JP5293866B2 - Operation method of heat treatment equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for operating a thermal treatment apparatus which restricts germanium contamination in a subsequent deposition process when, after a germanium-containing thin film is deposited, a thin film deposition process where germanium could be a contaminant follows. <P>SOLUTION: An operation method for a thermal treatment apparatus 1 where a workpiece W, while being held by a holding jig 25, is carried into a reaction vessel 2 before being subjected to thermal treatment comprises the steps of: heating the inside of the reaction vessel 2 while also supplying process gas thereinto and depositing a germanium-containing thin film on the workpiece W; removing the thin film deposited inside the reaction vessel 2 by supplying cleaning gas thereto when no workpieces W have been carried thereinto; supplying oxygen and hydrogen gases to the inside of the reaction vessel 2 and also removing residual germanium from inside the reaction vessel 2 by gases activated by heating; carrying a workpiece W into the reaction vessel 2, and supplying process gas thereto while also heating to deposit on the workpiece a thin film where germanium becomes a contaminant. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention is a method of operating a heat treatment apparatus for holding a target object in a holder and carrying it in a reaction vessel provided with a heating means around it to perform a heat treatment, in order to avoid germanium contamination. Technical field.

  As one of processes performed in a vertical heat treatment apparatus that heat-treats a large number of semiconductor wafers at once, a technique of forming a silicon germanium film is known (Patent Document 1). As a use of this silicon germanium film, germanium is a dopant with a high activation rate, and since it has an advantage that it is difficult to be depleted when a bias voltage is applied, it is considered to be used as a gate insulating film of a transistor, or It is also being considered for use in other devices such as diodes. The film forming process is performed by supplying a mixed gas of silane-based gas and monogermane gas into the reaction tube and heating it to a predetermined temperature.

  On the other hand, in a semiconductor manufacturing factory, various processes are performed using one vertical heat treatment apparatus. After a silicon germanium film is formed on a wafer of a lot, another thin film is formed on a wafer of another lot. For example, a silicon film may be formed. In many cases, for example, a silicon film to be obtained by a heat treatment performed later, germanium in the processing gas in the previous heat treatment becomes a contaminant, and the germanium is contained in the silicon film to obtain the device. Characteristics are degraded.

  Taking a silicon film as an example, a silicon germanium film previously attached to a reaction vessel or the like is formed by performing a so-called pre-coating process and masking the surface of the reaction vessel or the like before the silicon film is formed. Thus, germanium is prevented from being scattered in the processing atmosphere. However, when a polysilicon film is to be formed using a silane-based gas, the temperature at which silicon germanium is formed is lower than the temperature at which the polysilicon film is formed. In a place far from the temperature where the temperature is lowered, even if silicon germanium is formed, the polysilicon film is not formed, and the silicon germanium may not be sufficiently masked.

  On the other hand, in order to clean the inside of the reaction vessel, a gas containing halogen, such as fluorine gas, is generally supplied into the reaction vessel. However, in the case of a silicon germanium film, the reaction is performed even if etching is performed with, for example, fluorine gas. Germanium remains on the inner wall of the container and the surface of the wafer boat. Even when the pre-coating process is performed after cleaning, silicon germanium cannot be sufficiently masked in a region where the temperature is low such as the vicinity of the furnace opening and the polysilicon film is difficult to be formed. Further, in Patent Document 2, the adhesion film adhering to the inside of the reaction vessel is removed by a cleaning gas, and then hydrogen contained in quartz which is a material of the reaction vessel by supplying radicals of hydrogen gas and oxygen gas. However, there is no mention of a problem in the case where another film forming process is performed by the heat treatment apparatus used for forming the silicon germanium film.

Japanese Patent Laid-Open No. 2003-123532: Claim 1, FIG. JP 2008-283126 A: Paragraphs 0030 to 0031, FIGS. 1 and 2

  The present invention has been made on the basis of such a background, and in the case where a thin film containing germanium is formed after the thin film containing germanium is formed, the germanium in the subsequent film forming process is formed. An object of the present invention is to provide a method for operating a heat treatment apparatus that can suppress contamination.

The operation method of the heat treatment apparatus according to the present invention is a method of operating a heat treatment apparatus in which a workpiece is held in a holder and carried into a reaction vessel provided with a heating means around it to perform heat treatment.
A process of bringing a target object into the reaction container and supplying a processing gas and heating the inside of the reaction container with the heating means to form a thin film containing germanium on the target object;
Next, supplying a cleaning gas containing halogen in the reaction container in a state where the object to be processed is not carried into the reaction container, and removing the thin film formed in the reaction container in the process;
Thereafter, an oxidizing gas selected from oxygen gas, ozone gas and a compound gas of nitrogen and oxygen, and hydrogen gas are supplied into the reaction vessel, and the reaction vessel is heated to activate these gases. characterized in that it comprises a step of removing the germanium present in the reduction and reaction vessel by gas.

The operating method of the heat treatment apparatus may include the characteristics listed below.
(A) The film containing germanium is a silicon germanium film .

According to the present invention, after the thin film containing germanium is formed, the thin film is removed with a cleaning gas containing halogen, and then an oxidizing gas selected from oxygen gas, ozone gas, and a compound gas of nitrogen and oxygen, , activates the hydrogen gas, since followed by removal of the germanium present in the reaction vessel by the activated gas can be obtained with less reaction vessel gain Rumaniumu contamination.

It is a longitudinal cross-sectional view which shows the structure of the vertical heat processing apparatus which concerns on this Embodiment. It is the 1st explanatory view showing the operating method of the above-mentioned vertical heat treatment apparatus. It is the 2nd explanatory view showing the operating method of the above-mentioned vertical heat treatment apparatus. It is explanatory drawing which shows the result of having applied the operating method of this invention, and removing germanium.

  Hereinafter, an embodiment in which the operation method of the heat treatment apparatus according to the present invention is applied to a vertical heat treatment apparatus capable of forming both a silicon germanium film (SiGe film) and a silicon film (Si film) will be described with reference to FIG. I will explain. The vertical heat treatment apparatus 1 is configured as a film forming apparatus capable of forming a SiGe film or a Si film by, for example, a CVD (Chemical Vapor Deposition) method.

  In FIG. 1, reference numeral 2 denotes a reaction vessel formed of, for example, quartz in a vertically long cylindrical shape, and the lower end of the reaction vessel 2 is an opening portion 21 that is opened as a furnace port. The flange 22 is formed integrally with the reaction vessel 2. Below the reaction vessel 2 is provided a lid 23 made of, for example, quartz that abuts the lower surface of the flange 22 and hermetically closes the opening 21. The lid body 23 can be moved up and down by a boat elevator (not shown), whereby the opening 21 can be opened and closed.

  The lid body 23 is provided with a rotating shaft 24 penetrating through the central portion thereof, and a wafer boat 25 as a holder is mounted on the upper end portion of the rotating shaft 24. The wafer boat 25 is provided with three or more, for example, four support columns 26. A plurality of grooves (for example, 125 wafers W) to be processed can be held in the support column 26 in a shelf shape. Slot) is formed. However, in this example, among the 125 wafer W holding regions, a plurality of dummy wafers are held at the upper and lower ends, and the product wafer W is held in the region between them. A motor M that forms a drive unit for rotating the rotary shaft 24 is provided at the lower end of the rotary shaft 24, and the motor M can rotate the entire wafer boat 25 via the rotary shaft 24. In addition, a heat retaining unit 27 is provided on the lid 23 so as to surround the rotating shaft 24.

  An exhaust port 4 for exhausting the inside of the reaction vessel 2 is formed above the reaction vessel 2. An exhaust pipe 43 provided with a pressure control mechanism 24 composed of, for example, a pressure control valve is provided downstream of the exhaust port 4, and a vacuum pump 41 is connected to the exhaust pipe 43. The vacuum pump 41 serves to evacuate the reaction vessel 2 to a desired degree of vacuum. Around the reaction vessel 2, a heating furnace 3 provided with a heater 31 as a heating means for heating the inside of the reaction vessel 2 is provided. As the heater 31, a carbon wire heater is employed, thereby realizing a highly clean process with less contamination and rapid temperature rise / fall.

  Three L-shaped injectors (first injector 51 to third injector 53) for supplying a processing gas to the wafer W are inserted and fixed to the flange 22 at the bottom of the reaction vessel 2. Here, in FIG. 1, for convenience of illustration, these three injectors 51 to 53 are shown as being inserted from the same position of the flange 22, but actually these injectors 51 to 53 are easy to maintain. For example, they are arranged at equal intervals along the circumferential direction of the flange 22 at a certain position in consideration.

  Each of the three injectors 51 to 53 is composed of thin tubes having different lengths so that the processing gas can be supplied to different height positions in the reaction vessel 2, and its tip end (upper end) is formed. It opens as a gas supply hole. The tip of the lowest first injector 51 is positioned, for example, near the lower end of the wafer W holding region in the wafer boat 25, and the tip of the second injector 52 in the middle is, for example, the middle stage of the wafer W holding region. The tip of the highest third injector 53 is located, for example, between the uppermost stage of the holding region of the wafer W and the tip of the second injector 52. Yes. Here, arrangement | positioning of the front-end | tip part of each injector 51-53 is not limited to the above-mentioned layout, It can set to an appropriate position based on an experimental result.

The base end sides of the injectors 51 to 53 extend out of the flange 22 and are connected to the processing gas supply pipes 611 to 613, respectively. The processing gas supply pipes 611 to 613 are connected to the SiGe film and silicon of the Si film. Silane gas supply units 62 for supplying a silane-based processing gas as a raw material, such as monosilane gas (SiH ₄ gas), are connected via valves V11 to V13 and mass flow controllers M11 to M13, respectively. Further, the processing gas supply pipes 611 to 613 are provided with germane gas supply parts 63 for supplying germane processing gas, which is a germanium raw material of the SiGe film, for example, monogermane gas (GeH ₄ gas), respectively. They are connected via V23 and mass flow controllers M21 to M23. With this configuration, the mixed gas supplied from each of the injectors 51 to 53 can independently adjust the flow rates of the monosilane gas and the monogerman gas. Here, in this example, the germane gas diluted to 10% with, for example, hydrogen is supplied from the germane gas supply unit 63.

Further, a cleaning gas for removing (cleaning) deposits (reaction products, etc.) such as SiGe and Si adhering to the inside of the reaction vessel 2 during film formation is applied to the flange 22 of the reaction vessel 2. A cleaning gas injector 54 is provided to be supplied inside. The cleaning gas injector 54 is formed, for example, in an L shape, and its tip extends to the vicinity of the lower end of the wafer W holding region in the wafer boat 25 and opens. The rear end of the cleaning gas injector 54 extends out of the flange 22 and is connected to the cleaning gas supply pipe 71. A cleaning gas supply unit 74 is connected to the cleaning gas supply pipe 71 via a valve V5 and a mass flow controller M5. From the unit 74, for example, fluorine (F ₂ ), which is a halogen-based acidic gas, and fluorine is used. A gas containing hydrogen fluoride (HF) or a gas containing fluorine and hydrogen (H ₂ ) diluted with nitrogen (N ₂ ) can be supplied. Here, in FIG. 1, only “F ₂ ” is shown in the cleaning gas supply unit 74 for convenience of illustration. In this example, a case where a mixed gas of fluorine, hydrogen and nitrogen is used as the cleaning gas will be described.

Here, the vertical heat treatment apparatus 1 according to the present embodiment finishes the heat treatment including a step of forming a SiGe film, for example, and then performs a heat treatment including a step of forming a film not containing Ge, for example, a Si film. When performing, in order to purge germanium (Ge) which is not sufficiently removed by a cleaning gas such as F ₂ gas as described in the background art, a purge gas is supplied into the reaction vessel 2 It has a mechanism to do.

That is, for example, the cleaning gas supply pipe 71 connected to the above-described cleaning gas injector 54 is supplied with hydrogen (H ₂ ) gas as a purge gas and nitrous oxide as an oxidizing gas via valves V3 and V4 and mass flow controllers M3 and M4. A hydrogen supply unit 72 and an oxidizing gas supply unit 73 for supplying (N ₂ O) gas are connected. For example, a gas mixing unit 710 is provided at the introduction portion of these purge gases into the cleaning gas supply pipe 71, and the purge gas is supplied into the reaction vessel 2 in a sufficiently mixed state. In this example, the purge gas is supplied into the reaction vessel 2 by using the pipe 71 and the injector 54 common to the cleaning gas. However, it is needless to say that a supply pipe or injector dedicated to the purge gas may be provided.

  The vertical heat treatment apparatus 1 further includes a control unit 8 that controls operations of the heater 31, the pressure control unit 42, and the gas supply units 62, 63, 72, 73, and 74 described above. The control unit 8 includes a computer having a CPU and a program (not shown), for example. The program performs film formation on the wafer W by the vertical heat treatment apparatus 1 and performs cleaning of the reaction vessel 2 and purge of Ge. Steps (commands) for operations necessary to perform, for example, control related to output control of the heater 31, pressure adjustment in the reaction vessel 2, and adjustment of supply amounts of processing gas, cleaning gas, and purge gas to the reaction vessel 2 A group is formed. This program is stored in a storage medium such as a hard disk, a compact disk, a magnetic optical disk, or a memory card, and installed in the computer therefrom.

Next, an operation for forming a SiGe film on the wafer W using the vertical heat treatment apparatus 1 described above will be described.
First, a predetermined number of wafers W, which are substrates, are placed on the wafer boat 25 in a shelf shape, and a boat elevator (not shown) is raised to carry the wafers W into the reaction vessel 2.

  After the loading of the wafer boat 25 is completed and the opening 21 at the lower end of the reaction vessel 2 is closed by the lid 23, the reaction vessel 2 is evacuated by the vacuum pump 41 through the exhaust port 4, The pressure is adjusted to a reduced pressure atmosphere of 10 Pa to 130 Pa, for example. Further, the inside of the reaction vessel 2 is heated by the heater 31 to a process temperature set in a range of 350 ° C. to 650 ° C., for example.

  When the temperature rise is finished, monosilane gas and monogermane gas are supplied from the silane gas supply unit 62 and the germane gas supply unit 63, and the processing gas which is a mixed gas of these is supplied into the reaction vessel 2 through the three injectors 51 to 53. Supply (FIG. 2A). The mixing ratio of monosilane gas and monogermane gas, which is a processing gas, is different in each of the injectors 51 to 53. For example, the mixing ratio of monosilane gas and monogermane gas is 1200 sccm: 600 sccm in the first injector 51, and the second injector. 52 is adjusted to 300 sccm: 190 sccm, and the third injector 53 is adjusted to 300 sccm: 220 sccm.

  The monosilane gas and the monogermane gas thus supplied into the reaction vessel 2 are thermally decomposed, and a SiGe film (silicon germanium film) is formed on the wafer W. Here, since monogermane has low activation energy and high decomposition reactivity, when monogermane is supplied alone from the bottom of the reaction vessel 2, monogermane is insufficient on the upper side. However, since the three injectors 51 to 53 having different heights are provided in this example, the shortage of monogerman supplied from the first injector 51 provided on the bottom side is replenished by the upper injectors 52 and 53. Is done.

In addition, since monosilane gas and monogermane gas are supplied in a premixed state, the monogermane is diluted with monosilane having a lower activation energy and lower decomposition reactivity than monogermane, and the monosilane on the lower side of the wafer boat 25 is diluted. Excessive decomposition of germane is suppressed, and a uniform SiGe film can be formed with little difference in film thickness between the wafer W surfaces in the vertical direction of the wafer boat 25. Further, during the film formation period, the wafer boat 25 is rotated by the motor M, and a uniform SiGe film can be formed even within each wafer W surface.
Thus, after the film formation for a predetermined time, the supply of the processing gas and the evacuation are stopped, the inside of the reaction vessel 2 is replaced with an inert gas such as N ₂ gas, and then the wafer boat 25 is unloaded from the reaction vessel 2. To do.

In the film formation of the SiGe film executed by the operation described above, reaction products such as SiGe adhere to the surfaces of various members exposed to the atmosphere supplied with the processing gas, such as the reaction vessel 2 and the wafer boat 25, Since such reaction products gradually accumulate as the film formation is repeated, cleaning of the reaction container 2 with F ₂ gas is periodically performed. Also, when the film to be formed is switched from a SiGe film to another film type such as a Si film, cleaning with F ₂ gas was performed for the purpose of preventing Ge contamination in the film after switching. Thereafter, after Ge is further purged, an operation for starting the next film formation is performed. The cleaning and Ge purge will be described below.

When the film formation of the SiGe film is finished, for example, when the film type to be formed on the wafer W is switched to the Si film, cleaning with F ₂ gas is performed before the next film formation is started. In this cleaning, the wafer boat 25 in a state where the wafer W is not held is carried into the reaction vessel 2 purged with N ₂ gas, the lid body 23 is closed, and the inside of the reaction vessel 2 is reduced in an atmosphere of, for example, 13300 Pa. In addition, the temperature in the reaction vessel 2 is raised to, for example, about 400 ° C. Then, for example, 12000 sccm of F ₂ gas is supplied into the reaction container 2 from the cleaning gas supply unit 74. Here, as described above, the F ₂ gas according to this example is, for example, a mixed gas of fluorine (F ₂ ), hydrogen (H ₂ ), and nitrogen (N ₂ ), and each gas has, for example, F ₂ of 2000 sccm, H ₂ is supplied at 2000 sccm and N ₂ is supplied at 8000 sccm.

When F ₂ gas is supplied into the heated reaction vessel 2, fluorine in the gas is activated, and the activated fluorine causes the inside of the reaction vessel 2, such as the inner surface of the reaction vessel 2 or the wafer boat 25, to be activated. The SiGe deposited on the surfaces of the various members is etched, and deposits (such as reaction products) adhering to the surfaces of these members can be removed (FIG. 2B).

When cleaning is performed for a predetermined time in this way, the gas supplied into the reaction vessel 2 is switched from F ₂ gas to N ₂ gas to finish the cleaning, the inside of the reaction vessel 2 is decompressed to 46.55 Pa, for example, and the inside of the reaction vessel 2 The temperature is raised to, for example, 850 ° C. in the range of 750 ° C. to 950 ° C., for example. Then, H ₂ gas, for example, 1700 sccm and N ₂ O gas, for example, 2000 sccm are supplied into the reaction vessel 2 from the hydrogen supply unit 72 and the oxidizing gas supply unit 73 to remain on various members in the reaction vessel 2. The purged Ge is purged (FIG. 2C).

When H ₂ gas or N ₂ O gas is heated to the above-described temperature range, these gases are activated to generate active species such as hydrogen radicals and oxygen radicals, and these radicals are generated on various members in the reaction vessel 2. It reacts with the remaining Ge and takes in the Ge into the purge gas, and the purge gas containing Ge can be discharged out of the reaction vessel 2 (purge out).

When the purge of Ge is finished, supply of the purge gas is stopped, and the pressure and temperature in the reaction vessel 2 are adjusted to the conditions for forming the Si film while the wafer W is not placed on the wafer boat 25. As shown in 3 (a), monosilane gas is supplied into the reaction vessel 2, and the surface of the member in the reaction vessel 2 is precoated with a polysilicon film. Even after a small amount of metal remains on the surfaces of various members after F ₂ cleaning or radical purging, these contaminants are covered by the precoat, and the reaction vessel 2 is clean. . When the pre-coating is thus completed, the wafer W is again held in the wafer boat 25 in a shelf shape and carried into the reaction vessel 2, and for example, the formation of a Si film with monosilane gas is started to complete the film type switching (FIG. 3). (B)).

As described above with reference to FIGS. 2 and 3, the film type to be formed is switched by forming the SiGe film → cleaning with F ₂ gas → purging Ge with H ₂ gas and N ₂ O gas → Various processes are performed in the order of pre-coating of the polysilicon film → deposition of the Si film. Here, the pre-coating of the polysilicon film is performed at a temperature of, for example, about 450 ° C., whereas SiGe is formed at a temperature of, for example, 300 ° C. to 400 ° C., which is lower than the temperature at the time of this pre-coating.

For this reason, in the above-described series of switching operations, for example, after performing F ₂ cleaning, if the polysilicon film is precoated without purging Ge, the furnace of the reaction vessel 2 as described in the background art. Since silicon germanium cannot be sufficiently masked in areas where the temperature is low and the polysilicon film is difficult to form, such as near the mouth, the Si film deposited at the later stage is contaminated by Ge remaining on the surface of the member. Will be.

In addition, regarding the order of purging Ge after cleaning with F ₂ gas, if this order is changed and Ge is purged first, the SiGe film deposited on the surface of each member is caused by, for example, oxygen radicals. Since it is oxidized and an oxide film is formed, it is not etched with F ₂ gas and cannot be cleaned.
From the viewpoint described above, in order to effectively remove Ge remaining in the reaction vessel 2 at the time of film type switching in the vertical heat treatment apparatus 1, F in the order shown in FIGS. It can be said that it is preferable to perform cleaning with _two gases, purge of Ge, and pre-coating of a polysilicon film.

The operation method of the vertical heat treatment apparatus 1 according to the present embodiment has the following effects. For example, after forming a SiGe film containing germanium, the SiGe film is removed by a cleaning gas containing halogen (for example, F ₂ gas), and then nitrous oxide gas and hydrogen gas, which are oxidizing gases, are activated, Since the Ge present in the reaction vessel 2 is removed by the activated gas, germanium contamination can be suppressed in the subsequent film formation of, for example, a Si film.

Here, the reason why the N ₂ O gas is used for the purge of Ge is that the vertical heat treatment apparatus 1 for forming the Si film is used for an annealing process for reducing the grain size of the Si film. This is because a gas supply line may be provided in advance, but the oxidizing gas that can be used for the Ge purge is not limited to this example. For example, as an oxidizing gas for purging Ge, other types of nitrogen and oxygen compound gas such as NO and NO ₂ , oxygen gas, ozone gas, and the like may be used.

In the vertical heat treatment apparatus 1 shown in the above-described embodiment, after depositing about 5 μm of SiGe on the surface of the quartz substrate held on the upper side and the lower side of the wafer boat 25, each of the following examples, The treatment according to the comparative example was performed, and the number of Ge atoms per unit surface area [number / cm ² ] remaining on the substrate after each treatment was measured. The implementation conditions for each treatment were the same as the conditions described in FIGS. An ICP-MS (Inductively Coupled Plasma Mass Spectrometer) was used for measuring the number of Ge atoms.
A. Experimental conditions
(Comparative Example 1)
Wet cleaning was performed by immersing the SiGe film-formed substrate in a hydrofluoric acid solution for several minutes.
(Comparative Example 2)
Coating was performed to form a polysilicon film having a thickness of 1 μm on the surface of the quartz plate.
(Comparative Example 3)
F ₂ gas was supplied into the reaction vessel 2 and the quartz substrate placed on the wafer boat 25 was cleaned for about 1 hour.
Example 1
The quartz substrate after the F ₂ gas cleaning of (Comparative Example 3) was placed in the reaction vessel 2 again, H ₂ gas and N ₂ O gas were supplied, and Ge was purged for 5 hours.

B. Experimental result
The measurement results of Ge in each example and comparative example are shown in FIG. 4 indicates a measurement result of the substrate held on the upper side of the wafer boat 25, and B indicates a result on the lower side of the wafer boat 25.

According to the result of FIG. 4, in the wet cleaning of (Comparative Example 1), 1.0 × 10 ¹² [pieces / cm ² ] or more of Ge is present on the substrate surface on both the upper side and the lower side of the wafer boat 25. It can be seen that atoms remain and Ge cannot be sufficiently removed only by wet cleaning. Moreover, the cleaning liquid in the cleaning tank is also contaminated by Ge.

Even in the case of coating with the polysilicon film of (Comparative Example 2), the upper side of the wafer boat 25 is 3.0 × 10 ¹² [pieces / cm ² ] or more, and the lower side is 1.0 × 10 ¹¹ [ Ge atoms / cm ² ] or more remain. From this, it can be said that even if pre-coating is performed in a state where Ge remains, there is almost no effect of preventing Ge contamination.

Next, in cleaning with F ₂ gas in (Comparative Example 3), Ge atoms of 1.0 × 10 ^{11 to} 2.0 × 10 ¹¹ [pieces / cm ² ] or more on both the upper side and the lower side of the wafer boat 25. In this case, the sufficient removal effect of Ge is not observed.

As described above, even if each of the treatments of (Comparative Example 1) to (Comparative Example 3) was performed, the effect of removing Ge on the substrate surface was not seen, but the quartz substrate after the F ₂ gas cleaning was performed. On the other hand, when purging using H ₂ gas and N ₂ O gas as (Example 1), the Ge on the substrate surface is about 3.0 × 10 ⁸ [pieces / cm ² ] on both the upper and lower sides. Thus, it is removed to near the ICP-MS measurement lower limit, and the Ge removal effect is dramatically improved. From these experimental results, it was confirmed that purging using H ₂ gas and N ₂ O gas was effective in removing Ge remaining in the reaction vessel.

W Wafer 1 Vertical heat treatment apparatus 2 Reaction vessel 25 Wafer boat 3 Heating furnace 31 Heater 4 Exhaust port 51 First injector 52 Second injector 53 Third injector 54 Cleaning gas injectors 611 to 613
Process gas supply pipe 62 Monosilane supply part 63 Monogerman supply part 71 Cleaning gas supply pipe 710 Gas mixing part 72 Hydrogen supply part 73 Oxidation gas supply part 74 Cleaning gas supply part 8 Control part

Claims (2)

In a method of operating a heat treatment apparatus for holding a target object in a holder and carrying it in a reaction vessel provided with a heating means around it to perform heat treatment,
A process of bringing a target object into the reaction container and supplying a processing gas and heating the inside of the reaction container with the heating means to form a thin film containing germanium on the target object;
Next, supplying a cleaning gas containing halogen in the reaction container in a state where the object to be processed is not carried into the reaction container, and removing the thin film formed in the reaction container in the process;
Thereafter, an oxidizing gas selected from oxygen gas, ozone gas and a compound gas of nitrogen and oxygen, and hydrogen gas are supplied into the reaction vessel, and the reaction vessel is heated to activate these gases. And a step of removing germanium present in the reaction vessel with the gas that has been converted into a gas.   The operation method of the heat treatment apparatus according to claim 1, wherein the film containing germanium is a silicon germanium film.

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