JP3317247B2 - Crystal growth apparatus and semiconductor element manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a semiconductor device manufacturing process using crystal growth and an apparatus for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, as a method for producing a high-performance semiconductor device such as a hetero-bipolar transistor, an epitaxial growth technique of continuously growing crystals on a crystal of a substrate or the like by crystal engineering has attracted attention. Even in the case of the MBE method using a solid source, the UHV-
Even in the case of the CVD method, when an oxide film is present on the crystal surface at the time when epitaxial growth is started, these impurities cause crystal defects and deterioration of electrical characteristics. Therefore, at the start of crystal growth, the oxide film must be removed from the crystal surface.

However, the surface of the Si substrate is chemically very active and easily reacts with oxygen in the atmosphere to form a so-called natural oxide film. In the state where the natural oxide film exists, it is impossible to grow a good crystal on the substrate. Therefore, an oxide film is removed before crystal growth by heating in a crystal growth apparatus or etching with hydrochloric acid gas.

[0004] However, these cleaning methods, which have not been a problem when crystal growth is performed on a simple Si substrate, are used when fabricating a more advanced device.
When crystal growth is performed on a substrate on which a structure has already been formed, the etching process cannot be used because the structure is destroyed. Also in the case of heat treatment, there is a strong demand for shortening the heating time to a low temperature from the viewpoint of suppressing impurity diffusion.

[0005] One method of reducing the temperature of the oxide film at a low temperature for a short time is a protective oxide film method using an oxide film intentionally formed by a chemical solution treatment.

The chemical oxide formed on the surface when a Si substrate is treated with a chemical such as ammonia hydrogen peroxide can be removed at a lower temperature and a shorter time in a crystal growth apparatus than a natural oxide film. Further, the chemical oxide film covers the Si surface slightly thicker than the natural oxide film, and suppresses the direct reaction between the Si crystal and other impurities such as carbon. Further, impurities attached to the oxide film can be easily removed together with the oxide film. Therefore, if the chemical oxide is removed in the crystal growth apparatus, a clean surface without an oxide film can be easily obtained.

For details of the protective oxide film method, see I.
Shizaka and Shiraki in 1986
own of Electrochemical
A paper published in Society page 666,
atsumi et al., 1985 Japanese Jo
urnal of Applied PhysicsV
ol. 24, no. 4 L227.

In principle, the protective oxide film method must remove the oxide film in the crystal growth apparatus. Even for chemical oxides, heat treatment is required to remove them, and if the removal is insufficient, crystal defects are generated as in the case of a natural oxide film.

The above-mentioned Ishizaka and Shirak
In the case of i et al., the oxide film is removed by heating at 710 ° C. for 40 minutes in a vacuum.

In both the case of a natural oxide film and the case of a chemical oxide used in the protective oxide film method, it is necessary to perform a heat treatment in a vacuum vessel and at a treatment temperature (700 ° C.).
To 1200 ° C.) is higher than the temperature generally used for crystal growth (450 ° C. to 600 ° C.). From the viewpoint of device fabrication, it is desired that the heating time be as short as possible.

In order to minimize the heating for removing the oxide film, a device for detecting the removal of the oxide film is used. It is effective to avoid heating. As shown in FIG. 2, Ishizaka and Shiraki et al. Observe changes in oxide film thickness using Auger electron spectroscopy (hereinafter AES). However, since AES is a method of irradiating an evaluation sample with an electron beam and measuring the energy of secondary electrons emitted, it can be basically used only in a vacuum. In addition, although the measurement is performed in the same vacuum vessel, only the measurement results every 15 minutes are shown, and it cannot be said that the results are completely dynamic observations.

(Ellipsometry) On the other hand, ellipsometry, which irradiates a sample with polarized light and measures the polarization state of reflected light, uses a gas atmosphere process such as CVD in principle because only light is used for measurement. This is an observation method that can also be used below.

The two types of observations (Ψ, Δ) measured by ellipsometry are sensitive to changes in the type of the sample substrate, the temperature of the sample, the composition of the thin film on the substrate, the thickness, the roughness, etc. The process of removing the oxide film can be detected.

An example of observing the removal process of a Si oxide film using this ellipsometry is described in Pickering et al., Journal of Vacuums 1995.
science and technology magazine A1
No. 3, page 740. FIG. 3 is a diagram showing a change in the refractive index n of the substrate obtained by ellipsometry before and after removal of the oxide film described in the article. Since they remove the oxide film while increasing the substrate temperature, the change accompanying the substrate temperature change overlaps with the change in n accompanying the oxide film removal. From 26min to 26.5
It is considered that the rapid change toward min corresponds to the removal of the oxide film. In these cases, the oxide film is removed in a vacuum.

As described above, all of the reports on the dynamic observation of the process of removing the oxide film are in a vacuum. On the other hand, the desorption reaction of the Si oxide film is accelerated in a gas atmosphere containing Si such as Si ₂ H ₆ or SiH ₄ , a gas atmosphere such as GeH ₄ containing Ge, or a hydrogen atmosphere. After the oxide film removal treatment, it is confirmed by a method of taking out the crystal growth apparatus and evaluating the same.

However, it is impossible to perform the heat treatment only for the minimum necessary time by the method of evaluation using an apparatus outside the crystal growth apparatus. The heating must be performed for a time as long as possible to cope with the variation between the substrates obtained by the finite number of trials.

[0017]

In order to grow a good crystal on a Si substrate, the oxide film must be completely removed. Generally, the removal of the oxide film requires a temperature lower than the crystal growth temperature. High temperature heat treatment is required. In order to secure the characteristics of the device, it is strongly desired that the heat treatment for removing the oxide film be as short as possible.

However, the dynamic observation of the process of removing the oxide film has hitherto been performed only in a vacuum.

Accordingly, there is no report on a technique for dynamically monitoring the process of removing an oxide film while controlling the gas phase atmosphere in an apparatus which is considered to be effective for removing the oxide film. Was not done.

[0020]

SUMMARY OF THE INVENTION The present invention solves the above problem by monitoring the removal process of a protective oxide film by ellipsometry and controlling a crystal growth apparatus.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Apparatus Configuration) FIG. 1 shows a configuration diagram of a crystal apparatus equipped with an ellipso apparatus.

The crystal growth apparatus includes a vacuum vessel 100, a heating lamp 102 for heating the substrate, a lamp controller 103 for controlling the lamp and adjusting the substrate temperature, a gas inlet 104 for introducing gas into the vacuum vessel, and a gas supply port. It comprises a flow controller 105 for adjusting the flow, a vacuum pump 106, and a pyrometer 109 for measuring the substrate temperature. In addition, a gas supply unit is connected to the flow regulator 105 to supply gas to the crystal growth apparatus.

The ellipso part includes a light source 110, a polarizer 111 for adjusting the polarization state of the incident light, a modulator 112 for modulating the intensity of the incident light, an analyzer 114 for receiving the reflected light from the sample, and performing a spectrum to measure the signal intensity. And a control unit 116 for calculating Ψ and Δ, which are basic ellipsometric measurands, from the signals measured by the detector, judging the conditions, and sending control signals to the respective devices.

The apparatus is provided with a vacuum window 107 for guiding incident light 120 into the vacuum vessel and a vacuum window 108 for extracting reflected light 121 from the vacuum vessel for observing a sample in the vacuum vessel. are doing. As the vacuum windows 107 and 108, it is preferable to use low distortion vacuum windows that are commercially available for ellipsometric measurement.

In the case of the present embodiment, since a spectral ellipsometer capable of performing measurement at a plurality of wavelengths is used, a light source 110 having a wide wavelength range is used, and the detector unit also has a spectral function. However, the present invention can be practiced with an ellipso apparatus using only a single wavelength, in which case the light source 110 and the detector unit can use a single wavelength compatible one and the apparatus can be used. It can be simplified.

(Example of Observation of Process of Removing Protective Oxide Film Using Ellipsometry) FIG. 4 shows the result of actually observing the process of removing a protective oxide film of a sample in a crystal growth apparatus by ellipsometry.

As a sample, a Si substrate with a protective oxide film formed by immersing in a 1: 6: 20 mixed solution of ammonia, hydrogen peroxide, and pure water at 70 ° C. for 1 minute was used, and abruptly placed in a vacuum vessel. After heating to 800 ° C. and holding for 30 minutes, the mixture was cooled to room temperature, and the change during the observation was observed by ellipsometry using light having an energy of 2.5 eV. This experiment was performed to show that the observation of the removal process of the protective oxide film was possible by ellipso. Therefore, cooling is performed without performing crystal growth after heating at 800 ° C. for 30 minutes.

The heating started from room temperature in about 150 seconds, and reached 800 ° C. in about 150 seconds. 150 ~
The rapid change in Ψ and Δ observed in 300 sec is mainly due to the change in the substrate temperature. Of the 30 minutes of 300 to 2100 seconds in which the substrate temperature was kept constant at 800 ° C., Ψ and Δ changed with the decrease of the oxide film thickness during only the first 400 seconds, and removal of the oxide film At the time of completion, there is no change in Ψ and Δ. In particular, the change in the time variation rate of Δ before and after the completion of the oxide film removal is remarkable.

As can be seen from this figure, the completion of removal of the protective oxide film in the crystal growth apparatus can be detected by ellipso.

(Example of Removing Oxide Film in Si ₂ H ₆ Atmosphere) Next, when removing the oxide film from a similar substrate in a vacuum vessel,
FIG. 5 shows a change in ellipso signal when a very small amount of 1 sccm of Si ₂ H ₆ is introduced into the vacuum vessel for only 2 minutes at the tax office during the period of holding at 800 ° C. The results shown are again for an energy of 2.5 eV. Since the heating profile is similar to the heating experiment in vacuum shown in FIG.
The signal changes in 300 seconds or more and 2100 seconds or more are also associated with the substrate temperature change.

Also in this case, the changes in Ψ and Δ due to the removal of the oxide film were observed in the early stage of heating at 800 ° C., but the change time, that is, the time required for removing the oxide film, was measured in vacuum. 200 sec compared to 400 sec when heated
It can be seen that it is shortened below. This is because the oxide film removal process was accelerated by Si ₂ H ₆ .

As described above, for the first time, it was dynamically observed that the process of removing the oxide film progressed faster in a Si ₂ H ₆ atmosphere than in a vacuum. In other words, it is shown that the use of an ellipsometer like the one we used makes it possible to dynamically observe the oxide film removal process even in the gas phase, which was impossible with the conventional monitoring mechanism using electron beams. Was.

This time, it was shown that it is possible to dynamically monitor the oxide film removal process even in a gaseous atmosphere. Therefore, the completion of the removal of the oxide film was detected, and unnecessary high-temperature heating of the substrate was stopped. In addition, the supply of gas introduced into the crystal growth apparatus for removing the protective oxide film can be stopped.

(Wavelength Used for Measurement) In the experiment shown in FIG. 5, Ψ and Δ were measured simultaneously at a plurality of energies. FIG. 6 shows a typical change in energy Δ. At all the energies shown here, a change in the signal accompanying the removal of the oxide film is observed, but the change is gradual at an energy of 3.5 eV or more. Therefore, 3 eV
It can be seen that the use of the following energy makes it easier to detect the completion of oxide film removal.

(Process Embodiment) Next, the flow of the whole crystal growth process using the present invention will be described.

First, the substrate is washed with a mixed solution of sulfuric acid and hydrogen peroxide to remove metal and organic impurities. Next, after the chemical solution is sufficiently removed by washing with water, surface impurities are removed with an ammonia-hydrogen peroxide-based chemical solution, and washing with water is performed.

Since these cleaning processes are performed in order to obtain a clean Si surface, Ishizaka and Shi
Replacing with a process using another chemical solution such as an organic or nitric acid solution as described in the article by raki et al. does not affect the practice of the present invention.

At the stage where the cleaning is completed, an oxide film may be formed on the surface. In order to form a uniform protective oxide film, the substrate is immersed in about 3% diluted hydrofluoric acid for about 30 seconds. Then, all oxide films on the surface are removed. The wafer after the hydrofluoric acid treatment is lightly rinsed with pure water to confirm that the surface shows water repellency. If sufficient water repellency is not selected, the hydrofluoric acid treatment and washing with water are repeated because the oxide film may remain.

After the pure water rinsing is completed, the wafer exhibiting water repellency is treated with a chemical solution to form a protective oxide film.

As chemicals that can be used for forming the protective oxide film, there are mainly an aqueous hydrogen peroxide-based chemical and a hydrochloric acid-hydrogen peroxide-based chemical. The latter has defects in the crystal layer grown after the treatment. Because of the tendency to occur, it is easier to grow good crystals by using an aqueous solution of ammonia hydrogen peroxide.

As the chemical, a mixture of ammonia 1, hydrogen peroxide 6, and pure water 20 in a volume ratio can be used.
The temperature of the chemical is preferably about 70 ° C. By immersing the substrate in this chemical solution for one minute, an oxide film having a thickness of about 15 to 20 angstroms is formed on the substrate surface.

After rinsing with pure water and drying with nitrogen or the like so that no chemical solution remains on the surface of the wafer on which the protective oxide film is formed, the wafer is transported and loaded into a crystal growth apparatus.

In order to maintain the ultrahigh vacuum state in the crystal growth chamber, the substrate is once inserted into the load lock chamber. After the degree of vacuum is improved from atmospheric pressure to about 3 × 10 ⁻⁷ Torr, the wafer is transferred from the load lock to the crystal growth chamber.

When the degree of vacuum in the growth chamber is improved to about 10 ⁻¹⁰ Torr, the heat treatment is started. FIG. 7 shows changes in the substrate temperature and the gas flow rate in the growth chamber.

In our apparatus, since the substrate temperature is measured using a pyrometer usable in a temperature range of 300 ° C. or more, it is rapidly heated to 300 ° C. for about 2 minutes.

Next, the substrate is heated to about 800 ° C. In the case of the experiment shown in FIG. 4 and the like, in order to clarify the physical phenomenon in the process of removing the oxide film, the heating was rapidly performed to 800 ° C.
In actual device fabrication, if the temperature is raised too rapidly at this stage, thermal distortion is applied to the substrate and a slip line may be generated.
It is preferable to suppress the rate of temperature rise to about ° C / min.

Next, the process proceeds to the process of removing the protective oxide film. The protective oxide film can be removed at a temperature of about 710 ° C. or higher. However, the lower the temperature, the longer the time required to remove the protective oxide film. Therefore, in the case of this embodiment, 800 ° C.
To remove. In this embodiment mode, 1 sccm of Si is used from the time when the temperature reaches 800 ° C. in order to remove the oxide film in a short time.
Start introducing ₂ H ₆ into the crystal growth apparatus.

Since the signal of the ellipso changes depending on the substrate temperature change in addition to the removal of the oxide film, it is better to keep the substrate temperature constant before and after the completion to detect the signal change accompanying the completion of the oxide film removal. It becomes easier. Therefore, in the present embodiment, it takes 80 to complete the removal of the oxide film.
Keep the substrate temperature at 0 ° C. During this time, with removal of the oxide film,
Δ changes, and the change of Δ in particular becomes sharply gradual with the completion of oxide film removal. Based on this change, the completion of oxide film removal is detected by ellipso.

It should be noted that if the signal change is analyzed in consideration of the substrate temperature change, the oxide film removal point can be detected even during the temperature change.

At the time when the removal of the oxide film is detected by the ellipso, a control signal is sent to the lamp controller 103 and the flow rate controller 105 to start cooling to a temperature suitable for the crystal growth of the substrate and to remove the oxide film. Vacuum container 100
The supply of Si ₂ H ₆ introduced into the furnace is stopped. This control can be performed automatically and mechanically. However, instead of the automatic control, a person may make a determination based on the signal of the ellipso and change the settings of the lamp controller and the flow rate regulator.

Temperature suitable for crystal growth (450 ° C. to 600
When the temperature reaches about (° C.), a source gas for crystal growth (such as SiH ₄ or Si ₂ H ₆ when growing Si, or GeH ₄ in addition to the Si source when growing SiGe) is supplied to the vacuum chamber 100. Supply.

Ellipso can be used not only for detecting the removal process of an oxide film, but also for evaluating the composition and thickness of a thin film grown on a substrate. Therefore, the ellipsometer can be used from the process of removing the oxide film to the control of the crystal growth process. This point is also superior to conventional oxide film removal process detection techniques such as AES which could not be used during crystal growth using a gas source.

In this embodiment, the oxide film is removed in an atmosphere of Si ₂ H ₆ , but another gas such as SiH ₄ or H ₂ or a mixed gas thereof may be used. It may be processed inside. When the removal is performed in a vacuum, only the lamp controller needs to be controlled.

[0054]

By using the ellipsometer, the S
Even in a gas atmosphere such as i ₂ H _6, it is possible to detect the completion of the removal of the oxide film, and to appropriately control the substrate temperature and the gas flow rate during the transition from the oxide film removal process to the next crystal growth process. It is possible to do.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a configuration of a crystal growth apparatus according to an embodiment of the present invention.

FIG. 2 is a diagram showing a time change of an oxide film thickness measured using AES.

FIG. 3 is a diagram showing a change in refractive index measured by ellipso before and after removal of an oxide film described in the article of Pickering et al.

FIG. 4 is a diagram showing a time change of ellipsometric measurement data during a process of removing a protective oxide film in a vacuum.

FIG. 5 is a diagram showing an example of controlling a substrate temperature and a gas flow rate in time-dependent crystal growth of ellipso measurement data during a process of removing a protective oxide film in a Si ₂ H ₆ atmosphere.

FIG. 6 is a diagram showing a difference in Δ due to a difference in measurement wavelength (energy).

FIG. 7 is a diagram showing an example of controlling a substrate temperature and a gas flow rate in crystal growth.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 Substrate 102 Heating lamp 103 Lamp controller 104 Gas inlet 105 Flow rate controller 106 Vacuum pump 107,108 Vacuum window 109 Pyrometer 110 Light source 111 Polarizer 112 Modulator 114 Analyzer 115 Spectroscope / detector unit 116 Analysis control device 120 Incident light 121 reflected light 122 heating infrared light 123 radiated infrared light 130 gas supply unit 701 substrate temperature 702 disilane flow rate 703 germane flow rate

Continuation of the front page (56) References JP-A-6-77301 (JP, A) JP-A-3-82017 (JP, A) JP-A-5-190499 (JP, A) JP-A-9-64016 (JP) , A) JP-A-9-7909 (JP, A) JP-A-64-4026 (JP, A) JP-A-7-183348 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) H01L 21/205 C30B 25/12 C30B 25/14 H01L 21/203

Claims (8)

(57) [Claims] 1. A substrate was transferred into a crystal growth apparatus in a state in which a chemical oxide on the substrate surface is present, a method of manufacturing a semiconductor device having a step of removing the oxide film before the crystal growth start, ellipsometer変 動 time variation obtained from
A method for manufacturing a semiconductor device, comprising: reducing a substrate temperature or changing a flow rate or a pressure of a gas introduced into a crystal growth apparatus when a rate suddenly decreases. 2. A oxide film removal process, a method of manufacturing a semiconductor device according to claim 1, characterized in that introducing a gas to promote the oxidation film removal reaction in the crystal growth apparatus. 3. The gas for accelerating an oxide film removing reaction is S
3. The method according to claim 2 , wherein the gas contains i. 4. The gas for accelerating the oxide film removal reaction is G
3. The method according to claim 2 , wherein the gas contains e. 5. The method according to claim 2 , wherein the gas that promotes the oxide film removing reaction is hydrogen. 6. The method for manufacturing a semiconductor device according to claim 2 , wherein a plurality of types of mixed gases are used as the gas for promoting the oxide film removing reaction. 7. The method according to claim 1 , wherein a substrate temperature until completion of the oxide film removal is kept constant at least at the end of the oxide film removal step. 8. The method according to claim 1 , wherein light having an energy of 3.5 eV or less is used for measurement by the ellipsometer.