JP3084395B2 - Semiconductor thin film deposition method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for depositing a semiconductor thin film, and more particularly to an improvement in a method for depositing a semiconductor thin film from a gaseous raw material using heat.

[0002]

2. Description of the Related Art Conventionally, as one method of depositing a silicon thin film from a gaseous raw material using heat, a technique of depositing amorphous silicon and crystalline (including polycrystalline) silicon thin films from a silane-based gas is known. In the case of silane-based gas, the temperature is 500 ° C. or higher for monosilane (SiH ₄ ), 425 ° C. or higher for disilane (Si ₂ H ₆ ), and trisilane (Si
For ₃ H ₈₎ is the temperature of the real film formation than 400 ° C., but is a deposition rate of about 1000 angstroms in generally 1 hour at these temperatures, practical and more 50 ° C.
As described above, a high deposition temperature was required. Thus, film formation at a high temperature limits the type of substrate used, and in particular, a glass substrate cannot be used. Furthermore, the photoconductivity was at least two orders of magnitude lower than films deposited using plasma. On the other hand, however, thermal CVD amorphous silicon also had excellent characteristics such as little photodegradation.

[0003]

Therefore, thermal CVD
There has been a demand for a method of depositing a semiconductor thin film and a method of improving photoelectric properties, which take advantage of the advantages described above and have a high deposition rate. This problem was the same for the germanium thin film and the silicon thin film containing carbon.

It is known that photoelectric characteristics can be improved by bonding hydrogen to defects such as dangling bonds such as silicon, germanium, and carbon. However, even after a thin film was formed by thermal CVD, the film was once taken out of the film forming apparatus into the outside air and exposed to hydrogen plasma, and almost no improvement in photoelectric conductivity was observed.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for depositing a semiconductor thin film, comprising supplying at least a source gas to a heated substrate surface and depositing silicon, germanium, carbon, or a mixed thin film thereof by thermal CVD. After supplying a plasma containing excited hydrogen onto the substrate,
The method is characterized in that the substrate is heated without being exposed to the outside air and a source gas is supplied to perform thermal CVD. by this,
The present invention makes it possible to improve the photoconductivity of the thin film and increase the deposition rate.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to FIG. FIG. 1 shows a thermal CVD apparatus using disilane (Si ₂ H ₆ ). As shown, a susceptor 2 is provided in a quartz chamber 1, and substrates 3 and 3 ′ are placed on the susceptor 2. The susceptor 2 and the substrates 3, 3 'are designed to be heated by irradiating infrared rays from an infrared lamp 4. 5 is a reflection mirror. The temperature of the substrates 3, 3 'is detected by a thermocouple 6 inserted into the susceptor 2, and a signal of the thermocouple 6 is supplied to a control device 7, which controls the power supplied to the lamp according to the magnitude of the signal. Then, finally, the temperature of the substrates 3, 3 'is adjusted. The quartz chamber 1 is vacuum-sealed by a stainless steel flange 8 and can be depressurized by a connected vacuum pump 9. A preset gas (plurality) is supplied to the surface of the substrate from the gas mixing device 10 at a controlled flow rate.

A discharge electrode 12 shielded by quartz 11 is inserted into the quartz chamber 1, and an AC voltage is applied to this electrode from an AC electrode 14 having a switch 13. Plasma discharge occurs in the periphery.

Using such a thermal CVD apparatus, after supplying excited hydrogen onto a substrate, disilane (S
An example in which a silicon thin film is deposited using i ₂ H ₆ ) and hydrogen as a carrier gas will be described.

First, a quartz substrate 3 and a crystalline silicon substrate 3 '(for measuring the amount of bonded hydrogen) are placed on the illustrated SiC coated susceptor 2, hydrogen is introduced at 40 to 45 sccm, and the chamber pressure is reduced to about 0.6 Torr. Adjusted. With SW13 turned ON, an AC voltage is applied to the discharge electrode, hydrogen plasma is generated with AC power of 40W, and excited hydrogen is supplied onto the substrate for 5 minutes (at this time, the substrate is already heated to 425 ° C. ).

Then, Si ₂ H ₆ is flowed to reduce the chamber pressure to 1
The pressure was set to 0 Torr, and Si ₂ H ₆ was supplied onto the substrate heated to 425 ° C. The deposition rate of the obtained silicon thin film is 70 to 4
0 Å / min, and the deposition rate only changed within the above range from 3 minutes to 10 minutes after the supply of the excited hydrogen. However, these deposition rates were 5 to 3 times the deposition rates when ordinary thermal CVD was performed using the same apparatus without supplying excited hydrogen to the substrate in advance. When the source gas at the time of depositing the silicon thin film was Si ₂ H ₆ ′12 sccm + H ₂ (carrier gas) 40 sccm and the deposition temperature was 440 ° C., the deposition rate improvement ratio was 1.7 to 2 times.

The excited hydrogen is introduced into a decompression chamber, and a DC or AC voltage is applied between two electrodes provided inside or outside the chamber to form hydrogen plasma. It may be guided to the surface. Hydrogen plasma can be formed by forming a portion of a chamber formed of an insulating material and coupling an alternating current through inductive coupling from that portion, or by introducing microwaves from the insulating material portion. The plasma may be created in the space containing the substrate or in another space. Further, hydrogen may be introduced into the decompression chamber, and the hydrogen may be irradiated with an electron beam or X-ray to form excited hydrogen. Further, excited hydrogen can be produced by irradiating hydrogen with far ultraviolet rays or mixing it with an excited Hg gas (in this case, normal pressure may be used). Alternatively, if a material that easily releases molecules is placed in direct contact with the plasma, these impurities are also introduced into the film together with the excited hydrogen, and the film quality cannot be improved.Therefore, it is necessary to shield the metal part with quartz or the like. There is.

Also, an example in which a silicon thin film is deposited using disilane (Si ₂ H ₆ ) as a source gas has been described.
Monosilane (SiH ₄ ), trisilane (Si ₂ H ₈ ), other hydrogenated silane-based gases, and a gas in which an alkyl group is bonded to silicon can also be used.

[0013] For the germanium deposition hydrogenated gate <br/> Le Mans system _{(GeH 4, Ge 2 H 6} ···) may be used gas.

Using a hydrocarbon such as methane (CH4) or ethane (C2H6) as a source gas, a carbon film can be deposited in a similar manner.

Further, a thin film in which silicon, germanium, and carbon are mixed at an arbitrary ratio by mixing source gases such as the above-mentioned silane-based gas, germane-based gas, and alkyl-silane-based gas can be deposited in the same manner as described above.

[0016]

As described above, according to the present invention, (1) by supplying a plasma containing excited hydrogen onto a substrate, hydrogen bonding to a defective portion of a thin film deposited in the next step is achieved. Although it can be guessed, it is possible to effectively
Could be improved. (2) The optical band gap can be reduced to about 1.6 eV, and conversion of long wavelength light is possible accordingly. (3) Light degradation is as small as thermal CVD films. (4) There is an effect that the deposition rate is improved even at a lower temperature than the conventional thermal CVD.

[Brief description of the drawings]

FIG. 1 is a diagram showing an outline of a CVD apparatus used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Quartz chamber 2 Susceptor 3 Quartz substrate 3 'Crystal silicon substrate 4 Infrared lamp 6 Thermocouple 7 Control device 10 Gas mixing device 12 Discharge electrode 14 AC electrode

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) H01L 21/205 C23C 16/46

Claims (1)

(57) [Claims] 1. A hydrogenated silane system is applied to a heated substrate surface.
Gas, silicon with alkyl group bonded, germane hydride
Containing at least one selected from system gases and hydrocarbons.
Supplying a non-source gas, silicon or germanium or carbon, or any mixture of these films in the process of depositing a semiconductor thin film deposited by thermal CVD, and supplying a plasma containing excited hydrogen on the substrate, said plasma supplying step And heating the substrate without exposing the substrate to outside air to supply a raw material gas and performing thermal CVD.