JPH0978245A - Formation of thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a stable thin film having high performance at a low temp. at high speed by transporting the substrate formed with the thin film in a film forming chamber into a treating chamber and irradiating the thin film surface with UV rays in vacuum. SOLUTION: The substrate 102 is installed onto the anode 104 of the film forming chamber 101 and the inside of the film forming chamber 101 is evacuated. Prescribed gases (for example, SiH4 and H2 ) are introduced from a gas introducing pipe 106 into the film forming chamber 101 and while these gases are kept at a desired pressure, a DC voltage is impressed between an anode 104 and a cathode 103 from a power source 107 to form plasma near the cathode 103 and to form a thin film (for example, silicon nitride film) on the substrate 102 surface. The substrate 102 is then transported into a treating chamber 109 in such a manner that there is no difference pressure between the film forming chamber 101 and a treating chamber 109. The substrate is placed on a susceptor 110. The inside of the treating chamber 109 is held at about 10<-6> Torr via a discharge pipe 111 and UV rays are emitted from a light source 114 (for example, an ultra-high pressure mercury lamp, etc.). The film on the substrate 102 is irradiated with the required quantity of the UV rays through a quartz member 113.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thin film forming method, and more particularly to a thin film forming method for forming a high quality thin film at a low temperature.

[0002]

2. Description of the Related Art Microwave C as an example of a thin film forming method
The film formation on the polycarbonate by the VD method is performed as follows, for example. A substrate placed in the film forming chamber by introducing a source gas into the film forming chamber of a microwave plasma CVD apparatus and simultaneously inputting microwave energy to generate plasma in the film forming chamber to excite and decompose the gas. A thin film of the deposited film is formed on top. Further, if necessary, the substrate on which the thin film is formed is transported to the processing chamber for post-treatment.

A commonly used post-treatment method is an annealing method. In this method, first, a substrate after film formation is placed in a processing chamber, and thermal energy is applied to the processing chamber by evacuation or an air atmosphere with a heater or the like to process a thin film.

[0004]

However, in the above-mentioned conventional example, there is a problem that not only the thin film portion but also the temperature of the substrate rises and the substrate is thermally deformed when a plastic substrate such as polycarbonate is used. .

An object of the present invention is to solve the problems of the prior art and to form a thin film which is high in performance and stable at low temperature at high speed by treating the thin film immediately after forming the thin film while suppressing the temperature rise of the substrate. To provide a method.

[0006]

In the present invention, the electronic state of the molecules forming the thin film is excited by irradiating the thin film-formed substrate at a low temperature with ultraviolet rays selectively absorbed by the thin film. For example, a reaction such as a hydrogen dissociation reaction is induced.
This makes it possible to improve the film quality while suppressing the substrate temperature rise.

Now, a general structure of the thin film forming method of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view of a film forming chamber and a processing chamber. 101 is a film forming chamber, 102 is a substrate,
Reference numeral 103 is a cathode, 104 is an anode that also serves as a support for the substrate 102, 105 is an exhaust pipe, 106 is a gas introduction pipe, 107 is a DC power supply, 108 is a gate valve, 109 is a processing chamber, 11
Reference numeral 0 is a support for the base 102, 111 is an exhaust pipe, 112 is a gas introduction pipe, 113 is a quartz member, and 114 is a light source.

The substrate 10 is placed on the anode 104 in the film forming chamber 101.
2 is installed and the inside of the film forming chamber 101 is evacuated. Next, a specific gas is introduced into the film forming chamber 101 from the gas introducing pipe 106 according to the purpose, and a DC voltage is applied between the anode 104 and the cathode 103 while maintaining the pressure in the film forming chamber 101 at a desired pressure. Is applied. Plasma is generated in the vicinity of the cathode 103, and a film is formed on the surface of the base 102. After a predetermined thin film is formed on the substrate, the inside of the film forming chamber 101 and the inside of the processing chamber 109 are further decompressed to a value of 10 ⁻⁶ Torr through an exhaust system (not shown). After confirming that there is no pressure difference between the film forming chamber 101 and the processing chamber 109, the gate valve 108 is opened to deposit the substrate 102 on the film forming chamber 10.
1 to the processing chamber 109 and set on the support 110.
A conductance valve (not shown) provided on the exhaust pipe 111 side is fully opened to maintain the pressure at about 10 ^-6 Torr. Next, ultraviolet rays are emitted from a light source 114 (for example, an ultra-high pressure mercury lamp or the like), and a necessary amount of light is applied to the film on the substrate 102 through the quartz member 113.

In the thin film forming method of the present invention, a silicon nitride film, a silicon oxide film, a tantalum oxide film, a titanium oxide film, a titanium nitride film, an aluminum oxide film, an aluminum nitride film, or a fluoride is selected by appropriately selecting a gas to be used. Insulating film such as magnesium film, a-Si, poly-Si, Si
It is possible to form a semiconductor film of C, GaAs or the like, or a thin film of various deposited films.

The substrate formed by the thin film forming method of the present invention may be a conductive substance, an electrically insulating substance or a semiconductor, but especially on a substrate having low heat resistance. Is effective for forming a thin film.

As the conductive substrate, Fe, Ni, Cr, A
Examples thereof include metals such as 1, Mo, Au, Nb, Ta, V, Ti, Pt, and Pb or alloys thereof, such as brass and stainless steel.

As the insulating substrate, polyethylene, polyester, polycarbonate, cellulose acetate,
Examples thereof include films and sheets of organic materials such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide. Heat resistant temperature of substrate is 100
In the case of a material having a temperature of ℃ or less, the present invention is particularly preferable because the substrate hardly rises in temperature and is not deformed or melted.

The wavelength of ultraviolet rays preferably used in the thin film forming method of the present invention is 400 nm or less, and the wavelength region which is absorbed by the thin film and excites the electronic state of the molecules constituting the thin film is selected. If the thin film is a silicon nitride film and the refractive index is in the range of 2.1 to 2.4, the wavelength of ultraviolet rays to be irradiated is 300 to 400 nm, as compared with the case where the refractive index is out of this range.
Therefore, the object of the present invention can be achieved more preferably. For example, in the case of a silicon nitride film having a refractive index of 2.1 to 2.4, the transmittance is 300 to 400, which is 5 to 70%.
By irradiation with ultraviolet rays having a wavelength of nm, a high-quality film having a low hydrogen content is formed. If the transmittance is less than 5%, most of the ultraviolet rays are reflected on the surface of the film and the irradiation effect becomes insufficient, and if it exceeds 70%, 70% or more of the ultraviolet rays pass through the film, and a sufficient reaction cannot proceed. When ultraviolet rays having a wavelength of less than 300 nm are irradiated, the ultraviolet rays are absorbed near the surface of the thin film, the reaction of the entire thin film does not proceed, and the improvement of the film quality cannot be seen as a whole. Wavelength 4
Since the light having a wavelength longer than 00 nm penetrates through the film, the reaction hardly progresses.

As a light source for emitting ultraviolet rays, a lamp such as a xenon lamp, a mercury lamp, a halogen lamp, or A
Lasers such as r lasers, He-Ne lasers, N ₂ lasers and the like can be mentioned. Furthermore, when a pulsed light source such as a pulse laser or a flash lamp is used, the light energy is concentrated in a short time to promote the reaction of the thin film, and thus the effect of improving the film quality is exerted more effectively.

Since the thin film forming method of the present invention is based on the action of ultraviolet rays absorbed by the thin film, the effect can be obtained while keeping the substrate at a low temperature.

Further, the thin film forming method of the present invention is characterized by irradiating ultraviolet rays in the processing chamber, but it may be performed in a vacuum atmosphere in the processing chamber or in a gas atmosphere in which gas is introduced. For example, when a silicon nitride film is formed, by irradiating ultraviolet rays in a nitrogen gas atmosphere, a high-quality film having a lower hydrogen content than that in vacuum is formed.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 An example in which the thin film forming method of the present invention is applied to the formation of a silicon nitride film for a magneto-optical disk will be described with reference to FIG. FIG.
FIG. 3 is a cross-sectional view of a film forming chamber and a processing chamber.

As the base 102, a polycarbonate (PC) substrate [φ3.5 inch, heat resistant temperature 60 ° C.] was used. First, the substrate 102 was placed on the anode 104, and the inside of the film forming chamber 101 was evacuated. Next, from the gas introduction pipe 106, SiH
₄ and N ₂ are introduced into the film forming chamber 101, and the pressure in the film forming chamber 101 is kept in the range of 1 to 20 Torr while the anode 10
A DC voltage was applied between 4 and the cathode 103. Cathode 10
Plasma was generated in the vicinity of 3 and a silicon nitride film was formed on the surface of the substrate 102. Further, the inside of the film forming chamber 101 and the inside of the processing chamber 109 are passed through an exhaust system (not shown) to 10 ⁻⁶ Torr.
The pressure was reduced to the value of. After confirming that there is no pressure difference between the film forming chamber 101 and the processing chamber 109, the gate valve 108 is opened to open the substrate 1.
02 is transported from the film forming chamber 101 to the processing chamber 109 and the support 1
It was installed at 10. Fully open a conductance valve (not shown) provided on the exhaust pipe 111 side to adjust the pressure to 10 ^-6 To.
rr. Next, ultraviolet rays were emitted from the ultra-high pressure mercury lamp 114 to irradiate the silicon nitride film on the substrate 102 through the quartz member 113.

The following Table 1 shows the absorption coefficients of Si-N and Si-H (the value obtained by dividing the absorbance by the film thickness, unit: μm ^-1 ). It was confirmed that the absorption coefficient of Si-N did not change and the absorption coefficient of Si-H decreased by 13%, and the hydrogen content decreased correspondingly when comparing the one without ultraviolet treatment with the one treated with ultraviolet light in this vacuum. did it. Therefore, it is considered that the ultraviolet rays cut the Si—H bond and the released hydrogen atoms were released. Low temperature (6 because no deformation is seen on the PC board
At 0 ° C. or lower), a high-quality silicon nitride film having a low hydrogen content in the film could be formed.

[0021]

[Table 1] Example 2 An example in which the thin film forming method of the present invention is applied to a silicon nitride film for a magneto-optical disk will be described with reference to FIGS. FIG. 1 is a sectional view of a processing chamber.

As the base 102, a polycarbonate (PC) substrate [φ3.5 inch, heat resistant temperature 60 ° C.] was used. First, the substrate 102 was placed on the anode 104, and the inside of the film forming chamber 101 was evacuated. Next, from the gas introduction pipe 106, SiH
₄ and N ₂ are introduced into the film forming chamber 101, and the pressure in the film forming chamber 101 is kept in the range of 1 to 20 Torr while the anode 10
A DC voltage was applied between 4 and the cathode 103. Cathode 10
Plasma was generated in the vicinity of 3 and a silicon nitride film was formed on the surface of the substrate 102. Further, the inside of the film forming chamber 101 and the inside of the processing chamber 109 are passed through an exhaust system (not shown) to 10 ⁻⁶ Torr.
The pressure was reduced to the value of. After confirming that there is no pressure difference between the film forming chamber 101 and the processing chamber 109, the gate valve 108 is opened to open the substrate 1.
02 is transported from the film forming chamber 101 to the processing chamber 109 and the support 1
It was installed at 10. Fully open a conductance valve (not shown) provided on the exhaust pipe 111 side to adjust the pressure to 10 ^-6 To.
The pressure was reduced to rr. Next, nitrogen gas was introduced from the gas introduction pipe 112 and a conductance valve (not shown) provided on the exhaust pipe 111 side was adjusted to maintain the pressure at 760 Torr. Next, ultraviolet rays were emitted from the light source 114, and the silicon nitride film on the substrate 102 was irradiated through the quartz member 113.

Table 2 shows absorption coefficients of Si-N and Si-H. Comparing the one without UV treatment and the one with UV treatment in the nitrogen atmosphere this time, the absorption coefficient of Si-N did not change, the absorption coefficient of Si-H decreased by 26%, and the hydrogen content decreased by that amount. It could be confirmed.

[0024]

[Table 2] Example 3 An example in which the thin film forming method of the present invention is applied to the formation of a plastic lens antireflection silicon nitride film and a silicon oxide film will be described with reference to FIG.

The substrate 202 has a diameter of 50 mm plus
A tic convex lens was used. First, the base body on the support 203
202 is disposed, and the inside of the film forming chamber 201 is exhausted from the exhaust pipe 204.
I feel like 10^-6The pressure was reduced to the value of Torr. Then the first
From the gas introduction pipe 205 of SiH_Four 100 sccm, first
2 gas introduction pipe 206 to N₂ 150 sccm, third
Deposition chamber for Ar at a flow rate of 2 slm from the gas introduction pipe 207 of
A connector installed in the exhaust pipe 204 on the exhaust pipe 204 side.
The pressure of 1 mTorr is set by the cactance valve (not shown).
Hold. In addition, a 2.45 GHz microwave power source (not
1kW electric power oscillated from
Plasma is generated by introducing it into the film forming chamber 201 through a tube 208.
I let it. At this time, it is introduced through the second gas introduction pipe 206.
The generated nitrogen gas is excited and decomposed in the film forming chamber 201, and is decomposed.
It becomes an active species such as an elementary atom and is transported toward the substrate 202.
Is introduced through the first gas introduction pipe 205.
The silicon nitride film reacts with the run gas to form 2 on the substrate 202.
It was formed with a thickness of 1 nm. Further, in the film forming chamber 201 and
The inside of the processing chamber 215 is exhausted through an exhaust system (not shown) for 10 ^-6T
The pressure was reduced to the value of orr. Film forming chamber 201 and processing chamber 21
Check that there is no differential pressure of 5 and open the gate valve 210.
The substrate 202 is transported from the film forming chamber 201 to the processing chamber 215 and supported.
It was installed on the holding body 216. A connector provided on the exhaust pipe 211 side
Fully open the inductance valve (not shown) and set the pressure to 10
^-6The pressure was reduced to Torr. Next, from the gas introduction pipe 212
Conductor installed on the exhaust pipe 211 side by introducing nitrogen gas
Adjust the chest valve (not shown) to adjust the pressure to 760 Torr.
held at r. Next, the light source 214 emits ultraviolet rays,
To the silicon nitride film on the substrate 202 through the English member 213.
Irradiated.

Furthermore, inside the film forming chamber 201 and the processing chamber 21.
The inside of 5 was depressurized to a value of 10 ⁻⁶ Torr through an exhaust system (not shown). After confirming that there is no pressure difference between the film forming chamber 201 and the processing chamber 215, the gate valve 210 is opened to open the substrate 202.
Of the substrate 203 from the processing chamber 215 to the film forming chamber 201.
Installed in. The conductance valve (not shown) provided on the exhaust pipe 204 side is fully opened to adjust the pressure to 10 ^-6 Torr.
The pressure was reduced to. Next, from the first gas introduction pipe 205, Si
H ₄ 100 sccm, O from the second gas introduction pipe 206
₂ for 200 sccm, Ar from the third gas introduction pipe 207
Is introduced into the film forming chamber 201 at a flow rate of 2 slm, and the exhaust pipe 2
The pressure was maintained at 1 mTorr by a conductance valve (not shown) provided on the 04 side. Furthermore, 2.45G
1 kW of power oscillated from a microwave power source (not shown) of Hz through the slotted annular waveguide 208
1 and plasma was generated. At this time, the oxygen gas introduced through the second gas introducing pipe 206 is used as the film forming chamber 20.
Excited and decomposed in 1 to become active species such as oxygen atom,
The first gas introduction pipe 205 is transported in the direction of the substrate 202.
The silicon oxide film was formed on the base 202 to a thickness of 86 nm by reacting with SiH ₄ introduced through the substrate. Further, an exhaust system (not shown) is provided inside the film forming chamber 201 and the processing chamber 215.
The pressure was reduced to a value of 10 ⁻⁶ Torr via. It was confirmed that there was no pressure difference between the film forming chamber 201 and the processing chamber 215, the gate valve 210 was opened, and the substrate 202 was transported from the film forming chamber 201 to the processing chamber 215 and installed on the support 216. Exhaust pipe 21
The conductance valve (not shown) provided on the first side was fully opened, the pressure was reduced to 10 ^-6 Torr, and the pressure was maintained. Next, ultraviolet rays were emitted from the light source 214, and the silicon oxide film on the substrate 202 was irradiated through the quartz member 213.

It was confirmed that the film quality of the obtained silicon nitride film and silicon oxide film had a very good optical property with a reflectance of 0.3% in the vicinity of 500 nm. Moreover, the curvature of the lens surface was measured and compared with the reference lens by an interferometer, but no change due to film formation was observed.

Embodiment 4 An embodiment in which the thin film forming method of the present invention is applied to the formation of a silicon nitride film for a magneto-optical disk will be described with reference to FIG.

As the substrate 202, a polycarbonate (PC) substrate [φ3.5 inch, heat resistant temperature 60 ° C.] was used. First, the substrate 202 is placed on the support body 203, and the inside of the film forming chamber 201 is evacuated through the exhaust pipe 204 to reach 10 ⁻⁶ Torr.
The pressure was reduced to the value of. Next, 40 sccm of SiH ₄ from the first gas introducing pipe 205, 20 sccm of N ₂ from the second gas introducing pipe 206, and A from the third gas introducing pipe 207.
r is introduced into the film forming chamber 201 at a flow rate of 200 sccm,
A conductance valve (not shown) provided on the exhaust pipe 204 side keeps the pressure at 6 mTorr. Furthermore,
Electric power of 4 kW oscillated from a microwave power source (not shown) of 2.45 GHz was introduced into the film forming chamber 201 through the annular waveguide 208 with slots to generate plasma. On this occasion,
The nitrogen gas introduced through the second gas introducing pipe 206 is excited and decomposed in the film forming chamber 201 to become active species such as nitrogen atoms, which are transported toward the substrate 202, and the first gas introducing pipe 205. The silicon nitride film was formed on the substrate 202 in a thickness of 21 nm by reacting with SiH ₄ introduced through the substrate. Further, the inside of the film forming chamber 201 and the inside of the processing chamber 215 were depressurized to a value of 10 ⁻⁶ Torr via an exhaust system (not shown). After confirming that there is no pressure difference between the film forming chamber 201 and the processing chamber 215, the gate valve 210 is opened and the substrate 202 is attached to the film forming chamber 20.
It was transported from the No. 1 to the processing chamber 215 and installed on the support 216.
A conductance valve (not shown) provided on the exhaust pipe 211 side was fully opened to reduce the pressure to 10 ^-6 Torr. Next, a conductance valve (not shown) provided on the exhaust pipe 211 side by introducing nitrogen gas from the gas introduction pipe 212
Was adjusted and the pressure was maintained at 760 Torr. Next, ultraviolet light having a wavelength of 337.1 nm was emitted from the nitrogen laser 214, and the silicon nitride film on the substrate 202 was irradiated through the quartz member 213.

Comparing the one without nitrogen laser treatment and the one without nitrogen laser treatment, the absorption coefficient of Si-N did not change, and the absorption coefficient of Si-H decreased by about 20%, and the hydrogen content decreased accordingly. Thus, the effect of improving the film quality was confirmed.

Example 5 An example in which the thin film forming method of the present invention is applied to the formation of a silicon nitride film for a magneto-optical disk will be described with reference to FIG.

As the substrate 202, a polycarbonate (PC) substrate [φ3.5 inch, heat resistant temperature 60 ° C.] was used. First, the substrate 202 is placed on the support body 203, and the inside of the film forming chamber 201 is evacuated through the exhaust pipe 204 to reach 10 ⁻⁶ Torr
The pressure was reduced to the value of. Next, 40 sccm of SiH ₄ from the first gas introducing pipe 205, 20 sccm of N ₂ from the second gas introducing pipe 206, and A from the third gas introducing pipe 207.
r is introduced into the film forming chamber 201 at a flow rate of 200 sccm,
A conductance valve (not shown) provided on the exhaust pipe 204 side keeps the pressure at 6 mTorr. Furthermore,
Electric power of 4 kW oscillated from a microwave power source (not shown) of 2.45 GHz was introduced into the film forming chamber 201 through the annular waveguide 208 with slots to generate plasma. On this occasion,
The nitrogen gas introduced through the second gas introducing pipe 206 is excited and decomposed in the film forming chamber 201 to become active species such as nitrogen atoms, which are transported toward the substrate 202, and the first gas introducing pipe 205. The silicon nitride film was formed on the substrate 202 in a thickness of 21 nm by reacting with SiH ₄ introduced through the substrate. Further, the inside of the film forming chamber 201 and the inside of the processing chamber 215 were depressurized to a value of 10 ⁻⁶ Torr via an exhaust system (not shown). After confirming that there is no pressure difference between the film forming chamber 201 and the processing chamber 215, the gate valve 210 is opened and the substrate 202 is attached to the film forming chamber 20.
It was transported from the No. 1 to the processing chamber 215 and installed on the support 216.
A conductance valve (not shown) provided on the exhaust pipe 211 side was fully opened to reduce the pressure to 10 ^-6 Torr. Next, a conductance valve (not shown) provided on the exhaust pipe 211 side by introducing nitrogen gas from the gas introduction pipe 212
Was adjusted and the pressure was maintained at 760 Torr. Next Xe
Ultraviolet rays are emitted from the flash lamp, and the quartz member 213
The silicon nitride film on the substrate 202 was irradiated with the light.

Xe without flash lamp treatment and X
Compared with the one treated with flash lamp,
The absorption coefficient of -N did not change, and the absorption coefficient of Si-H decreased by about 20%, and the hydrogen content decreased correspondingly, so that the effect of improving the film quality could be confirmed.

Example 6 An example in which the thin film forming method of the present invention is applied to the formation of a pin junction type photovoltaic layer for a solar cell will be described with reference to FIG.

The base 202 is made of stainless steel (SUS4
30) which was coated with an Al film as the lower electrode was used. First, the substrate 202 is placed on the support 203, and the inside of the film forming chamber 201 is evacuated through the exhaust pipe 204, and 10 ⁻⁶
The pressure was reduced to Torr. Further, the substrate 202 was heated to 350 ° C. and held by using a heating means (not shown). Next, 60 scc of SiH ₄ is fed from the first gas introduction pipe 205.
m, H ₂ at 100 sccm, 1% PH ₃ / H ₂ at 10 sccm from the second gas introduction pipe 206, and SiF ₄ at 5 sccm from the third gas introduction pipe 207. Next, a pressure of 15 mTorr is maintained by a conductance valve (not shown) provided on the exhaust pipe 204 side. In this state, 800 W of power oscillated from a 2.45 GHz microwave power source (not shown) is used to form the slotted annular waveguide 20.
The film was introduced into the film forming chamber 201 via 8 and plasma was generated to form an n-type a-Si: H: F film on the substrate 202. Further, the inside of the film forming chamber 201 and the inside of the processing chamber 215 were depressurized to a value of 10 ⁻⁶ Torr via an exhaust system (not shown). After confirming that there is no pressure difference between the film forming chamber 201 and the processing chamber 215, the gate valve 210 is opened and the substrate 202 is attached to the film forming chamber 20.
It was transported from the No. 1 to the processing chamber 215 and installed on the support 216.
A conductance valve (not shown) provided on the exhaust pipe 211 side was fully opened to reduce the pressure to 10 ^-6 Torr and maintained at that pressure. Next, ultraviolet rays are emitted from the light source 214, and the n-type a on the substrate 202 is passed through the quartz member 213.
-Si: H: F film was irradiated.

Furthermore, inside the film forming chamber 201 and the processing chamber 21.
5 is 10^-6Confirm that the pressure has been reduced to the value of Torr
Then, the gate valve 210 is opened and the substrate 202 is attached to the processing chamber 2.
15 is transferred to the film forming chamber 201 and installed on the support 203.
Was. Conductance valve provided on the exhaust pipe 204 side
(Not shown) fully open and set the pressure to 10^-6Decompress to Torr
I let it. Next, from the first gas introduction pipe 205, SiH_Four 3
00 sccm, H from the second gas introduction pipe 206₂ 10
0 sccm, SiF from the third gas introduction pipe 207 _Four 1
It was introduced at a flow rate of 0 sccm. Further on the exhaust pipe 204 side
10 by the conductance valve (not shown) provided
Hold at a pressure of mTorr. 2.45GH in this state
1200W oscillated from a microwave power source (not shown) of z
Power of the film through the annular waveguide with slot 208
01-type a-Si:
An i-type a-Si: H: F film was formed on the H: F film. Further
The inside of the film forming chamber 201 and the processing chamber 215 are exhausted (not shown).
Via) 10^-6The pressure was reduced to the value of Torr. Success
Check that there is no differential pressure between the membrane chamber 201 and the processing chamber 215, and
The valve 202 is opened to remove the substrate 202 from the film forming chamber 201.
It was transported to the processing chamber 215 and installed on the support 216. Exhaust pipe
Conductance valve provided on the 211 side (not shown)
Fully open and set the pressure to 10^-6Reduce the pressure to Torr,
Maintained at pressure. Next, the ultraviolet rays are emitted from the light source 214,
I-type a-Si on the substrate 202 through the quartz member 213:
The H: F film was irradiated.

Furthermore, inside the film forming chamber 201 and the processing chamber 21.
After confirming that the inside of the chamber 5 is depressurized to a value of 10 ⁻⁶ Torr, the gate valve 210 is opened and the substrate 202 is placed in the processing chamber 2.
It was transported from 15 to the film forming chamber 201 and installed on the support 203. A conductance valve (not shown) provided on the exhaust pipe 204 side was fully opened to reduce the pressure to 10 ^-6 Torr. SiH ₄ from the first gas inlet pipe 205 for 20s
ccm, 200 sccm of H ₂ , second gas introduction pipe 20
6 to 0.3% B ₂ H ₆ / H ₂ was introduced at a flow rate of 10 sccm, and SiF ₄ was introduced at a flow rate of 5 sccm from the third gas introduction pipe 207. Next, the pressure is maintained at 20 mTorr by a conductance valve (not shown) provided on the exhaust pipe 204 side. In this state, 1200 W of electric power oscillated from a 2.45 GHz microwave power source (not shown) is introduced into the film forming chamber 201 through the annular waveguide with a slot 208 to generate plasma to generate i-type a-Si: H: p-type aS on F film
An i: H: F film was formed. Further, the inside of the film forming chamber 201 and the inside of the processing chamber 215 are passed through an exhaust system (not shown) to 10 ⁻⁶ To
The pressure was reduced to the value of rr. Deposition chamber 201 and processing chamber 215
After confirming that there is no differential pressure, the gate valve 210 was opened and the substrate 202 was transported from the film forming chamber 201 to the processing chamber 215 and installed on the support 216. Fully open the conductance valve (not shown) provided on the exhaust pipe 211 side to adjust the pressure to 10 ^−6.
The pressure was reduced to Torr and maintained at that pressure. Next, ultraviolet rays were emitted from the light source 214, and the p-type a-Si: H: F film on the substrate 202 was irradiated through the quartz member 213.

Photoelectric conversion rate of the solar cell thus manufactured
Was evaluated. 0.1 W / cm ² With the intensity of
Under irradiation, the photoelectric conversion rate shows a good value of 8.8%,
The characteristics were stable.

Embodiment 7 An embodiment in which the thin film forming method of the present invention is applied to the formation of a silicon oxide film on a liquid crystal display substrate will be described with reference to FIG.

As the substrate 302, glass having electrodes (ITO film, Al film, etc.) formed thereon was used. First support 3
03, the base 302 is placed on the base plate 03, and the film formation chamber 3
The inside of 01 was evacuated and the pressure was reduced to a value of 10 ⁻⁶ Torr.
Next, 100 sc of SiH ₄ is introduced through the first gas introduction pipe 305.
cm, O ₂ 200 scc from the second gas introduction pipe 306
m, Ar is introduced from the third gas introduction pipe 307 into the film formation chamber 301 at a flow rate of 2 slm, and 1 mTorr by a conductance valve (not shown) provided on the exhaust pipe 304 side.
Hold at pressure. Further, 1 kW of electric power oscillated from a microwave power source (not shown) of 2.45 GHz was introduced into the film forming chamber 301 through the annular waveguide with slots 308 to generate plasma. At this time, the oxygen gas introduced through the second gas introduction pipe 306 is excited and decomposed in the film forming chamber 301 to become active species such as oxygen atoms, which are transported toward the substrate 302, and the first gas is supplied. By reacting with SiH ₄ introduced through the introduction pipe 305, a silicon oxide film was formed on the substrate 302. Further, the inside of the film forming chamber 301 and the inside of the processing chamber 311 were depressurized to a value of 10 ⁻⁶ Torr through an exhaust system (not shown). After confirming that there was no pressure difference between the film forming chamber 301 and the processing chamber 311, the gate valve 310 was opened and the substrate 302 was transported from the film forming chamber 301 to the processing chamber 311 and installed on the support 313. A conductance valve (not shown) provided on the exhaust pipe 312 side was fully opened to reduce the pressure to 10 ⁻⁶ Torr, and the pressure was maintained. Next, excimer lamp 3
Ultraviolet rays were emitted from No. 15 to irradiate the silicon oxide film on the substrate 302 through the quartz member 314.

The withstand voltage of the obtained silicon oxide film was evaluated. The withstand voltage was a good value of 12 MV / cm, and the characteristics were stable.

[0042]

As described above, after the thin film is formed, by irradiating with ultraviolet rays having a thin film transmittance of 5 to 70%, for example, hydrogen bonds are dissociated to suppress the temperature rise of the substrate and, for example, the dehydrogenation reaction proceeds. There is an effect of improving the film quality such that the hydrogen content in the film decreases.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a cross section of a film forming chamber / processing chamber according to Examples 1 and 2 of the present invention.

FIG. 2 is a diagram schematically showing a cross section of a film forming chamber / processing chamber according to Examples 3 to 5 of the present invention.

FIG. 3 is a diagram schematically showing a cross section of a film forming chamber / processing chamber according to a sixth embodiment of the present invention.

[Explanation of reference numerals] 101 deposition chamber 102 substrate 103 cathode 104 anode 105 exhaust pipe 106 gas introduction pipe 107 direct current power supply 108 gate valve 109 processing chamber 110 support 102 of substrate 102 111 exhaust pipe 112 gas introduction pipe 113 quartz member 114 light source 201 Deposition chamber 202 Base body 203 Support body of base body 204 Exhaust pipe 205 First gas introduction pipe 206 Second gas introduction pipe 207 Third gas introduction pipe 208 Waveguide 209 Quartz member 210 Gate valve 211 Exhaust pipe 212 Gas Introducing pipe 213 Quartz member 214 Light source 215 Processing chamber 216 Support for substrate 202 301 Film forming chamber 302 Substrate 303 Support for substrate 302 304 Exhaust pipe 305 First gas introducing pipe 306 Second gas introducing pipe 307 Third gas Introduction tube 308 Microwave waveguide 309 Stone Support 314 quartz member 315 of the member 310 a gate valve 311 processing chamber 312 exhaust pipe 313 base 302 sources

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location H01L 21/31 H01L 21/31 C

Claims (13)

[Claims] 1. A step of forming a thin film on a substrate in a film forming chamber by a chemical vapor phase method, a step of transporting the substrate from the film forming chamber to a processing chamber without exposure to the atmosphere, and a gas in the processing chamber. And a step of irradiating the surface of the thin film with ultraviolet light in an atmosphere or in a vacuum. 2. The transmittance of the thin film for the ultraviolet rays is 5 to 70.
2. The method for forming a thin film according to claim 1, wherein ultraviolet rays having a wavelength of% are used. 3. The method for forming a thin film according to claim 1, wherein the ultraviolet light is pulsed light whose intensity changes with time. 4. The method of forming a thin film according to claim 1, wherein the substrate has a heat resistant temperature of 100 ° C. or lower. 5. The substrate is polyethylene, polyester, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, acrylic resin, gelatin, or a polymer compound containing these as main components. The thin film forming method according to any one of claims 1 to 4, characterized in that 6. The method for forming a thin film according to claim 1, wherein the substrate is polycarbonate or a polymer compound containing it as a main component. 7. The thin film formed in the film forming chamber is a silicon nitride film, a silicon oxide film, a tantalum oxide film, a titanium oxide film, a titanium nitride film, an aluminum oxide film, an aluminum nitride film, a magnesium fluoride film, or the like. The thin film forming method according to claim 1, wherein the thin film forming method is an insulating film. 8. The method for forming a thin film according to claim 7, wherein the thin film is a silicon nitride film having a refractive index of 2.1 to 2.4. 9. The wavelength of the ultraviolet light is 300 nm to 400 n.
The method for forming a thin film according to claim 1, wherein the thickness is in the range of m. 10. The thin film forming method according to claim 1, wherein the gas is nitrogen. 11. The method for forming a thin film according to claim 1, wherein the thin film is a semiconductor film made of amorphous silicon, polycrystalline silicon, SiC, GaAs or the like. 12. The thin film forming method according to claim 1, which is a method for manufacturing a magneto-optical disk. 13. The thin film forming method according to claim 1, which is a method for manufacturing a liquid crystal display element.