate glass, soda glass, quartz, etc.), Si wafer substrate (F _Z (100), C _Z (100)).
Etc.) and ceramics substrates (Al ₂ O ₃ , SiC, etc.). Further, it also includes those in which various films are provided on these substrates. As various coatings, for example, Al, Mo, T
a, SiN, TiN, a-Si, etc. are mentioned. Further, one in which an electronic element or circuit, a magnetic element or circuit, an optical element or circuit, and the like are provided on the substrate by stacking these films and processing the shape is also an example of the substrate according to the present invention. .

As the substrate having an electronic element or circuit,
For example, TFT (Thin Film Transistor), MOSFET
(Metal Oxide Semiconductor Field Emittion Transi
stor), or those provided with a Diode Capacitor. Above all, an LCD cell (Liquid Crystal Display Cell) having a TFT (Thin Film Transistor) circuit, that is, an active matrix LCD, or an LCD having segment electrodes and common electrodes formed of transparent electrodes.
When manufacturing a cell (Liquid Crystal Display Cell), that is, a simple matrix type LCD, the substrate processing method and the processing apparatus according to the present invention are preferably used.

As the substrate having the magnetic element or the circuit,
Examples include magnetic disks, magnetic heads, and magnetic cards. Examples of the substrate having an optical element or circuit include various light emitting and receiving devices represented by LEDs and semiconductor lasers, and optical (magneto-optical) disks.

(Ozone Gas) The ozone gas according to the present invention is a mixed gas composed of O ₃ , O ₂ and N ₂ .
O ₃ concentration is 1 ppm to 1000 ppm (O ₃ : (O ₂ +
Those in the range of N ₂ ) = 1: 10 ⁶ to 10 ³ ) are preferably used. Gas components other than O ₃ , O ₂ and N ₂ are impurities contained in ozone gas, such as H ₂ O, CO ₂ and C.
H ₄ may be mentioned. When the concentration of impurities contained in the ozone gas is 1000 ppb or less, the detected amount of the organic gas impurities during TDS measurement is greatly reduced, and the effect of removing the organic gas impurities becomes remarkable, which is preferable. Further, when the impurity concentration is set to 10 ppb or less, the amount of the organic gas impurities is saturated in a state in which the detected amount is small, so that it can be determined that the amount of the organic gas impurities present on the surface of the substrate is almost the minimum value. preferable.

The ozone gas used in the present invention is a commercially available O ₃ generator (SG-manufactured by Sumitomo Precision Industries Co., Ltd.) arranged near the airtight chamber.
01A1) with partially improved impurity concentration of 1pp
It was manufactured by supplying O ₂ and N ₂ of b or less. The impurity concentration of the obtained ozone gas was 1 ppb or less, and the ozone gas was introduced into the airtight chamber through the ozone gas resistant pipe. In addition, a known impurity of 10 pp was added to the pipe section connecting the O ₃ generator and the airtight chamber.
ozone gas to be introduced into the hermetic chamber by adding an appropriate amount of impurities to ozone gas having an impurity concentration of 1 ppb or less from an impurity addition system consisting of a gas dilution system in which a multi-stage N ₂ gas supply system and a mass flow controller are added. The impurity concentration contained in was changed from 100 ppm to 1 ppb.

(Heated Gas) As the heated gas according to the present invention, it is easy to transfer heat to the substrate through the gas,
Moreover, a gas species capable of removing water molecules from the surface of the substrate is preferable. For this reason, one gas selected from rare gas (He, Ar, etc.), nitrogen gas, ozone gas or hydrogen gas is preferably used.

Gas components other than each heated gas are impurities contained in each heated gas, such as H ₂ O and C.
Examples include O ₂ and CH ₄ . When the heated gas is nitrogen gas, the concentration of impurities contained in the nitrogen gas is the same as that of the nitrogen gas in which 100 ppm of known impurities are added to the pipe part connecting the supply system of nitrogen gas having a contained impurity concentration of 1 ppb or less and the hermetic chamber An appropriate amount of impurities is added to the nitrogen gas with an impurity concentration of 1 ppb or less from the impurity addition system consisting of a gas dilution system in which different supply systems and mass flow controllers are combined in multiple stages, and is included in the nitrogen gas introduced into the hermetic chamber. The impurity concentration to be generated was changed in the range of 100 ppm to 1 ppb. The impurity concentration contained in each heated gas is 1000 p
When the content is pb or less, the amount of H ₂ O detected during TDS measurement is greatly reduced, and the effect of removing H ₂ O becomes remarkable, which is preferable. Further, when the impurity concentration is set to 10 ppb or less, the amount of H ₂ O is saturated in a small amount.
It is more preferable because it can be judged that the amount of H ₂ O existing on the surface of the substrate has reached the minimum value.

As a method of applying heat to the gas, for example, a method of attaching a heater to a gas introducing pipe to the airtight chamber and indirectly heating via the pipe can be mentioned. When the temperature of each heated gas is 50 ° C. or higher, the amount of H ₂ O detected during TDS measurement is greatly reduced, and the effect of removing H ₂ O becomes remarkable, which is preferable. Further, when the temperature is set to 80 ° C. or higher, the amount of H ₂ O existing on the surface of the substrate becomes almost the minimum value because it saturates in a state where the amount of H ₂ O detected is small. preferable.

(Substrate Processing Apparatus Having At least Airtight Chamber Equipped with Exhaust Means and Processing Chamber) In the substrate processing apparatus according to the present invention, the above-mentioned airtight chamber is provided with a processing chamber via a gate valve. The processing chamber is provided with at least exhaust means. The exhaust means is appropriately selected similarly to the airtight chamber depending on the operating pressure in the airtight chamber. Depending on the case, it is possible to provide an appropriately selected exhaust means independently of the operating pressure in the airtight chamber. Therefore, the internal pressure of the processing chamber is not particularly limited.

In the processing chamber, a thin film is formed on the substrate which has been subjected to the predetermined processing in the airtight chamber, but any thin film forming method may be used. For example, under atmospheric pressure, a coating method, a plating method, and the like, and under a reduced pressure, an evaporation method, a sputtering method, a CVD method, and the like can be given.

The material of the thin film to be formed is not limited, but for the purpose of controlling various characteristics and adhesion of the thin film, the substrate may be appropriately heated or cooled when the thin film is formed.
Further, an electric field and / or a magnetic field may be introduced into the space where the thin film is formed.

(Substrate Evaluation Method) The substrate evaluation method according to the present invention will be described below with reference to FIGS. 2 and 3.

(1) When the pressure in the TDS analysis chamber is near atmospheric pressure: The substrates I and II were set in a rotatable substrate holder in an airtight chamber. The substrate I was moved to a TDS apparatus that was always purged with high-purity Ar having an impurity gas concentration other than Ar of 1 ppb or less and was in a clean atmosphere. The substrate I was heated from room temperature to 500 ° C. while supplying Ar at 2 l / min, and the carrier Ar gas containing the gas desorbed in the process was analyzed by APIMS. After moving the substrate I to the airtight chamber, the substrates I and II were treated with ozone gas and / or heated gas. Substrate II was transferred to a TDS instrument and analyzed by APIMS as described above and.

(2) When the pressure in the TDS analysis chamber is under reduced pressure'Substrates I and II were set in a rotatable substrate holder in an airtight chamber. 'After depressurizing the airtight chamber to 1 × 10 ^-6 Torr, 2 × 1 in advance
The substrate I was moved to the TDS apparatus which was depressurized to 0 ^-9 Torr. The substrate I was heated from room temperature to 500 ° C., and the gas desorbed in the process was analyzed by QMS. 'After moving the substrate I to the airtight chamber, the substrates I and II were treated with ozone gas and / or heated gas. Substrate II was transferred to a TDS instrument and analyzed by APIMS as in'above 'and'.

(Evaluation Method of Thin Film) The evaluation items of the Al thin film according to the present invention include specific resistance, hillock, hot pure water oxidation and crystallinity. Each of these evaluation methods is described below.

[Specific Resistance] The specific resistance (Ω · cm) was calculated from the product of the sheet resistance (Ω / □) and the film thickness (nm). The sheet resistance was measured using HA-6100 / RG-1000E manufactured by Napson on the thin film (on the substrate) immediately after film formation. After that, the thin film is subjected to a patterning process so that the film thickness at the sheet resistance measuring portion is DEKTAK-30 manufactured by ULVAC.
It was measured at 30.

[Hillock] Hillock was measured by the following procedure. Observe the thin film (on the substrate) immediately after film formation with an optical microscope,
I took a picture. The above thin film (for each substrate) was set to 400 under N ₂ atmosphere.
It was annealed at 2 ° C. for 2 hours. The thin film (on the substrate) that had been subjected to the above treatment was observed with an optical microscope and a photograph was taken. The number of hillocks shown in the above photograph (magnification: 825) was measured, the difference between them was determined, and the presence or absence of increase in hillocks per unit area was examined. A hillock size of several hundreds nm or more was measured.

[Warm pure water oxidation] The warm pure water oxidation was measured by the following procedure. The thin film (on the substrate) after film thickness measurement with the above-mentioned specific resistance is
It was immersed in warm ultrapure water at ℃ for 20 minutes. The film thickness of the thin film (on the substrate) after the above treatment was measured. When the film thickness after the immersion was larger than that before the immersion, it was judged that Al was oxidized and changed to AlO _x , and the volume increased.
The presence or absence of this oxidation state is determined by XPS (Xray Photoelectron S
It was separately confirmed using pectroscopy and X-ray photoelectron spectroscopy.

[Crystallinity] The crystallinity was measured by measuring the diffraction intensity with an X-ray diffractometer made by Riken after cutting a substrate having a thin film immediately after film formation attached thereto into a 3 cm square.

[0049]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Example 1) In this example, a substrate is placed in the airtight chamber shown in FIG. 2, and the residual amount of organic impurities existing on the substrate before and after being exposed to ozone gas in the vicinity of atmospheric pressure is determined. The examination was carried out in a TDS analysis room provided in the airtight chamber through a gate valve. In the TDS analysis room, heat is applied to the substrate to remove organic impurities adhering to the surface of the substrate,
The released gas was quantitatively evaluated using APIMS.
A Si wafer (F _Z (100)) or glass (# 7059) was used as the substrate.

The following is a description according to the experimental procedure. (1) The following treatments shown in and were sequentially performed to wash the two substrates. A cassette (material: Tefzel) containing a substrate was immersed in ultrapure water (specific resistance: 18 MΩ), and megasonic (0.8 MHz) was added to the ultrapure water for 10 minutes. The substrate after the above treatment is spin dried (850 r
pm, 2 minutes). (2) After inserting the cassette containing the two substrates that have been subjected to the treatment of (1) above into the airtight chamber, one substrate is transferred to the TDS analysis chamber without treatment, and the organic system adhered to the surface of the substrate. Impurities were released and the amount of removal was measured by APIMS. (3) Another substrate was exposed to ozone gas by introducing ozone gas into the airtight chamber under the following conditions.・ Supply gas: O ₃ 100 ppm / O ₂ : N ₂ = 1: 4 ・ Ozone gas impurity concentration: 1 ppb or less ・ Internal pressure of airtight chamber: 760 Torr ・ Supply time: 10 min (4) Substrate that has undergone the treatment of (3) above Was transferred to the TDS analysis room, and the organic impurities adhering to the surface of the substrate were released in the same manner as in (2) above, and the amount of release was measured.

FIG. 1 shows the measurement results of the amount of organic impurities (mass number 28) separated from the substrate surface before and after exposure to ozone gas. From FIG. 1, it was found that the organic impurities were removed on the surface of the substrate exposed to the ozone gas without depending on the material of the substrate.

(Embodiment 2) This embodiment differs from Embodiment 1 in that the substrate is placed in the airtight chamber shown in FIG. 3 and the substrate is exposed to ozone gas in the airtight chamber under reduced pressure. The TDS analysis chamber was also under a reduced pressure at the same level as the airtight chamber, and the substrate was heated to release organic impurities adhering to the substrate surface, and the released gas was quantitatively evaluated using QMS.
Other points were the same as in Example 1.

The following is a description according to the experimental procedure. (1) Two substrates were washed in the same manner as in step (1) of Example 1. (2) After inserting the cassette containing the two substrates, which has undergone the treatment of (1) above, into the airtight chamber, the airtight chamber is set to 1 × 10 ^−6.
The pressure was reduced to Torr. (3) One substrate is left untreated and 2 × 10 ^{-9 in} advance
Transfer to a TDS analysis chamber that has been depressurized to Torr to separate organic impurities adhering to the substrate surface,
Measured by MS. (4) Another substrate was exposed to ozone gas by introducing ozone gas into the airtight chamber under the following conditions.・ Supply gas: O ₃ 100 ppm / O ₂ : N ₂ = 1: 4 ・ Ozone gas impurity concentration: 1 ppb or less ・ Internal pressure of hermetic chamber: 700 Torr ・ Supply time: 10 min (5) Substrate that has undergone the treatment of (4) above 2 x 1 in advance
The sample was transferred to a TDS analysis chamber that had been depressurized to 0 ^-9 Torr, and the organic impurities adhering to the surface of the substrate were detached in the same manner as in (2) above, and the detached amount was measured.

FIG. 4 shows the measurement results of the amount of organic impurities (mass number 28) separated from the substrate surface before and after exposure to ozone gas. From FIG. 4, it was found that the organic impurities were removed on the surface of the substrate exposed to ozone gas even under reduced pressure without depending on the material of the substrate.

(Embodiment 3) In this embodiment, the substrate is arranged in the airtight chamber shown in FIG. 2, and the residual amount of water molecules existing on the substrate before and after being exposed to the heated gas in the vicinity of atmospheric pressure. Was examined in a TDS analysis room provided in the airtight chamber through a gate valve. Nitrogen gas at 50 ° C. was used as the heated gas.

In the TDS analysis room, heat was applied to the substrate to release water molecules attached to the substrate surface, and the released gas was quantitatively evaluated using APIMS. As the substrate, Si wafer (F _Z (100)) or glass (# 70)
59) was used. Other points were the same as in Example 1.

The following is a description of the experimental procedure. (1) Two substrates were washed in the same manner as in step (1) of Example 1. (2) After inserting the cassette containing the two substrates that have been subjected to the treatment of (1) above into the airtight chamber, one substrate is transferred to the TDS analysis chamber without treatment, and water molecules attached to the substrate surface Was withdrawn, and the amount of withdrawal was measured by APIMS. (3) Another substrate was exposed to nitrogen gas by introducing nitrogen gas into the hermetic chamber under the following conditions.・ Supply gas: N ₂ (Temperature: 50 ° C., Flow rate: 50 SLM) ・ Impurity concentration of nitrogen gas: 1 ppb or less ・ Internal pressure of airtight chamber: 760 Torr ・ Supply time: 10 min (4) TDS of the substrate after the treatment of (3) above The sample was transferred to an analysis room, and water molecules attached to the surface of the substrate were released in the same manner as in (2) above, and the amount of release was measured.

FIG. 5 shows the measurement results of the water molecular weight (mass number 18) separated from the surface of the substrate before and after the exposure to the heated nitrogen gas. From FIG. 5, it was found that water molecules were removed on the surface of the substrate exposed to the heated nitrogen gas, regardless of the material of the substrate.

(Embodiment 4) This embodiment differs from Embodiment 3 in that the substrate is placed in the airtight chamber shown in FIG. 3 and the substrate is exposed to heated nitrogen gas in the airtight chamber under reduced pressure. .
The TDS analysis chamber was also under a reduced pressure at the same level as the airtight chamber, and the substrate was heated to release water molecules attached to the substrate surface, and the released gas was quantitatively evaluated using QMS.
Other points were the same as in Example 3.

The following is a description according to the experimental procedure. (1) Two substrates were washed in the same manner as in step (1) of Example 1. (2) After inserting the cassette containing the two substrates that have undergone the treatment of (1) above into the airtight chamber, the airtight chamber is set to 1 × 10 ^−4.
The pressure was reduced to Torr. (3) One substrate is left untreated and 2 × 10 ^{-9 in} advance
The sample was transferred to a TDS analysis chamber where the pressure was reduced to Torr, water molecules adhering to the substrate surface were released, and the amount of separation was measured by QMS. (4) Another substrate was exposed to nitrogen gas by introducing nitrogen gas into the hermetic chamber under the following conditions.・ Supply gas: N ₂ (Temperature 50 ° C., Flow rate 50 SLM) ・ Impurity concentration of nitrogen gas: 1 ppb or less ・ Internal pressure of airtight chamber: 700 Torr ・ Supply time: 10 min (5) Preliminarily the substrate after the treatment of (4) above 2 x 1
The sample was transferred to a TDS analysis chamber where the pressure was reduced to 0 ^-9 Torr, and water molecules adhering to the surface of the substrate were released in the same manner as in (2) above, and the amount of separation was measured.

FIG. 6 shows the measurement results of the water molecular weight (mass number 18) desorbed from the surface of the substrate before and after the exposure to the heated nitrogen gas. From FIG. 6, the surface of the substrate exposed to the heated nitrogen gas even under reduced pressure does not depend on the material of the substrate,
It was found that water molecules were removed.

In Examples 3 and 4, nitrogen gas was used as the heated gas, but a similar effect can be obtained by using a rare gas (eg He, Ar, Xe, etc.), ozone gas or hydrogen gas instead of nitrogen gas. It was separately confirmed that there is. In particular, when ozone gas is used as the heated gas, the effects of Example 1 or 2 and Example 3 or 4 can be realized at the same time. That is, since the organic impurities and water molecules existing on the surface of the substrate can be removed at the same time, the treatment process can be shortened, and the substrate treatment method capable of reducing the cost can be obtained.

(Embodiment 5) This embodiment differs from Embodiment 1 in that the concentration of impurities contained in ozone gas is changed within the range of 1 ppm to 1 ppb. As the substrate, glass (# 705
9) was used. Other points were the same as in Example 1.

FIG. 7 shows the results of measuring the concentration of impurities contained in ozone gas and the amount of organic impurities remaining on the surface of the substrate after the treatment. From FIG. 7, it was found that when the concentration was 1 ppm or less, the amount of organic impurities released from the substrate surface during TDS measurement drastically decreased, so that the amount of organic impurities remaining on the substrate surface decreased. Also, 10
When it was ppb or less, the decreasing gradient of the amount of organic impurities released from the surface of the substrate was remarkably alleviated, so that it was determined that the amount of organic impurities remaining on the surface of the substrate approached the minimum value.

Example 6 This example differs from Example 3 in that the concentration of impurities contained in the heated nitrogen gas was changed within the range of 1 ppm to 1 ppb. Glass (# 7059) was used as the substrate. Other points were the same as in Example 3.

FIG. 8 shows the results of measuring the concentration of impurities contained in the heated nitrogen gas and the amount of water molecules remaining on the surface of the substrate after the treatment. From FIG. 8, it was found that when the concentration was 1 ppm or less, the amount of water molecules released from the substrate surface during TDS measurement drastically decreased, so that the amount of water-containing molecules remaining on the substrate surface decreased. Further, when it was 10 ppb or less, the decreasing gradient of the amount of water molecules released from the surface of the substrate was remarkably alleviated, so that it was judged that the amount of water molecules remaining on the surface of the substrate approached the minimum value.

(Embodiment 7) This embodiment is different from Embodiment 3 in that the heating temperature of nitrogen gas is changed in the range of room temperature (about 20 ° C.) to 400 ° C. As the base material, glass (# 7059)
Was used. Other points were the same as in Example 3.

FIG. 9 shows the results of measuring the temperature of nitrogen gas and the amount of water molecules remaining on the surface of the substrate after the treatment. FIG.
From this, it was found that when the temperature was 50 ° C. or higher, the amount of water molecules released from the surface of the substrate was rapidly reduced, and the amount of water molecules remaining on the substrate surface was reduced. 80 ° C
In the above case, since the decreasing gradient of the amount of water molecules released from the surface of the substrate is remarkably relaxed, it was determined that the amount of water molecules remaining on the surface of the substrate was close to the minimum value.

Example 8 In this example, a thin film was formed in the processing chamber on the substrate whose surface was exposed to the gas heated in the airtight chamber shown in FIG. 10, and various characteristics of the produced thin film were examined. It was

Nitrogen gas was used as the heated gas, glass (# 7059) was used as the substrate, and aluminum was used as the thin film. The film properties evaluated are resistivity, hillock, hot pure water oxidation and crystallinity.

The following is a description according to the experimental procedure. (1) The same substrate cleaning as in step (1) of Example 1 was performed. (2) The cassette containing the substrate that has undergone the treatment of (1) above was inserted into the airtight chamber. (3) The airtight chamber was evacuated to 1 × 10 ⁻⁴ Torr. (4) Heated nitrogen gas (temperature 1
50 ° C. and a flow rate of 50 SLM) were introduced, and the exhaust conductance was adjusted to adjust the pressure in the airtight chamber to 5 Torr, and purging was performed for 1 minute. (5) After stopping the supply of nitrogen gas to the airtight chamber, the airtight chamber was evacuated to 1 × 10 ^-2 Torr. (6) The above steps (4) to (5) were repeated four times. (7) The airtight chamber was evacuated to 5 × 10 ⁻⁷ Torr. (8) The substrate was moved from the hermetic chamber to a processing chamber which was separately evacuated to 5 × 10 ⁻⁷ Torr. (9) In the processing chamber, high frequency power (or power density 4 with a power density of 1.5 W / cm ² and frequency of 13.56 MHz).
DC power of W / cm ² ) is supplied to the cathode to generate plasma, and the thickness is 20 on the heated substrate (150 ° C.).
An aluminum film of 0 nm was formed.

The sample produced by the above steps (1) to (9) was designated as trial sample 8.

(Comparative Example 1) In this example, pretreatment of the substrate in Example 8, that is, steps (3) to (6) in Example 8 were performed.
Was deleted. The other points were the same as in Example 8.

The sample prepared in this example was designated as trial ratio 1.

Table 1 shows the evaluation results of the specific resistance, hillock, hot pure water oxidation, and crystallinity, which were performed on the samples prepared in Example 6 and Comparative Example 1 described above.

[0077]

[Table 1]

From Table 1, it was found that Sample 6 was a more stable thin film than Sample 1. Therefore, it was determined that the stability of the film structure can be improved by using the substrate processing method according to the present invention when various thin films are produced in the fields of display devices and semiconductors.

In general, since the crystallinity was improved, it was judged that the substrate processing method according to the present invention showed almost no increase in roughness or decrease in flatness on the processed surface.

In this example, the method of treating the substrate according to the present invention was examined using a single layer film having a simple structure. However, various semiconductor devices having a multi-layer structure or a complicated structure and TFT-LC
It goes without saying that it is also effective in the step of producing D and the like.

[0081]

As described above, according to the present invention,
The organic substances removed from the substrate do not redeposit, water molecules can be removed efficiently without increasing the number of treatment steps, and various drying treatment steps are not required before forming a thin film on the treated substrate. Roughness increase and flatness decrease are small,
In addition, it is possible to obtain a substrate processing method and a substrate processing device that are less dependent on the material of the substrate.

[Brief description of drawings]

FIG. 1 is a graph showing the measurement results of the amount of organic impurities released from the substrate surface before and after exposure to ozone gas in the vicinity of atmospheric pressure according to Example 1 of the present invention.

FIG. 2 is a schematic cross-sectional view of a substrate processing apparatus including an airtight chamber and a TDS analysis chamber according to the first embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view of a substrate processing apparatus including an airtight chamber and a TDS analysis chamber according to a second embodiment of the present invention.

FIG. 4 is a graph showing the measurement results of the amount of organic impurities released from the substrate surface before and after exposure to ozone gas under reduced pressure according to Example 2 of the present invention.

FIG. 5 is a graph showing the measurement results of the amount of water molecules released from the substrate surface before and after exposure to heated nitrogen gas in the vicinity of atmospheric pressure according to Example 3 of the present invention.

FIG. 6 is a graph showing the measurement results of the amount of water molecules released from the substrate surface before and after exposure to heated nitrogen gas under reduced pressure according to Example 4 of the present invention.

FIG. 7 is a graph showing the measurement results of the concentration of impurities contained in ozone gas and the amount of organic impurities remaining on the substrate surface after the treatment according to Example 5 of the present invention.

FIG. 8 is a graph showing the measurement results of the concentration of impurities contained in heated nitrogen gas and the amount of water molecules remaining on the surface of the substrate after the treatment according to Example 6 of the present invention.

FIG. 9 is a graph showing the measurement results of the temperature of nitrogen gas and the amount of water molecules remaining on the surface of the substrate after the treatment according to Example 7 of the present invention.

FIG. 10 is a schematic cross-sectional view of a substrate processing apparatus including an airtight chamber and a processing chamber according to Example 8 of the present invention.

[Explanation of symbols]

200, 300, 900 Airtight chamber, 201, 301, 901 TDS device, 202 APIMS, 203, 303, 903 O ₃ generator, 204, 304, 904 Hot gas generation mechanism, 205, 305, 905 Gas diluter, 206, 306, 906 Standard gas cylinder, 207, 307, 907 Substrate I, 208, 308, 908 Substrate II, 209, 309, 909 Substrate holder (cassette), 210, 310, 320, 910, 931 Turbo molecular pump, 211, 311, 911 Gate valve, 212, 312 Substrate for TDS measurement, 213, 313 TDS device substrate holder, 214 Infrared lamp, 215 High-purity Ar introduction line, 216 Ar line between TDS device and APIMS, 217, 218, 317, 318 , 917, 918 Kojun Degree N ₂ line, 219, 319, 919 high-purity O ₂ line, 302 QMS, 314 infrared introducing device, 912 substrate in processing chamber, 930 processing chamber, 932 Ar line, 933 Al target, 934 substrate holder / cathode.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor, Jie Kubota, 3-31, Meidori, Izumi-ku, Sendai-shi, Miyagi Frontech Co., Ltd. Incorporated company Frontech (72) Inventor Tadahiro Omi 1-17 of 2 Yonegabukuro, Aoba-ku, Sendai-shi, Miyagi 301-301

Claims (9)

[Claims] 1. A method of treating a substrate, wherein the substrate disposed in an airtight chamber provided with at least an exhaust means is exposed to ozone gas. 2. A method for treating a substrate, wherein the substrate disposed in an airtight chamber provided with at least an exhaust means is exposed to a heated gas. 3. A method for treating a substrate, wherein the substrate disposed in an airtight chamber provided with at least an exhaust means is exposed to ozone gas and heated gas. 4. The method for treating a substrate according to claim 1, wherein the concentration of impurities contained in the ozone gas is 10 ppb or less. 5. The impurity concentration contained in the heated gas is 10 ppb or less.
Or the method of treating a substrate according to item 3. 6. The method for treating a substrate according to claim 2, wherein the temperature of the heated gas is 80 ° C. or higher. 7. The heated gas is one gas selected from a rare gas, a nitrogen gas, an ozone gas or a hydrogen gas, and the heated gas is any one of claims 2, 3, 5 and 6. The method for treating a substrate according to item 1. 8. An apparatus for treating a substrate, which uses the method for treating a substrate according to any one of claims 1 to 7. 9. A substrate treating apparatus having an airtight chamber having at least exhaust means and a treatment chamber, wherein the substrate is subjected to the substrate treating method according to any one of claims 1 to 7 in the airtight chamber. 1. A substrate processing apparatus, wherein a thin film is formed in the processing chamber.