JP4133490B2 - Deposition method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a thin film.
[0002]
[Prior art]
Currently, an amorphous silicon (a-Si) thin film is mainly used to form a thin film transistor (TFT) used for a liquid crystal display (LCD) or the like. However, the a-Si thin film has an electron mobility of 0.5 to 1.0 cm due to the field effect.²Since / Vs is very small and the leakage current in the off state is large, it cannot be used for a transistor requiring high-speed operation such as a memory or a logic circuit that pursues processing speed. Along with such problems of the a-Si thin film and the increasing demand for further miniaturization and higher definition of the LCD, the mobility is 30 to 200 cm.²A polycrystalline silicon (Polycrystalline Silicon) thin film that has a large / Vs and a small leakage current in an off state has attracted attention.
[0003]
Examples of a method for forming a poly-Si thin film include a hot wall low pressure chemical vapor deposition (LPCVD) method, a laser annealing method, and the like. Hot wall LPCVD is 1.33 × 10²SiH, which is a raw material gas, by setting the gas and the entire apparatus to a high temperature of 500 ° C. or higher at a low pressure of Pa or lower._FourIn which a poly-Si thin film is formed on a substrate. However, in order to form the above-described transistor that requires high-speed operation, it is necessary to further improve the crystallinity of the crystal thin film, which requires a high-temperature process of 1000 ° C. or higher. The laser annealing method is a method in which an a-Si thin film deposited by a plasma enhanced chemical vapor deposition (PECVD) method is heated by an excimer laser to be melted and recrystallized. However, the manufacturing process is multi-stage and the cost is high.
[0004]
As an alternative to these methods, studies on the formation of crystalline thin films such as poly-Si and microcrystalline silicon (μc-Si) by PECVD that can be directly formed at a low temperature at a single process are being actively conducted (for example, Non-Patent Document 1). Note that a microcrystalline thin film is a thin film that includes nano- or μ (micro) -sized crystal components in the thin film, and has a structure in which an amorphous thin film includes several tens of percent or more of crystals.
[0005]
[Non-Patent Document 1]
“The 62nd JSAP Scientific Lecture Proceedings 14a-ZF-3”, September 2001, p. 736
[0006]
[Problems to be solved by the invention]
However, a crystalline thin film formed at a low temperature using the PECVD method currently being studied cannot obtain a mobility as high as that of the poly-Si thin film formed by other methods described above, and has not yet been put into practical use. In order to improve the mobility, it is necessary to unify the crystal orientation, that is, the orientation, in addition to improving the crystallinity of the crystal thin film.
Further, when a TFT having a MOS structure is formed by a low temperature process, an amorphous film used as a gate insulating film is also formed at a low temperature. However, an amorphous thin film formed at a low temperature has a low density and does not function well as a gate insulating film.
[0007]
The present invention has been made to solve such problems, and an object of the present invention is to make it possible to form a high-quality thin film at a low temperature and in a small number of processes.
[0008]
[Means for Solving the Problems]
  In order to achieve such an object, the present invention provides positive ions on a workpiece.Including plasmaAnd negative ionsIncluding plasmaAnd supplyForming a thin film on the object to be processed, and generating positive plasma and negative ions to the surface of the object by generating plasma using electric power pulse-modulated with a predetermined duty ratio.Using the energy produced when these positive ions and negative ions recombine,Increase surface temperatureIt is characterized by that.
  Here, the thin film may be a crystalline thin film or an amorphous thin film.
  Further, the negative ions may include negative ions containing a halogen element or negative ions made of molecules containing a halogen element. For example, F^-Or Cl^-May be included. Negative ions are H^-Or O^-May be included.
  On the other hand, the positive ions may include positive ions including at least Si or C. For example, SiH_Three ⁺, SiH_XF⁺, SiH_XF_Three ⁺Or CH_Three ⁺May be included. Positive ions are H⁺Or H_Three ⁺May be included.
[0009]
  Also, DeThe duty ratio may be set to a predetermined value of 30% to 70%, or may be switched alternately between 70% and 30%. Alternatively, a first step of forming a film with a duty ratio of 30% and a second step of forming a film with a duty ratio of 70% may be provided.
  Alternatively, negative ion source gas may be introduced onto the object to be processed in synchronization with the pulse-modulated power changing from on to off.
  Further, a negative ion source gas is introduced toward the first space on the object to be processed, and a positive ion source gas is introduced toward the second space farther from the object to be processed than the first space. You may do it.
[0010]
In the above-described film formation method, a positive ion beam and a negative ion beam may be irradiated toward the object to be processed.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(First embodiment)
FIG. 1 is a cross-sectional view showing a configuration of a microwave plasma CVD apparatus used in the film forming method according to the first embodiment of the present invention. This CVD apparatus forms a μc-Si thin film on a glass substrate W as an object to be processed.
[0012]
A susceptor 2 on which the glass substrate W is placed is accommodated inside the process chamber 1. The susceptor 2 is provided with an electrostatic chuck or a mechanical chuck (not shown) for bringing the glass substrate W into close contact with the susceptor 2. The susceptor 2 further includes a heater 3 that heats the glass substrate W to a predetermined temperature. An exhaust port 4 is provided at the lower part of the chamber 1, and the interior of the chamber 1 is 10 by a vacuum pump (not shown) communicating with the exhaust port 4.^-FiveVacuum is drawn to Pa level. A gas introduction nozzle 5 is provided in the upper portion of the chamber 1, and a raw material gas is introduced into the chamber 1 from the nozzle 5. The source gas contains SiH containing Si element that composes the μc-Si thin film._Four, SiF_FourH containing no Si element₂, Xe are used.
[0013]
A disk antenna 6 is arranged in the upper space in the chamber 1 so as to face the susceptor 2. A circular ground plane 8 is disposed on the disk antenna 6 with a quartz plate 7 interposed therebetween. An inner conductor and an outer conductor of a coaxial waveguide 9 are connected to the disk antenna 6 and the ground plane 8, respectively. A microwave power source 11 is connected to the coaxial waveguide 9 via a rectangular waveguide 10. The microwave power source 11 can perform pulse modulation to turn ON / OFF the output power at a predetermined cycle. The ratio of the power ON time to the ON time + OFF time (ON time / (ON time + OFF time)) is called the duty ratio. The rectangular waveguide 10 or the coaxial waveguide 9 is provided with a load matching device 12.
[0014]
Using such a CVD apparatus, a μc-Si thin film is formed on the glass substrate W as follows. A glass substrate W is disposed on the susceptor 2, the glass substrate W is brought into close contact with the susceptor 2 by an electrostatic chuck or the like, and the substrate temperature is set to 400 ° C. by the heater 3. The inside of the chamber 1 is evacuated and the source gas is fed into the chamber 1 from the nozzle 5_Four/ SiF_Four/ H₂/ Xe = 4/1/200/50 sccm (standard cubic centimeter / minute) is introduced, and the pressure in the chamber 1 is maintained at 1.5 Pa. In this state, a microwave having a power of 800 W and a frequency of 2.45 GHz is pulse-modulated and supplied from the microwave power source 11. The pulse modulation frequency is 10 kHz and the duty ratio is 70%. Under such process conditions, a μc-Si thin film with good crystallinity can be formed on the glass substrate W.
[0015]
Next, the experimental result regarding this Embodiment is shown.
FIG. 2 shows a spectrum obtained by Raman spectroscopy of the μc-Si thin film (hereinafter referred to as Raman spectrum). The μc-Si thin film has a pulse modulation frequency duty ratio of 30%, 70% and C.I. W. It is formed by changing (Carrier Wave without pulse modulation). From FIG. 2, it is 520 cm when the duty ratio is 70%.^-1The crystal peak appears strongly, indicating that the crystallinity is the best. The crystallization rate at this time was 92%.
[0016]
FIG. 3 shows the area intensity ratio (I) between the crystalline component and the amorphous component of the Raman spectrum of the μc-Si thin film._c/ I_a) Shows the duty ratio dependency. The μc-Si thin film is made of SiF as a source gas under the process conditions described above._FourFormed without addition of SiF and SiF_FourIs formed. In addition, FIG. 4 shows F measured by quadrupole mass spectrometry (QMS) during the above-described process.^-The duty ratio dependence of the total (area) of ion signal intensity is shown.
First, referring to FIG. 3, SiF_FourWhen no is added (dotted line in FIG. 3), the crystallinity is improved as the duty ratio is increased, and a saturation tendency is shown at a duty ratio of 70% or more. SiF_FourWhen no is added, the crystallinity is greatly affected by the impact of H atoms and positive ions. As the duty ratio is increased, the crystallinity is improved due to an increase in H atoms, and the ion bombardment is also increased at the same time. W. It is possible that the improvement in crystallinity was suppressed.
[0017]
On the other hand, SiF_FourWhen Si is added (solid line in FIG. 3), SiF_FourCompared with the case where C. was not added, C.I. W. In this case, the crystallinity is slightly improved. However, when the pulse modulation is performed, the crystallinity is improved as a whole, and the crystallinity is most improved when the duty ratio is 70%. SiF_FourWhen SiF is added, SiF_FourReacts with electrons in the plasma P and F^-Ions are generated. Looking now at FIG. 4, F in the process^-The ions have the same tendency as the crystallinity of the μc-Si thin film (solid line in FIG. 3), and both show a peak at a duty ratio of 70%. From this, SiF_FourWhen Si is added, the crystallinity is affected to some extent by the impact of H atoms and positive ions, but F is more than that.^-It can be seen that ions greatly contribute to crystallinity.
[0018]
F for improving crystallinity^-The contribution of ions can be explained as follows. As shown in FIG. W. When the pulse is ON, F^-Although ions cannot reach the substrate surface, as shown in FIG. 5B, the sheath disappears when the pulse is OFF, and F^-Ions can reach the substrate surface. Therefore, by generating a plasma P by pulse-modulating the power, F^-Ions can be used directly in the process.
F^-Ion is H⁺Ion and H_Three ⁺Ion, SiH_Three ⁺As soon as it collides with positive ions such as ions, recombination occurs. For example,
H⁺+ F^-→ HF
The generation energy of recombination is 1544 kJ / mol. Such recombination near the surface of the thin film causes a temperature increase (local heating) only on the surface of the thin film electrode and promotes crystallization.
[0019]
From the above knowledge, the principle of the film forming method according to this embodiment can be described as follows. First, SiF as source gas_FourBy adding F^-Ions are generated. Further, F is generated by generating a plasma P by pulse-modulating electric power with a predetermined duty ratio.^-Ions are supplied to the substrate surface. And F on the substrate surface^-Ion and H⁺Ion and H_Three ⁺Ion, SiH_Three ⁺As a result of recombination with positive ions such as ions and use of the generated energy for crystallization of Si, a μc-Si thin film with good crystallinity is formed.
[0020]
In this embodiment, F^-Ion and H⁺Unlike the LPCVD method, which is one of the methods for forming a poly-Si thin film, a high-temperature process at 1000 ° C. or higher is not necessary because the energy generated upon recombination with positive ions such as ions is used. Further, since recombination causes a temperature rise only on the surface of the thin film, it is not necessary to use a thermally strong but expensive quartz substrate, and an inexpensive glass substrate or plastic film can be used. In addition, a multi-stage process such as a laser annealing method is not necessary, and it can be directly formed by a single process. Therefore, according to the present embodiment, a μc-Si thin film with good crystallinity can be formed at a low temperature and in a single process.
[0021]
In addition, by applying the film formation principle of the film formation method according to this embodiment, it is possible to form a crystalline thin film with good crystallinity using various source gases. For example, in this embodiment, F^-SiF to generate ions_FourAdded, but F₂, SiHF_Three, SiH₂F₂, SiH_ThreeF may be added. Moreover, what can be used as a negative ion is F.^-Not limited to ions, negative ions containing a halogen element or negative ions made of molecules containing a halogen element may be used. Specifically, Cl^-Ion and Br^-Ions may be used. Cl^-In order to generate ions, the source gas is SiCl._Four, SiHCl_Three, SiH₂Cl₂, SiH_ThreeCl may be added. Br^-To generate ions, SiHBr is used as a source gas._Three, SiH₂Br₂, SiH_ThreeBr may be added. Moreover, H as a negative ion^-Ions may be used. As positive ions, H⁺Ion, H_Three ⁺Ion, SiH_Three ⁺In addition to ions, SiH_XF⁺Ion, SiH_XF_Three ⁺Ions can also be used.
[0022]
Furthermore, by applying the principle of the film forming method according to the present embodiment, it is possible to form a crystal thin film other than Si-based. For example, F as negative ions^-Using ions and CH as positive ions_Three ⁺By using ions, a carbon-based crystal thin film such as diamond, microcrystal, nanocrystal diamond, and carbon nanotube can be formed with good crystallinity. In this case, CH as the source gas_Four, CH_ThreeF, CH₂F₂, CHF_Three, CF_FourMay be used.
[0023]
In addition, by applying the principle of the film forming method according to this embodiment, ZrO, which is important in the semiconductor process, is used._X, HfO_X, Al₂O_Three, HfAlO_X, ZrSi_XO_Y, HfSi_XO_Y, HfAl_XSi_YO_Z, TaO_X, LaO_X, YO_X, CeO_X, PrO_XIt is also possible to form an amorphous thin film of a metal oxide film made of the same or a mixture thereof at a low temperature and a high density. That is, a high-quality amorphous thin film can be formed at a low temperature by using the generation energy when recombination of positive ions and negative ions. Therefore, when this method is used, an amorphous thin film can be formed on an organic material, and an organic transistor in which a MOS gate insulating film is formed of an amorphous thin film can be realized. In this case, O as negative ions.^-Is used. TiO_XThe crystal thin film can be formed at a low temperature and a high density.
[0024]
In addition, by adopting a film formation method that uses generated energy when positive ions and negative ions recombine in a series of processes for forming a TFT having a MOS structure, a source layer and a drain formed of a crystalline thin film It becomes possible to form a layer, a drift layer, etc. and a gate insulating film formed of an amorphous thin film at a low temperature. In particular, the TFT can be formed on the organic film or the organic EL (electro luminescent panel) by forming it at a low temperature below the glass conversion temperature of the organic film or the organic EL (electro luminescent panel).
[0025]
In this embodiment, the optimum duty ratio of the pulse modulation frequency is 70%, but the value may vary depending on the raw material gas used.
The power for pulse modulation with a predetermined duty ratio may be any of microwave power, high frequency power, electron beam, and laser ablation.
[0026]
(Second Embodiment)
In the film forming method according to the second embodiment of the present invention, SiF is used as a source gas under the process conditions of the first embodiment._FourOnly the duty ratio of the pulse modulation frequency is changed while adding.
[0027]
The experimental result regarding this Embodiment is shown.
FIG. 6 shows a spectrum (hereinafter referred to as an XRD spectrum) obtained by X-ray diffraction (XRD) with respect to the μc-Si thin film. The μc-Si thin film uses SiF as a source gas._FourAnd the duty ratio of the pulse modulation frequency is 30%, C.I. W. Is formed. In FIG. W. In this case, the strongest peak appears at (111), whereas when the duty ratio is 30%, the strongest peak appears at (220), and the orientation can be controlled. I understand.
[0028]
FIG. 7 shows the duty ratio dependence of the area intensity ratio of (220) and (111) of the XRD spectrum of the μc-Si thin film. The μc-Si thin film uses SiF as a source gas._FourFormed without addition of SiF and SiF_FourIs formed. SiF_FourIn both cases of adding and not adding, (220) is preferentially oriented as the duty ratio decreases. SiF_FourIn the case of adding, the orientation is further (220).
[0029]
The following can be said from these experimental results. That is, SiF as a source gas_FourIs added to improve the orientation of the μc-Si thin film. In addition, the orientation can be controlled by generating the plasma P by changing the duty ratio for pulse-modulating the electric power. In particular, good orientation can be obtained at a duty ratio of 30%.
Note that in this embodiment mode, a microcrystalline thin film can be formed with good orientation by using various source gases similar to those in the first embodiment mode. In this case also, the value of the optimum duty ratio may change.
[0030]
In describing the first and second embodiments described above, the process conditions are defined by specific values. However, these process conditions are merely examples, and the present invention is not limited to these process conditions. . In addition to a microcrystalline thin film, a crystalline thin film such as a polycrystalline thin film can be formed.
[0031]
(Third embodiment)
In the film forming method according to the third embodiment of the present invention, the plasma P is generated by alternately switching the duty ratio for pulse-modulating the power between 70% and 30% under the process conditions of the first embodiment. To do. When the duty ratio is 70%, μc-Si with good crystallinity is deposited, and when the duty ratio is 30%, μc-Si with good orientation is deposited. Therefore, a μc-Si thin film having both crystallinity and orientation can be formed. It should be noted that alternately switching the duty ratio between 70% and 30% includes performing the respective duty ratios in appropriate time divisions.
[0032]
Alternatively, a μc-Si thin film with good orientation may be deposited with a duty ratio of 30%, and then a μc-Si thin film with good crystallinity may be deposited with a duty ratio of 70%. When the film is formed in two steps as described above, the orientation of the upper thin film is affected by the orientation of the lower thin film. Accordingly, it is possible to form a μc-Si thin film having both crystallinity and orientation as a whole.
The duty ratio may be fixed to a predetermined value of 30% to 70% to achieve both the crystallinity and orientation of the μc-Si thin film.
[0033]
(Fourth embodiment)
FIG. 8 is a diagram for explaining a film forming method according to the fourth embodiment of the present invention. Also in this embodiment, as in the first embodiment, the plasma P is generated by pulse-modulating the power. However, the power ON / OFF and the negative ion source gas introduction ON / OFF are synchronized. More specifically, as shown in FIGS. 8A and 8C, SiF is intermittently used as a negative ion source gas in synchronization with the pulse-modulated power changing from ON to OFF._Four, F₂Are introduced into the chamber 1.
[0034]
When the power changes from ON to OFF, the energy of electrons in the plasma P, that is, the electron temperature, decreases. For this reason, electrons combine with F and F^-Ions are easily generated. Therefore, by introducing negative ion source gas before and after the power changes from ON to OFF, negative ions can be efficiently generated and used for film formation.
As shown in FIG. 8B, SiH_FourThe positive ion source gas such as may be introduced constantly regardless of the ON / OFF of the electric power.
[0035]
(Fifth embodiment)
FIG. 9 is a diagram showing a main configuration of a microwave plasma CVD apparatus used in the film forming method according to the fifth embodiment of the present invention. The gas introduction system of this CVD apparatus has a two-stage configuration. In the lower stage, SiF is used as a negative ion source gas toward the first space 21 close to the susceptor 2 (ie, away from the antenna 6)._Four, F₂Negative ion source gas introduction nozzles 51A and 51B are provided, and SiH as a positive ion source gas toward the second space 22 close to the antenna 6 (that is, away from the susceptor 2) is provided in the upper stage._Four, H₂There are provided positive ion source gas introduction nozzles 52A and 52B for introducing the above.
[0036]
In the space 22 close to the antenna 6, the electron temperature of the plasma P is high and positive ions are likely to be generated. Therefore, SiH as a source gas of positive ions toward the space 22_Four, H₂Etc., and the generated SiH_Three ⁺, H⁺Thus, positive ions can be efficiently supplied onto the glass substrate W by supplying positive ions such as diffusing or electric fields onto the glass substrate W.
On the other hand, in the space 21 close to the susceptor 2, the electron temperature of the plasma P is low and negative ions are easily generated. Therefore, SiF is used as a negative ion source gas toward the space 21._Four, F₂Etc., F^-Thus, negative ions can be efficiently supplied onto the glass substrate W.
[0037]
(Sixth embodiment)
FIG. 10 is a diagram for explaining a film forming method according to the sixth embodiment of the present invention. In the present embodiment, a positive ion beam 31 A is extracted from the positive ion beam source 31, a negative ion beam 32 A is extracted from the negative ion beam source 32, and these are irradiated toward the glass substrate W. Thereby, positive ions and negative ions can be supplied onto the glass substrate W without using plasma.
The fourth embodiment described above is an example in which the magnitude and magnitude of electron energy are temporally separated. In the fifth and sixth embodiments, the magnitude and magnitude of electron energy are spatially separated. This is an example of separation.
[0038]
(Seventh embodiment)
In the above, film formation by the plasma CVD method has been described as an example, but the present invention can also be applied to film formation by the plasma sputtering method. For example, Al₂O_ThreeWhen forming a thin film, the Al knocked out of the target⁺Ions and O introduced into the chamber 1₂O generated from gas^-By supplying ions onto the glass substrate W, Al⁺Ion and O^-Uses the energy generated when ions recombine to produce low temperature and good crystallinity.₂O_ThreeA thin film can be formed. O^-Ions are generated when pulse-modulated power is turned off.
Similarly, AlO_x ^-Metal oxide negative ions and Ar⁺Or O⁺You may utilize the production | generation energy at the time of recombining with positive ions, such as.
La_XO_YAnd Yr_XO_YIt is also possible to form a thin film made of or the like.
The present invention can also be applied to film formation by a laser ablation method.
[0039]
Although an example using a microwave plasma CVD apparatus has been described above, any plasma CVD apparatus such as a capacitively coupled plasma CVD apparatus, an inductively coupled plasma CVD apparatus, or an ECR plasma CVD apparatus may be used. In addition, a reactive sputtering apparatus is also included in the CVD apparatus.
[0040]
【The invention's effect】
As described above, according to the present invention, positive ions and negative ions are supplied onto an object to be processed, and the object to be processed is generated using the energy generated when these positive ions and negative ions recombine. Since a thin film is formed thereon, a good quality thin film can be formed at a low temperature and with a small number of processes.
In addition, by generating plasma using power that is pulse-modulated with a predetermined duty ratio, the sheath disappears when the pulse is OFF, and the negative ions generated by the plasma reach the surface of the object to be processed. It can be efficiently used for film formation.
[0041]
In addition, by setting the duty ratio to a predetermined value of 30% to 70%, a high-quality crystal thin film can be formed. In particular, the crystallinity of the crystal thin film can be improved by setting the duty ratio to 70%, and the orientation of the crystal thin film can be improved by setting the duty ratio to 30%.
In addition, by switching the duty ratio between 70% and 30% alternately, a crystal thin film having both crystallinity and orientation can be formed.
[0042]
Also, negative ions can be efficiently generated and used for film formation by introducing a negative ion source gas onto the object in synchronization with the pulse-modulated power changing from on to off. it can.
Further, a negative ion source gas is introduced toward the first space on the object to be processed, and a positive ion source gas is introduced toward the second space farther from the object to be processed than the first space. Thus, negative ions and positive ions can be efficiently generated and used for film formation.
Further, by irradiating the object to be processed with a positive ion beam and a negative ion beam, positive ions and negative ions can be efficiently supplied onto the object to be processed.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of a microwave plasma CVD apparatus used in a film forming method according to an embodiment of the present invention.
FIG. 2 is a diagram showing a Raman spectrum of a μc-Si thin film formed by changing a duty ratio of a pulse modulation frequency.
FIG. 3 is a diagram showing the duty ratio dependence of the area intensity ratio between the crystalline component and the amorphous component of the Raman spectrum of a μc-Si thin film.
[Figure 4] F^-It is a figure which shows the duty ratio dependence of the sum total (area) of ion signal strength.
FIG. W. It is a figure for demonstrating the change of the behavior of the negative ion in a pulse modulation.
FIG. 6 is a diagram showing an XRD spectrum of a μc-Si thin film formed by changing a duty ratio of a pulse modulation frequency.
FIG. 7 is a diagram showing the duty ratio dependence of the area intensity ratio of (220) and (111) of the XRD spectrum.
FIG. 8 is a diagram for explaining a film forming method according to a fourth embodiment of the present invention.
FIG. 9 is a diagram showing a main configuration of a microwave plasma CVD apparatus used in a film forming method according to a fifth embodiment of the present invention.
FIG. 10 is a diagram for explaining a film forming method according to a sixth embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Process chamber, 2 ... Susceptor, 3 ... Heater, 4 ... Exhaust port, 5 ... Gas introduction nozzle, 6 ... Disk antenna, 7 ... Quartz plate, 8 ... Ground plane, 9 ... Coaxial waveguide, 10 ... Rectangular guide Wave tube, 11 ... microwave power source, 12 ... load matching device, P ... plasma, W ... glass substrate (object to be processed), 21 ... first space, 22 ... second space, 31 ... positive ion beam source 31A ... Positive ion beam, 32 ... Negative ion beam source, 32A ... Negative ion beam, 51A, 51B ... Negative ion source gas introduction nozzle, 52A, 52B ... Positive ion source gas introduction nozzle.

Claims (14)

A method of forming a thin film on the object to be processed by supplying a plasma including plasma negative ions containing positive ions on the target object,
By generating the plasma using electric power pulse-modulated with a predetermined duty ratio, positive ions and negative ions reach the surface of the object to be processed ,
A film forming method, wherein the temperature of the surface of the object to be processed is increased by using generated energy when these positive ions and negative ions are recombined. In the film-forming method described in Claim 1,
The film forming method, wherein the thin film is a crystalline thin film. In the film-forming method described in Claim 1,
The film forming method, wherein the thin film is an amorphous thin film. In the film-forming method described in Claim 1,
The film forming method, wherein the negative ion includes a negative ion containing a halogen element or a negative ion made of a molecule containing a halogen element. In the film-forming method described in Claim 4,
The negative ions, F ^- or Cl ^- deposition method characterized in that it comprises a. In the film-forming method described in Claim 1,
The negative ions, H ^- or O ^- film forming method, which comprises a. In the film-forming method described in Claim 1,
The film forming method, wherein the positive ions include positive ions containing at least Si or C. In the film-forming method described in Claim 7,
The film forming method, wherein the positive ions include SiH ₃ ⁺ , SiH _x F ⁺ , SiH _x F ₃ ⁺ or CH ₃ ⁺ . In the film-forming method described in Claim 1,
The film forming method, wherein the positive ions include H ⁺ or H ₃ ⁺ . In the film-forming method described in Claim 1,
The film forming method, wherein the duty ratio is a predetermined value of 30% to 70%. In the film-forming method described in Claim 1,
A film forming method, wherein the duty ratio is alternately switched between 70% and 30%. In the film-forming method described in Claim 1,
A first step of forming a film at a duty ratio of 30%;
And a second step of forming a film at a duty ratio of 70%. In the film-forming method described in Claim 1,
A film forming method, wherein the negative ion source gas is introduced onto the object to be processed in synchronization with the pulse-modulated power changing from on to off. In the film-forming method described in Claim 1,
The negative ion source gas is introduced toward the first space on the object to be processed, and the positive ion source gas is directed toward the second space farther from the object to be processed than the first space. A film forming method characterized by introducing the above.

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