JP2650050B2 - Thin film formation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Technical Field The present invention relates to an amorphous silicon (a-Si: amorphous silic) formed by a plasma CVD method under a pressure near the atmospheric pressure.
on) and the like.

For example, an amorphous silicon a-Si film that usually contains several at% to several tens at% (atomic percent) of H in a film is promising as a material for a low-cost solar cell.
There are also other uses such as image sensors, optical sensors, thin film transistors, and photosensitive materials for copying machines. There is an advantage that it is cheaper than single-crystal Si and a large-area one is easily obtained.

Such thin film formation methods include thermal CVD and plasma CVD.
The law is known.

Since the thermal CVD method requires heating the substrate, it can be used only for heat-resistant materials.

On the other hand, the plasma CVD method can form a thin film at a lower temperature than the thermal CVD method.

Therefore, a thin film can be formed on a low-cost glass substrate, a polymer film, or the like having poor heat resistance, and is widely used.

In the plasma CVD method, the excitation energy is provided not in the form of heat but in the form of kinetic energy of electrons and ions in the plasma and chemical energy of neutral radicals. For this reason, the temperature of the substrate can be lower than that of the thermal CVD method.

As an example, amorphous silicon a-Si is
Invented a method of forming a thin film by glow discharge, and it was possible to incorporate an appropriate amount of H into the film and to reduce the defect density in the film, thereby producing a device that can withstand device applications such as solar cells and sensors. Is now available.

WESpear, PG Lecomber: Solid Commun., 17, p1193 (197
5) This involves applying an alternating voltage of 100 kHz to 13.56 MHz to a parallel plate type electrode, and applying SiH ₄ / H ₂ , SiH ₄ -S at a low pressure of 0.1 to ₂ Torr.
Glow discharge is caused in a mixed gas such as iF ₄ / H ₂ .

Of course, a dopant may be added. This is the PH
It is performed by mixing gas such as ₃ / H ₂ and B ₂ H ₆ / H ₂ .

(B) Prior art Since the invention of Spear, a-Si manufacturing equipment has been continuously improved, but basically glow discharge was performed at a low pressure.

Glow discharge does not occur unless the pressure is as low as about 0.1 to 10 Torr. If the pressure is higher than this, the discharge shifts to local arc discharge, and film formation on a substrate having poor heat resistance and uniform film formation over a large area cannot be performed. Thus, such a pressure is chosen.

Therefore, the container required an expensive vacuum chamber and a vacuum pump had to be installed.

In particular, in the case of a photoelectric conversion material such as a solar cell using a-Si or the like, it is strongly required that a large-area thin film can be formed at once in terms of cost.

However, the plasma CVD method maintains a stable plasma by maintaining a glow discharge. Glow discharge is carried out in a vacuum (0.1-1
Only about 0 Torr).

Since a film can be formed only in a vacuum, if a large-area product is to be manufactured, the entire vacuum container must be enlarged.

 A high-power evacuation device is required.

Then, the equipment becomes extremely expensive.

(C) Atmospheric pressure plasma CVD method For practical use of thin films such as a-Si films, cost reduction is an important factor.
The law had a major problem of high equipment costs.

However, recently, under atmospheric pressure, plasma CVD
An invention was made that enabled the law.

 For example, i JP-A-63-50478 (S.63.3.3 published).

The present inventors, ii Japanese Patent Application No. 63-199647 (S.63.8.10 application) iii Japanese Patent Application No. 63-199647
No. 199648 (S.63.8.10 application) iv Japanese Patent Application No. 63-199649 (S.6
3.8.10 application).

FIG. 2 shows a slightly modified version of what is indicated by iv.

In the film forming chamber 1, electrodes 2 and 3 facing each other are provided. One is grounded, and this is connected to ground electrode 3
Call. The other is referred to as a non-ground electrode 2.

The high resistance body 4 is arranged on the electrode 2. Also, the sample substrate 5 is placed on the electrode 3. Here, the electrode 2 and the high resistance body 4
The high-resistance body 4 is also a perforated plate, also serving as a gas supply port to the discharge space.

Here, the reason why the high resistance body 4 is inserted is not to cause the glow discharge to occur locally but to cause the glow discharge to occur widely in the entire electrode plate, and to insert the high resistance body between the electrode 3 and the sample substrate 5. You may.

The reason why the high resistance body 4 is a perforated plate and a gas supply port is to effectively perform gas replacement at the center of the plasma and obtain a uniform film. Here, the distance g between the sample substrate 5 and the high-resistance body 4 is set to 10 mm to 0.1 mm.

A high frequency power supply 7 is connected to the non-ground electrode 2. This can use, for example, a 13.56 MHz RF oscillator and amplifier.

A mixed gas obtained by diluting the source gas with He gas in a large amount is introduced from a gas inlet 6, supplied to a discharge space via an electrode 2 and a high-resistance body 4, and discharged from a gas outlet 9 to the outside of the film forming chamber 1. Is discharged. Further, the flow rate Q of the mixed gas with respect to the volume S of the discharge space is set so that Q / S is 1 sec ^-1 to 10 ² sec ^-1 .

(G) Problems to be solved by the invention Thin film formation by plasma CVD under atmospheric pressure is a very promising method for cost reduction, but its film properties are poor when applied to devices. Nothing happens. For example, in the case of an a-Si film, application to a solar cell, an image sensor, an optical sensor, a thin film transistor, an electrophotographic photoreceptor, and the like is progressing, but as a film characteristic, a photoelectric conductivity (Δσ _ph ) is high, It is desirable that the photosensitivity (ratio of photo-electric conductivity to dark electric conductivity (σ _d ): Δσ _ph / σ _d ) be high, and the defect density (N _s ) in the film, which greatly affects the device characteristics, be increased. Preferably it is low.

For a thin film, for example, an a-Si film, manufactured by a conventional atmospheric pressure plasma CVD method, Δσ _ph and Δσ _ph / σ _d have the same values as the a-Si film obtained by the low-pressure plasma CVD method.
However, Ns is 1 × 10 ¹⁶ spin / cc, which is lower than the value of a-Si film (Ns <5 × 10 ¹⁵ spin / cc) formed by low pressure plasma CVD and used for devices such as solar cells. high,
There was a problem in application to the device.

In order to solve this problem, the present inventors have made various studies on the cause of the high Ns of the a-Si film formed by the conventional atmospheric pressure plasma CVD method.

As a result, constituent elements of the electrode or the high-resistance body are sputtered by high-density plasma near the atmospheric pressure from the electrode or the high-resistance body facing the film-forming substrate via the plasma, and a large amount of the a-Si film is formed in the a-Si film. And found to be incorporated as impurities into the present invention.

(K) Object The object of the present invention is to provide a method for forming a thin film having good film properties that can be used for device applications in a thin film formation method by plasma CVD under atmospheric pressure, which is promising for cost reduction. Is the thing.

(S) Configuration of the Invention and Means for Solving the Problems The present invention provides an electrode facing a sample substrate via plasma or a sample substrate facing plasma via plasma in order to prevent impurities from being mixed by plasma sputtering. Among the constituent elements of the thin film to be formed as a high-resistance body,
A material composed of at least one element is used.

Alternatively, a material made of at least one of the constituent elements of the thin film to be formed is coated or attached to a surface of the electrode or the high resistance body facing the sample substrate.

As the material facing the sample substrate, it is preferable to use the same material as the thin film to be formed or the main constituent material of the thin film to be formed.

FIG. 1 shows, as a specific example of the present invention, a thin film 10 to be formed on a facing surface of a high-resistance body 4 facing a sample substrate 5.
The following shows an example in which is coated.

It is the same as that of FIG. 2 except that the film-forming material is coated on the surface facing the sample substrate.

In the film forming chamber 1, electrodes 2 and 3 facing each other are provided. One is grounded, and this is called a ground electrode 3. The other is referred to as a non-ground electrode 2.

The high resistance body 4 is arranged on the electrode 2. Also, the sample substrate 5 is placed on the electrode 3. Here, the electrode 2 and the high resistance body 4
The high-resistance body 4 is also a perforated plate, also serving as a gas supply port to the discharge space.

Here, the reason why the high resistance element 4 is inserted is that the glow discharge does not occur locally but occurs widely in the entire electrode plate. When the sample substrate 5 is conductive, the electrode 3 and the sample substrate It is preferable to insert a high-resistance element between 5.

The reason why the high resistance body 4 is a perforated plate and a gas supply port is to effectively perform gas replacement at the center of the plasma and obtain a uniform film.

Here, the distance g between the sample substrate 5 and the high resistance body 4 is 10 mm /
Make it 0.1mm.

A high frequency power supply 7 is connected to the non-ground electrode 2. This can use, for example, a 13.56 MHz RF oscillator and amplifier.

A mixed gas obtained by diluting the source gas with He gas in a large amount is introduced from a gas inlet 6, supplied to a discharge space via an electrode 2 and a high-resistance body 4, and discharged from a gas outlet 9 to the outside of the film forming chamber 1. Is discharged. Further, the flow rate Q of the mixed gas with respect to the volume S of the discharge space is set so that Q / S is 1 sec ^-1 to 10 ² sec ^-1 .

(X) Function As shown in FIG. 1, in the present invention, if a-Si is formed on the surface of the high resistance body facing the sample substrate, for example, a-Si (including hydrogen) Or not necessarily)
In the case of depositing crystalline Si or aC, a film of aC or graphite is deposited, so even if plasma sputtering occurs, the element to be sputtered is the target thin film Can prevent impurities from being mixed into the film, reduce the defect density in the film, and form a promising thin film for device use.

Further, when forming a B-doped p-type a-Si film or a P-doped n-type a-Si film, a non-doped Si film containing no doping element is used as a material facing the sample substrate.
A membrane may be used. When forming an a-SiGe film, an a-SiGe film or a crystalline Si
It may be a Ge material, an a-Si film (which may or may not contain hydrogen), a crystalline Si, an a-Ge film (which may or may not contain hydrogen), or a crystalline Ge material. This is because elements mixed in a film formed from a material facing the sample substrate are constituent elements of the formed film.

(S) Example Using FIG. 1 (the present invention) and FIG. 2 (comparative example), an a-Si film was formed under the conditions shown in Table 1, and the film characteristics were compared. Note that SiO ₂ was used as the high-resistance body 4, and the surface coating material 10 of the high-resistance body was an a-Si film (5 μm in thickness).

Table 1 Deposition conditions Source gas flow rate SiH ₄ 10sccm He gas flow rate 5000sccm Substrate temperature 250 ° C Pressure Atmospheric pressure RF power 200W RF frequency 13.56MHz Electrode area 10cm × 10cm High resistance, distance between substrates 3mm Substrate Quartz glass Deposition time 30min Table 2 shows the properties of the obtained film.

Table 2 Film characteristics The present invention Comparative Example Eg (eV) 1.78 1.89 Δσ _ph (S / cm) 7 × 10 ^-5 1 × 10 ^-5 σ _d (S / cm) 6 × 10 ^-9 5 × 10 ^-10 Ns (spin / cc) 6 × 10 15 1 × 10 16 oxygen impurity concentration (Ke ^{/ cc) 2 × 10 19 8} × 10 19 bandgap (Eg) measures the transmittance of visible light region, Tauku measurements This is a value calculated by plotting.

Δσ _ph is a value measured using a light source of AM1.5 100 mW / cm ² .

Ns is a value of an unpaired electron pair (a terminal bond and one of defects in the film) in the film obtained by electron spin resonance (ESR).

The oxygen impurity concentration is a value determined by secondary ion mass spectrometry (SIMS).

In the present invention, there is no plasma sputtering of O from SiO ₂ used as the high resistance element 4, and the oxygen content in the film is reduced.
It can be seen that Ns decreases and Δσ _ph also increases.

(C) Effect According to the present invention, impurities in a thin film such as an a-Si film can be reduced by using an atmospheric pressure plasma CVD method that can be expected to reduce equipment costs, and solar cells, image sensors, optical sensors, It is possible to form a thin film having excellent film properties which is promising for device applications such as thin film transistors and electrophotographic photosensitive members.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an apparatus used for the thin film forming method of the present invention. FIG. 2 is a schematic cross-sectional view of an apparatus used for a thin film forming method disclosed in Japanese Patent Application No. 63-199649, the present inventor. DESCRIPTION OF SYMBOLS 1 ... Film-forming chamber 2 ... Non-ground electrode 3 ... Ground electrode 4 ... High-resistance perforated plate 5 ... Sample substrate 6 ... Gas inlet 7 ... High frequency power supply 8 ... Heater 9 ... Gas exhaust Exit 10: Thin film intended for film formation

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuuji Tomikawa 1-1-1, Koyokita, Itami-shi, Hyogo Prefecture Inside Itami Works, Sumitomo Electric Industries, Ltd. (72) Inventor Norihiko Fujita 1 Kunyokita, Itami-shi, Hyogo No. 1-1, Itami Works, Sumitomo Electric Industries, Ltd. (56) References JP-A-1-138242 (JP, A) JP-A-63-50478 (JP, A)

Claims (1)

(57) [Claims] A high-resistance body having a resistivity of 10 ¹¹ Ωcm or more is provided on at least one of the opposing surfaces of two electrodes facing each other, and a sample substrate is placed on the electrode or high-resistance body facing the high-resistance body. The distance between the sample substrate and the electrode facing the sample substrate, or the distance between the sample substrate and the high-resistance body facing the sample substrate is 10 mm or less, 0.1 mm or more, A value Q / S obtained by dividing the gas flow rate Q by the volume S of the discharge space of the mixed gas composed of the film forming gas and He.
Is supplied to the discharge space on the sample substrate so as to be ¹ to 10 ² sec ⁻¹ , and is opposed to the sample substrate and the sample substrate by a high frequency voltage applied to the counter electrode under a pressure near the atmospheric pressure In a method of forming a thin film on a sample substrate by causing a glow discharge between the electrodes or between the sample substrate and the high-resistance body facing the sample substrate, the glow discharge faces the sample substrate on which the thin film is to be formed. The electrode to be formed, or that the surface of the high-resistance body facing the sample substrate on which the thin film is to be formed is coated with a material comprising at least one of the constituent elements of the thin film to be formed, or The electrode facing the sample substrate on which the thin film is to be formed, or the high-resistance body facing the sample substrate on which the thin film is to be formed is made of a material comprising at least one of the constituent elements of the thin film to be formed. Feature Thin film forming method.