JPS62163316A - Manufacture of semiconductor element - Google Patents

Abstract

PURPOSE:To eliminate the need for masking on etching, and to simplify a process, in which a semiconductor layer and the like are patterned and isolated, by isolating a deposit film according to a desired pattern through etching by oxidation reaction of a substance constituting the deposit film and a gaseous halogen group oxidant. CONSTITUTION:A gaseous halogen group oxidant is introduced from a gas introducing port 302 and a gaseous source material through a solenoid valve from a gas introducing port 303 to a gas transport tube 301 having a multitubular structure. A deposit film is formed in a limited region in a base body fixed on a stage by the gaseous raw material and the halogen group oxidant discharged from a nozzle-shaped gas discharge opening for the gas transport tube 301. The flow rate of the gaseous raw material is reduced or stopped, and the deposit film is isolated through etching by the halogen group oxidant.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to semiconductor devices having one or more semiconductor deposited films, such as image forming members for electrophotography, optical input sensors for optical image input devices, and image pickup devices. The present invention relates to a method for manufacturing devices, photovoltaic elements, etc.

[Prior art and its problems]

Etching of semiconductor layers in conventional semiconductor device forming methods includes liquid phase etching (wet etching) and vapor phase etching (dry etching).

Liquid phase etching involves masking the required portions of the semi-dedicated device, immersing it in an etching solution, and etching away the portions other than the masked portions through a chemical reaction. However, if the adhesion of the mask is insufficient, there is a problem in that the etching 'lfi'7 (l) penetrates and unnecessary parts are etched.

In addition, gas-phase etching includes plasma etching, and in particular, methods that combine plasma etching and the Subanokling effect enable control of the etching percentage and anisotropic etching through the action of reactive gas and sputtering action. Therefore, it is currently becoming the mainstream etching technology for fine processing.

However, masking is required in vapor phase etching as well as in liquid phase etching, and the number of steps for patterning and separation of semiconductor layers increases, which does not improve star productivity and complicates film quality control. There was a problem.

〔the purpose〕

An object of the present invention is to eliminate the drawbacks of the above-described semiconductor film forming method and at the same time provide a novel method for forming a semiconductor element that does not rely on conventional forming methods.

Another object of the present invention is to provide a method for separating a semiconductor layer formed within a vacuum chamber without taking the semiconductor layer out of the vacuum chamber and exposing it to the atmosphere.

Another object of the present invention is to save labor and energy in terms of mass production, and at the same time facilitate control of film quality.

[Means for solving problems]

In order to solve the conventional problems and achieve the above object, a method for manufacturing a semiconductor device according to the present invention includes a method for manufacturing a semiconductor device having at least one layer of semiconductor deposited film, in which a gas for forming the deposited film is used. a gaseous halogen-based oxidizing agent having the property of oxidizing the raw material;
chemically generate a plurality of precursors including excited state precursors by introducing and contacting them into the reaction space, and using at least one of these precursors as a source of deposited film components. forming the deposited film, and then contacting a limited area of the deposited film 9 with the gaseous halogen-based oxidizing agent or a gas in which the proportion of the gaseous halogen-based oxidizing agent is larger than that of the gaseous source material; The method is characterized in that the deposited film is separated in a desired pattern by etching caused by an oxidation reaction between a substance constituting the deposited film and the gaseous halogen-based oxidizing agent.

[Function] By forming the semiconductor element in this way, masking during the etching process described above becomes unnecessary, and the process of patterning and separating the semiconductor layer etc. is simplified, and at the same time, energy saving is achieved in terms of mass production. Membrane quality can be easily controlled.

In addition, since etching is performed using a gas to form the deposited film, patterning and separation can be performed without contaminating the deposited film, improving film quality and the state of the interface between deposited films, improving the quality of semiconductor devices. Characteristics improve.

[Example 1] Hereinafter, an example of the present invention will be described in detail based on the drawings.

Example 1 A pin-type photovoltaic device is formed according to a first implementation of the present invention.

First, FIG. 1 is a schematic diagram of a deposited film forming apparatus used in this example.

In the same figure, the substrate 8 that has been pushed out from the feed roller 1 has deposition spaces 6a, 6b, in which a p-type layer, an i-type layer, and an n-type layer are deposited, respectively. 3 and 6C, a pin structure is formed and is wound up by a winding roller 1'.

Gas introduction pipes 2a are provided in the deposition spaces 5a, 5b, and 5c.

A gaseous halogen oxidizing agent is introduced from 2b and 2c, and a gaseous raw material is introduced from gas introduction pipes 3a, 3b and 3c, respectively. In addition, the gas release lowers 07a, 707 of each deposition space
b, 707c have gas release holes scattered radially.

Furthermore, heaters 5a, 5b, and 5c are provided opposite the gas discharge ports of these gas introduction pipes to heat the base 8 to a desired temperature.

In this way, the pin-type laminated structure is free from impurities (,
A photoelectric transformer that can be formed continuously and has high quality and high photoelectric conversion efficiency because it does not involve a plasma reaction! ! ! ! You get layers.

Hereinafter, a method for manufacturing a photovoltaic device using this example will be specifically explained.

First, in the deposition space 6a, 20 sec of Plh gas diluted by 3000 ppm with the gaseous source material (1)e and 305 ccn+ of I4 gas) are supplied from the four-gas pipe 3a to the gaseous halogen oxidizer (5i) from the gas introduction pipe 2a. F2 gas L
2 sccm) were introduced, and an n-type semiconductor layer 201 was deposited to a thickness of 400 layers on a sheet-like substrate 8 made of stainless steel.

Next, in the deposition space 6b, SiL gas is supplied for 45 seconds from the gas introduction pipe 3b, and F2 gas is supplied for 15 seconds from the gas salt introduction pipe 2b.
sec each to a thickness of 600 sec on the n-type semiconductor layer.
An i-type soil conductor layer 202 was deposited.

Next, in the deposition space 6C, B2H6 gas diluted to 3000 ppm with 1) e is introduced from the gas introduction pipe 3C for 22 seconds.
, 5il14 gas for 25sec and C1)4 gas for 4sec, F2 gas from gas introduction pipe 2C for 12S
CCm is introduced onto the l-type semiconductor layer to a thickness of 600 mm.
A p-type semiconductor layer 203 was deposited.

Note that the temperature of the base 8 when depositing each semiconductor layer is 25
It was maintained at 0°C.

Subsequently, a SnO□ layer 204 having a thickness of 500 layers was formed on the p-type semiconductor layer 203 by vacuum evaporation.

The thus produced photovoltaic device stored in the roll shape was cut into a square shape of approximately 12 cm x 1 2 cm. FIG. 2 is a perspective view thereof.

Next, a process of separating the square elements thus cut out into a desired pattern will be described.

First, FIG. 3(A) is a perspective view showing the main parts of the deposited film forming apparatus, and FIG. 3(B) is a schematic cross-sectional view of the gas transport pipe.

Four gaseous halogen-based oxidizers are introduced from the gas inlet 302 into the gas transport pipe 301 having a multi-pipe +74 construction as shown in FIG. 3(B). A gaseous raw material is introduced from the fifth population 303 via a solenoid valve 304 . and,
The gaseous source material and halogen-based oxidizing agent or halogen-based oxidizing agent discharged from the nozzle-shaped gas outlet of the gas transport pipe 301 come into contact with a limited area of the base fixed on the stage 305, and the deposited film is Perform partial formation or partial etching.

The gas transport pipe 301 is movable in the direction of arrow A and/or arrow B by the main scanning rail 306 and the sub-scanning rail 307, and the stage 305 is movable by the main scanning rail 306 and the sub-scanning rail 307.
08 and sub-scanning rail 309 to
Or it can move in the direction of the arrow. Therefore, the gas transport pipe 301 can be moved to any position on the substrate on the stage 305, and a deposited film can be formed in a desired pattern or etched in a desired pattern.

Further, the base on the stage 305 has a halogen lamp 31
heated by 0.

Using such an apparatus, the photovoltaic element shown in FIG. 2 was separated. First, the photovoltaic element is fixed on the stage 305, the solenoid valve 304 is closed to stop the supply of gaseous raw materials such as S i I+ 4, and 20% diluted F2 gas is supplied to the gas transport pipe 301 for 80 seconds. to measure the internal pressure
It was held at orr. Then, the gas transport pipe 301 was moved relative to the stage 305 as described above, and the photovoltaic element and the deposited film were separated by etching. FIG. 4 is a perspective view of the photovoltaic device showing a state in which the gas transport pipe 301 is scanned in a grid pattern so that the photovoltaic devices are completely independently separated in a grid pattern.

Each of the photovoltaic devices produced in this way showed a photoelectric conversion rate sufficient for practical use.

In this example, a deposited film was formed using the deposited film forming apparatus shown in FIG. 1, and it was separated using the apparatus shown in FIG. 3, but the apparatus shown in FIG. It can also be used for forming. Therefore, the substrate is placed on stage 30.
5, the gaseous raw material and the halogen-based oxidizer are discharged from the gas transport pipe 301 to form a deposited film in a desired pattern, and then the flow of the gaseous raw material is reduced or stopped to complete the deposition process. , the membrane may be separated.

(Example 2) Similarly to Example 1, the production of a photovoltaic device will be described.

The structure of the photovoltaic device was similar to that shown in FIG. 2, but a hatch-shaped stainless steel substrate was pretreated as follows. Immediately, this stainless steel hatch-shaped substrate was surface-treated using fluorine gas using an apparatus as shown in FIG. 5.

Add a description of the device. In FIG. 5, 501 is a gaseous raw material introduction pipe, 502 is a gaseous halogen-based oxidant introduction pipe, 503 is a chamber, 50.4 is a vacuum exhaust valve, 505 is a substrate support, and 506 is a heater for heating the substrate. , 507 is a heater power source for heating the substrate, 508 is a thermal lightning pair for monitoring substrate temperature, 509 is a substrate temperature monitor, 51
0 Stainless steel hatch-shaped base.

In this embodiment, the gaseous raw material introduction pipe 501 is not used.
Gaseous halogen-based oxidizer thickness from inlet pipe 502 lle dilution 5
000 ppm fluorine gas was introduced at 20 sccm, the evacuation valve 504 was adjusted, and the pressure inside the chamber 503 was set to 100 mTorr. Base temperature is 250°
C was constant. This state was left for 5 minutes to etch the surface of the stainless steel hatch-shaped substrate 510. The purpose of this is to wash/7 roughen the surface of the substrate 510 so that the photovoltaic element does not have a texture effect, that is, an improvement in the efficiency of light absorption.

FIG. 6(A) is a schematic cross-sectional view of a substrate 510 whose surface has been etched in this manner.

After performing such an r+i treatment, a tumor similar to that shown in Example 1 is introduced through the gas introduction pipes 501 and 502, and an n-type amorphous silica 7 with a thickness of 500 mm is deposited on the substrate 510. layer 201, i-type amorphous silicon layer 202 with a thickness of 5000 nm, and 7 layers of n-type amorphous silicon 203 with a thickness of 500 nm.
Then, approximately 300 people formed a SnO□ layer 204 as a transparent electrode. FIG. 6(B) is a schematic cross-sectional view of this photovoltaic element.

This batch photovoltaic device was installed in the position shown in FIG. 3 in the same manner as in (Example 1) of the present invention, and by repeating the same operation as in (Example 1), the photovoltaic device as shown in FIG. 4 was obtained. It was possible to separate them into a grid pattern. When one of the separated photovoltaic saw elements was taken out and irradiated with AM-1 as a light source, it was found that it was a practical photovoltaic element.

(Example 3) Using the deposited film forming apparatus shown in FIG. 7, an optical sensor was produced according to the third embodiment H of the present invention as follows.

FIG. 8 is a schematic diagram of the optical sensor manufactured according to this example.

First, a glass substrate 827 was placed on the substrate support 712, the distance between the gas discharge port of the gas introduction tube 71) and the substrate 827 was set to 3.4 cm, and the substrate temperature was set to 250°C. Subsequently, the F2 gas filled in the cylinder 706 was flowed at a rate of 'ff 3 sec, and the TIE gas filled in the cylinder 707 was introduced into the vacuum chamber 720 through the gas introduction pipe 71) at a rate of '/R'' fk 40 sccm. did.

At this time, the pressure inside the vacuum chamber 720 was adjusted to 800 mTorr by adjusting the opening/closing degree of the vacuum valve 719.

Hold this state for 30 minutes, and then remove the glass substrate 8270.
The surface was etched.

Next, 5i) I4 gas filled in the cylinder 701 was introduced into the vacuum chamber half 20 through the gas introduction pipe 709 at a flow rate of 30 sec.

When gas was allowed to flow in this state for 45 minutes, an a-5::II:F film 826 was deposited on the surface of the glass base +Fj, 827. The obtained a-5i:II:F film 826 is placed on a stage 305 shown in FIG.
Fixed. After separating the a-3i:tl:F film 826 into a desired shape in the same manner as in Example 1, as shown in FIG. and fabricated an optical sensor.

When the optical sensor was irradiated with monochromatic light from a 1le-Ne laser with a wavelength of 6,328 people and an emission intensity of 0 and 5 mW, the dark power ratio was 2. OXl0−”Ω”1cm−1,
It has been shown to have a photoconductivity of 3.5×10 −6 Ω−I Cm −1 for 6 years.

(Example 4) Using the deposited film forming apparatus shown in FIG.
In some embodiments, a thin film transistor (hereinafter referred to as TPT) is used.

) was created. FIG. 9 is a schematic diagram of the TPT.

First, a glass substrate 934 was placed on the substrate support 712, and the distance between the gas discharge port of the gas introduction pipe 71) and the substrate 934 was set to 3 cm, and the substrate temperature was set to 420'C.

Subsequently, the Fz gas filled in the cylinder 706 was introduced into the vacuum chamber half 20 at a flow rate of 3 seconds, and the Lie gas filled in the cylinder 707 was introduced into the vacuum chamber half 20 at a flow rate of 4 Q sccm.

At this time, the pressure inside the vacuum chamber half 20 was adjusted to 800 mTorr by adjusting the opening/closing degree of the vacuum valve 719 (31).

This state was maintained for 20 minutes, and the surface of the glass substrate 934 was etched.

Next, what about the SiH4 gas filled in the cylinder 701? A
The gas was introduced into the vacuum chamber half 20 from the gas introduction pipe 709 at a rate of 120 seconds.

When gas was allowed to flow in this state for one hour, a polycrystalline Si:H:F film 933 was deposited on the glass substrate 934.

This polycrystalline S i:II:F film 933 was fixed on the stage 305 shown in FIG. 3 centering around the part where the film thickness was uniform, and separated into a desired pattern in the same manner as in Example 1.

An n layer 932 was formed to obtain ohmic contact, and a gate insulating layer 931 made of silicon nitride or the like was formed thereon to a thickness of 0.3 μm. Then, a source electrode 928 and a drain electrode 930 are formed through the contact holes formed in the insulating layer 931 on the n° layer 932, and the polycrystalline Si
A gate electrode 929 was formed to face the :tl:F film 933 with an insulating layer 931 in between.

As described above, the TPT manufactured using the present invention exhibited excellent electrical characteristics with a good 0N10FF resistance ratio because it had a high-quality semiconductor layer.

(Example 5) FIG. 10 is a schematic diagram of a photoconductive member for electrophotography manufactured according to a fifth example of the present invention. Note that a deposited film forming apparatus shown in FIG. 7 was used for fabrication.

In FIG. 10, an a-3i:Ge:O:H:F:B amorphous layer 1002 is on a stainless steel substrate 1001.
, p-type a-5i:0:If:F:B amorphous layer 1003
, amorphous layer 1004 of a-SiJ:F exhibiting photoconductivity
, and an a-5i:C:H:F amorphous layer 1005 which is a surface protective layer.

First, the stainless steel substrate 1001 is placed on the base support 712, and the gas outlet of the gas introduction pipe 71) and the substrate 1001 are placed on the substrate support 712.
The distance from the substrate was set to 3c+n', and the substrate temperature was set to 250°C.

Next, the F2 gas filled in the cylinder 706 is added at a flow rate of 3
Qsccm, He gas filled in the cylinder 707 was introduced into the vacuum chamber 720 through the gas introduction pipe 71) at a flow rate ffi 50 sec. At this time, the pressure inside the vacuum chamber 720 was adjusted to 300 mTorr by adjusting the opening/closing degree of the vacuum valve 719. 15 in this state
to etch the surface of the substrate 1001,
The surface of the substrate 1001 was cleaned and smoothed.

Next, the 0□ gas filled in the cylinder 708 is added at a flow rate of 1
The SiH gas filled in the cylinder 701 is introduced into the vacuum chamber half 20 from the gas introduction pipe 71) at 0 sec.
4 gas is introduced into the vacuum chamber 720 from the gas introduction pipe 709 at a flow rate of 15 seconds, and the Ge1) 4 gas filled in the cylinder 702 is introduced into the vacuum chamber 720 at a flow rate of 15 seconds, and the gas is reduced to 1% with the II2 filled in the cylinder 703. diluted B
21) 6 gas (hereinafter referred to as BZI+6/1)□.

) in a vacuum chamber 720 with a flow rate of Yt 10 sec.
The pressure inside the vacuum chamber 720 was set to 300 mTorr without changing the flow rates of I7□ gas and He gas.
maintained at r.

This state was maintained for 10 minutes, and an amorphous layer 1002 made of a-5i:Ge:0:H:F:B having a thickness of 1 μm was formed on the substrate 1001.

Hereinafter, under the film forming conditions shown in Table 1, the a-Si:0:
0.5 pm thick amorphous layer 1003 made of II:F:B, 1003 thick made of a-Si:II:F
A 0.4 pm thick amorphous layer 1005 made of 8 μm amorphous 1)004, a-3i:C:It:F was sequentially formed to produce the photoconductive member for electrophotography. Furthermore, C2II
The four gases filled in a cylinder 704 were introduced into a vacuum chamber 720 through a gas introduction pipe 710.

The photoconductive member thus produced was fixed to a stage 305 shown in FIG. 3, and the ends were removed to complete the process.

When image characteristics were evaluated for the photoelectric member for electrophotography obtained as described above, the potential unevenness was ±5■, the number of image defects was initially 9 (Ill, 1 after 50,000 sheets durability test),
After the 150,000 sheet durability test, the number of sheets was 15, indicating sufficient performance for practical use.

〔Effect of the invention〕

As explained in detail above, the present invention is semi-! The manufacturing method of the aluminum element has excellent productivity and mass production, and can easily form a deposited film with high quality and excellent physical properties such as electrical, optical, and semi-solid properties. Since it is possible to separate the film in a desired pattern, masking during etching is no longer necessary, and the process of patterning and separating the half-gate layer is simplified, which saves energy in mass production and also improves film quality control. can be facilitated.

In addition, since etching is performed using a gas to form the deposited film, it is possible to perform buttering and separation without contaminating the deposited film, improving film quality and the interface state between the deposited films, and improving semiconductor devices. characteristics are improved.

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram of a first example of the deposited film forming apparatus, FIG. 2 is a perspective view of a cut out photovoltaic element, and FIG. 3(A) is a second example of the deposited film forming apparatus. FIG. 3(B) is a schematic cross-sectional view of the gas transport pipe, FIG. 4 is a perspective view of photovoltaic elements separated into a grid, and FIG. 5 is a perspective view showing the main parts of the example. A schematic block diagram of a third example of a deposited film forming apparatus; FIG. 6(A) is a schematic cross-sectional view of a substrate whose surface has been etched; FIG. 6(B) is a schematic cross-sectional view of a photovoltaic element; FIG. 7 is a schematic diagram showing a fourth example of a deposited film forming apparatus. FIG. 8 is a schematic configuration diagram of an optical sensor. FIG. 9 is a schematic diagram of a TPT. FIG. 10 is a photoelectric member for electrophotography. FIG. 301... Gas transport pipe, 302... Gaseous halogen-based oxidant dedicated pipe, 303... Gaseous raw material introduction pipe,
304... Solenoid valve, 305... Stage, 306° 308... Main scanning rail, 307, 309... Sub-scanning rail, 31O... Halogen run '7', 201...
. . . n-type semiconductor layer, 202 . . . i-type semiconductor layer, 203
... p-type semiconductor layer, 204-3nO2 layer, 826-a
-5i:it:Fli, 827...Glass substrate, 92
8... Source electrode, 929... Gate electrode, 930
... Train electrode, 931 ... Gate insulating layer, 93
2...n' layer, 933...Polycrystalline Si:Il:F layer, 934...Glass substrate, 1001...Stainless steel substrate, 1002-a-5i:Ge:0:lI:F:8 layer, 1003- p-type a-3i:0:It:F:8 layer, 1
00i・・a-5il(:F layer 3.1005・”a-5
i:C:it:F layer. Agent Patent Attorney Jo Taira Yamashita Figure 3 (B) ↓ Guide Figure 4 Figure 5 Figure 6 (A). De(B) 7o knee γOB 'O8; o7 Blade・ )8C )8f- )7f
f1: 3JI281) 1 Purport 1) 1 Length 'IX' Michibu Uga Patent Application No. 1981-4369 2 Title of Invention Method for Manufacturing Conductor Element 3 Supplementary tI:・Relationship to 1) Patent applicant name (100) Canon Co., Ltd. 4, agent address 40 Toranomon 5-cho [1) 3-1 Toranomon, Minato-ku, Tokyo
Mori Hill Akira 1ii1) The purity of calligraphy and drawings! J-7 and power of attorney 6 Contents of amendment

Claims (1)

[Claims] (1) A method for manufacturing a semiconductor element having at least one layer of a semiconductor deposited film, comprising: a gaseous raw material for forming the deposited film; and a gaseous halogen-based oxidizing agent having the property of oxidizing the raw material. chemically producing a plurality of precursors, including excited state precursors, by introducing and contacting them into the reaction space, and using at least one of the precursors as a source of the deposited film component. forming a deposited film, and then contacting a limited area of the deposited film with the gaseous halogen-based oxidizing agent or a gas in which the proportion of the gaseous halogen-based oxidizing agent is larger than that of the gaseous source material; 1. A method for manufacturing a semiconductor device, characterized in that the deposited film is separated in a desired pattern by etching caused by an oxidation reaction between a substance constituting the film and the gaseous halogen-based oxidizing agent.