JPS59231878A - Manufacture of semiconductor device - Google Patents

Abstract

PURPOSE:To reduce contact resistance with a P type semiconductor applied on the surface of an electrode in a light-transmitting conductive film consisting of tin oxide while improving ohmic properties by exposing the surface of the electrode in the light-transmitting conductive film formed on a substrate in a liquid or a gas containing fluorine and activating the surface. CONSTITUTION:A light-transmitting conductive film consisting of ITO and tin oxide such as SnO2 is applied onto a transparent glass substrate 1, and a first opening 13 is bored by using a YAG laser processing machine and a first electrode 2 with a plurality of regions 11 and 13 is formed. The substrate 1 is immersed in fluoric acid diluted to treble or centuple water to activate the surface of the electrode 2, and an amorphous Si layer 3 with a PN or PIN junction is deposited on the whole surface containing the electrode 2 through a plasma CVD method, etc. and a second opening 18 is bored. The whole surface is coated with a thin amorphous Si layer 4 and a third opening 20 is bored, and these regions are each divided while including the electrode 2. An Al electrode 22 is laminated on the whole surface through a thin oxide film 21, and a photoelectric conversion device connected in series, from which currents do not leak, is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention activates the surface of a translucent mounting body having an oxide soot surface formed on a substrate with fluorine to reduce the contact resistance with a P-type semiconductor formed on the upper surface. The purpose is to lower the resistance and improve ohmic contact.

The present invention provides a P-type semiconductor formed on the upper surface of tin oxide by removing oxygen and hydrogen adsorbates on the surface of the tin oxide.
The average oxygen concentration in the type semiconductor is 1 xiolgc, respectively.
The purpose of the present invention is to make a photovoltaic conversion device less than 5XIO cn+, preferably less than 1xlO'cd, eliminate the factor of deterioration due to light irradiation, and produce a highly reliable photoelectric conversion device.

This invention provides a first electrode having soot oxide on the surface provided on a substrate having an insulating surface made of a non-single crystal semiconductor including an amorphous semiconductor having at least one junction capable of generating a photovoltaic force when irradiated with light. In addition, fluorine is added to or near this surface to activate the surface and improve the ohmic contact between the tin oxide and the semiconductor on its top surface.
Second, the present invention relates to a method for manufacturing a highly efficient photoelectric conversion device (also simply referred to as a device) by preventing oxygen from entering the semiconductor by removing oxides adsorbed on the surface. The present invention relates to a method for manufacturing a semiconductor device in which a plurality of such photoelectric conversion devices -r- are electrically connected in series and can generate a voltage of 11.

This invention is a maskless process that reduces the area required for connecting multiple elements to 1/10 to 1/100 of the conventional mask alignment method, and uses a laser scribe method or a laser chemical scribe method. (hereinafter LS
It is characterized by the use of

The arrangement, size, and shape of the elements in the device of the present invention are determined by the installation specifications.

However, in order to simplify the content of the present invention, in the detailed description below, the first
The pattern is based on the case where the electrode is directly electrically connected to the second electrode of the second element placed on the right side thereof (on the semiconductor, that is, on the side facing away from the gate 11 from the substrate).

In such a pattern, an opening groove separating the non-single crystal semiconductors of the first element and the second element is provided over the transparent conductive H9 (hereinafter referred to as CTO) having soot oxide on the surface of the first element, Furthermore, the grooves that separate the second electrodes of each element are provided over half of the first element, thereby providing redundancy that improves yield. .

In this invention, the electrical connection at the connection part is made between the first element and the first element.
The second electrode component of the second element is provided as a connecting conductor (hereinafter referred to as a connector) in close contact with the surface or side surface of the transparent conductive film constituting the electrode.

In the present invention, LS is performed on CTO in an inert gas, halide gas, or liquid atmosphere at a temperature of 1 ni that the laser beam has. Ladder LS,
In the J-culm, silicon oxide constituting the substrate glass and CTO constituting the first electrode mix or react, forming semi-porous, dummy (semi-insulating) silicon oxide (lower silicon oxide and oxide indium). - or a mixture with oxidized soot) may be formed. In the case of bending, it is only possible to electrically separate the first electric current 1 and 91 of the first element and the second element due to leakage in the mixture.

For this reason, the CTO substrate having such oxidized soot on its surface is quenched with a fluoride solution to activate the oxidized soot surface and to dissolve the residual material.

Conventionally, a method of manufacturing a photoelectric conversion device integrated with LS is known. For example, it would be an application filed by four unexploited persons.58--0213210.028211
(February 22, 2013) "Photoelectric conversion device".

However, in this method using LS, when trying to further improve its characteristics, especially the fill factor, it is important to sufficiently reduce the leakage current between adjacent elements and to improve the manufacturing yield. It is.

As a result of thorough investigation into such characteristics, we found that LS
When the first conductive film is scribed (cut) by -1, the oxide of its constituents and the conductive film are scribed (cut) by -1. A mixture or compound of 1XllW and a semiconductor is produced. the result,
The contact resistance at the connection part varies widely (9 to 10M07cm), and is more than IMΩ/cn+ or more preferably IOM
This was completely inadequate for a photoelectric conversion device that would like to have a resistance of Ω/cm or less.

Therefore, an object of the present invention is to have a conductive film having an oxidized soot surface that is not very reactive, to make the surface active, and to remove adsorbed substances. For this purpose, fluoride, such as hydrofluoric acid, is diluted 5 to 50 times with water and then immersed in a liquid after LS to remove the products produced by LS.

The details of the invention are shown below in accordance with the drawings.

FIG. 1 is a longitudinal sectional view showing the manufacturing process of the present invention.

On one side, a transparent substrate (1) such as a glass plate (for example, thickness 0.3-2.2 mm, e.g. 1.2 mm, length [
In the drawing, the horizontal direction) GOam, 11120 cm) was used.

Furthermore, a light-transmitting conductive film (CTO) having soot oxide on the entire surface of this "-" surface, such as ITO (300
~1500 people) +5n02 (200-400 people) Also /Sl A transparent conductive film (1000-2000 people) whose main component is tin oxide doped with a cogen element, especially fluorine, is deposited using a vacuum deposition method.1. I”Cν1) method or plasma CVD
It was formed by a method or a photo plasma CVD method.

After this, the surface of this substrate was treated with argon gas from the top side.
Egishima laser manoko is Y/IG laser, f row is Y/IG laser machining 11 (NEC crack), output (1, 3~3W (focal length 50mm) is added, Suboso L
Typically, 5011φ is controlled by a microcomputer, and the laser beam is emitted from the downstream side.
The first open groove (13) for the flyline is formed by the scanning, and each inter-element region (31),
<II) The first electrode (2) was produced.

Such a first open groove is formed, and its surface is covered with a cristal tube (
As a result of measuring the step film thickness (it), it was found that there was a residue (7), and the laser beam irradiation clearly formed an open groove and the two regions (31> and <II) were electrically separated. It turns out that it hasn't.

Further investigation of this residue revealed that it was ITO.
It is a mixture of soot monoxide and silicon oxide, and the substrate and the conductor on its upper surface are coated with a liquid containing fluoride, such as hydrofluoric acid diluted with water, and diluted 3 to 100 times, for example, 1 () times I/l0.
IIP (1/10 dilution) for 1 second to 3 minutes, generally 3
It was immersed for 0 seconds. Then, the oxidized soot is dissolved away at 1/1011F, and the molten 1' product becomes extremely liquid.
easy to be

Therefore, between that region: 1O unless fluoride treatment is applied
It varied widely from KΩ to ■Ω, making it completely impractical. However, when this was immersed in 4 fluoride/8 solution, the solution was 20μ and 11. However, it has now become possible to overcome a resistance of Ω that is greater than IMΩ.

IJ, 1. CTF constituting the first electrode by the S method
(2) was cut and analyzed to form a first open groove (13).

After this, apply the plasma CVI) method to the top surface. cVI
) method, 1st plasma CVD method or 1. PcVD
A non-single crystal semi-conductor that forms a PN or PIN junction by a method. Body layer (3) 0.2-0.8 meters! Typically LSI
O, 5/ノ) V samu, two formations - l.

A typical example is 1) type-゛1'
A conductor is formed. Furthermore, this I) type semiconductor (
SixC + - + c x = 0.8 approximately 1 (1 (1 person)
"Secondly, ■-type amorphous or semi-amorphous silicon semiconductor (approximately 0.5p') or N-type microcrystalline (approximately 20p')
A non-single-crystal semiconductor having two gate N junctions was fabricated by stacking semiconductors of 0 rr).

Tin oxide is an oxygen-rich N type, and in order to obtain a large recombination current on this surface, it is extremely important to bring the 1.1) type 4if η bodies into close contact with each other. In order to increase this recombination current, it is necessary to completely remove the adsorbed matter on the surface of the soot n2 oxide, and furthermore, when manufacturing the semiconductor coating 1191''1, the adsorbed matter, especially oxygen, is mixed into the semiconductor, This prevents inducing the cause of photodeterioration (photodeterioration).

In addition to this structure, P-type semiconductor (SixC□-x)'1
type, N type, P type Si semiconductor-I type 5ixGc semi-concentrated-N
Two I'IN junctions made of type Si semiconductor and one p
Tandem type I'lN111N with HJ concubination...
, , llN1f, : may be used as the ``1'' conductor (3).

The non-01 crystal semiconductor (3) was formed as a uniform film over the entire surface.

As described above, after activating the soot oxide surface by the method of the present invention, a semiconductor having an I'IN junction is fabricated, and an SI
The amount of oxygen was measured using MS. As a result, it was possible to reduce the oxygen concentration in the P-type semiconductor to 5 × 10' c + a or less and the oxygen concentration in the I-type semiconductor to 5 × J (1' c + a or less. As a result, the process of the present invention was performed. In the conventionally known photoelectric conversion device 6, the type layer and type layer formed on a tin oxide film each have a size of 2-5 x 1.
0207. 1 to 10 x 1 (120 ct?I) and the concentration of oxygen as an impurity was large, and there was only one variation.

However, as mentioned above, the charge conversion device made by the method of the present invention contains only 1/10 or less of the oxygen impurity of the conventional example, and as a result, the Testebralonski effect can hardly be observed. It is noteworthy that this is no longer the case for photoelectric conversion devices that require high reliability.

In the drawings, the first
The second open groove (1B) extends over the left side (first element example) of the open groove (13) of the second open groove (13). Form as much as S and T-U, Sarani 1/5 IIF Near 30 seconds immersion lr
J. Schiff, ) Improved contact at the joint.

In FIG. 1 (B), the first and second open grooves (13)
, <18) are shifted by 50μ.

Thus, the second open groove (I8) is formed as shown in FIG. 2(B).
The side surfaces (8>, <9) of the first electrode were exposed by removing the lower silicon oxide insulator.

The side surface (9) of this second open groove may be on the left side of the side surface (16) of the first electrode of the first element, and is 1() to 10.
0 tt shift to the first electrode side. l'1. I
/' is characterized in that it is provided over the first electrode position of the first element.

As an extreme example, as shown in FIG. 2(B), it may enter the inside (9) of the first electrode (37).

In FIG. 2, a second electrode (4) on the back side is further formed on this - side as shown in FIG. Open groove (2
0) was obtained.

Is this second electrode (4) conductive? li oxidation (c'ro)
Ill was formed to a thickness of 50 to 1400 people.

As this CTO, ITO (in-youmusus) was formed here. Furthermore, a reflective metal of silver or aluminum with a thickness of 300 to 300
It is effective to improve the efficiency by forming the film with a thickness of 0 J and reflecting light on the back surface.

The ITO and reflective metal are used to promote reflection of long wavelength light on the back surface side and to effectively photoelectrically convert long wavelength light of 600 = 800 nm.

This shows the case where the second electrode is irradiated with a laser beam from the L direction and cut 1IJi apart to form an open groove (20).

This light is in close contact with the semiconductor, especially the top surface.
40) Adjacent first element (31) second element (11)
This prevents the occurrence of crosstalk (leakage current) due to residual conductors or conductive semiconductors in the open grooves between the two.

Thus, as shown in FIG. 1(C), a plurality of elements (
31>, (H) were connected in series at the connecting part.

FIG. 1 (1) shows the present invention being completed as a photoelectric conversion device, in which a silicon nitride film (21) with a thickness of 300 nm is formed as a banshihation layer by a plasma vapor phase method.
It was formed uniformly to a thickness of ~2,000 to prevent leakage current between each element from occurring due to adsorption of moisture, etc.

In addition, an external lead-out terminal was installed on the periphery (5).

These were filled with an organic resin (22) such as polyimide 1°, polyamide, Kapton or epoxy.

Thus, for the irradiation light (10), on a substrate (60 cm x 20 cm) as in this example, each sp is 150/1 in the connection part with a length of 4.35 mm, a length of Q mm in the external extraction electrode part, and a width of 4 mm in the peripheral part. , substantially 58
It has 40 stages within 0mm x 192mm, and the effective area (
192mm x 14.35mm 40 steps 1102cJ
That is, 91.8%) was able to be obtained.

That is, by surface-activating the first electrode with fluorine of the present invention, segment 1- becomes I■, 5% (1, (15c
J) high conversion efficiency could be obtained. . However, when the tin oxide surface was not cleaned with hydrofluoric acid, the efficiency was only 7.5%, and cleaning the tin oxide surface with fluorine was extremely effective. Furthermore, if the photoelectric conversion element obtained by the method of the present invention is applied to a panel structure, the effective conversion efficiency will be 7.2% (theoretically 9.7%, but due to the 40 stages of connected resistance). decreased) (^Ml
(100mW/ctll')), 76.2W
It was possible to have an output power of .

Figure 2 shows the cross-section of A-Δ'' in Figure 1 (D) obtained by SIMS (Secondary Ion Microscope) and shows the depth distribution of oxygen as an impurity in a photoelectric conversion device at a depth of 61M.5n02 (37), P-type 5ixC+-x (42)
, I-type silicon (43), N-type few-crystalline silicon (44〉, IT
When the surface active treatment according to the present invention was performed, curve (33) was obtained, and when no conventional treatment was performed, curve (32) was obtained. [211 et al. To explain these profiles, in the conventional example]) type semiconductor is 1~
5XIO”cJ, type 1 semiconductor is 2~20X10”
cn? However, in the method of the present invention, the P-type semiconductor contains 5X10" to 1XIQ"ca, and the ■-type semiconductor contains 5XIQ"ca.
X I (11 acJ or less. This impurity, oxygen, lowers the electrical conductivity and changes the I-type semiconductor body to N-type. What is more important is that it is an extremely harmful impurity that promotes deterioration due to light irradiation. Therefore, it is extremely important that the method of the present invention can lower the oxygen concentration.

Regarding the fact that this oxygen concentration promotes photodeterioration, there is a paper by the four unexploded people rlnLernaLional Sympo
siumor 5structure and Bon
ding of non-crystalline of
5olid 19'83.5.23-5.264.

When the photoelectric conversion device of the present invention was subjected to an AMI light irradiation test, only 8% characteristic deterioration was observed in 1000 hours.

On the other hand, in the curve 1 of the conventional example shown in FIG. 2 (32), a 14% deterioration in characteristics was observed in 20 hours under the AMI light irradiation condition.

FIG. 3 is a diagram and a plan view (end) showing the most typical positional relationship of the grooves formed during three LSI cycles.

The numbers and steps are the same as in FIG. 1 except for the method of surface activation of the Nzl electrode.

FIG. 3 has a first open groove (13), a first element (31), a second element (11), and a connecting part (12).

Before forming the first open groove, CTO (
2) The surface of the tin oxide is treated with a fluoride-containing gas, such as CF4. The material was immersed in a CFBBr atmosphere, and fluorine radicals were created by applying plasma or ultraviolet light energy. Using this effect, the surface of the oxidized soot was subjected to 11 gas sputtering or optical sputtering to activate the surface. Thereafter, a P-type semiconductor was laminated on the two sides in the same manner as in FIG.

Further, the second groove (18) is provided across the first electrode (37) side of the semiconductor (3) that constitutes the first element.
A portion of the first conductive film is removed. Therefore, the first electrode (37) of the first element (31) and the second electrode of the second element (11) are electrically quickly connected at the connecting part (12), and the two elements are connected in series.

Furthermore, in the drawing, l'Nmanoζ is a semiconductor (3) having at least one I''IN junction, here one 5ix
C+-x (0<x<1) P type-I type Si i'y'
One l'I consisting of i crystallized N-type Sj (44)
A semiconductor having an N junction is provided.

Thus, STMST: According to research, it is a P-type semiconductor and ■
The oxygen concentration in the type semiconductor is conventionally 1 to 5XIO”cl
, 1 to 10
7 Xl0F3cta, 1~20 X 10” CId
The concentration of beneficent oxygen impurities could be reduced.

The result is Ml (100mW/cn of light 11(
By using a single irradiation, it became possible to reduce the deterioration characteristics to 5% or less after 1000 hours of irradiation. It is known that the depletion layer becomes shorter especially when it deteriorates due to light irradiation, but this depletion h4 is not particularly shortened in the present invention. The impurity in the depletion layer of the region x35) with a thickness of about 1000 is 10
il, i? , iri11
J, It is very noteworthy that -0 In this drawing, the first, second, and third grooves are 60~
20μ, typically 150-80μ in the connecting part
I was able to self-serve 20μ.

In the present invention, this panel, for example 40c, m
3 or 4 pieces of 40cm or 60cm x 20cm
By assembling the panels in series within an aluminum sash frame, it is possible to create a 120 cm x 40 cm NEDO standard high power panel.

In addition, it is also effective for this NEDO standard panel to have a fluorine-based protective film attached to the reflective surface side (upper side in the drawing) of the photoelectric conversion device of the present invention using Seaflex to increase mechanical strength against wind pressure, rain, etc. .

In the present invention, the substrate used is glass, especially the back side of the light-transmitting insulating substrate.

However, it is effective to use a composite substrate made of a flexible metal film coated with an insulating film as this substrate.

Particularly when this composite substrate is applied to the above-mentioned practical series, in addition to creating an integrated structure, aluminum oxide, silicon oxide or silicon nitride can damage the CTO on the top surface, causing a mixture of substrate and CTO. It was especially effective because it prevented the so-called Zo 117 King effect from being created.

Further, embodiments of the present invention will be described below to supplement the details.

Example 1 This embodiment is illustrated according to the drawing in FIG.

That is, using a photosensitive substrate (1), chemically strong FTL glass, 1.1 mm thick, 60 cm long, and 20 cm LC was used.

A silicon nitride film was formed on this upper surface to a thickness of 0.1 μm to serve as a blocking layer.

Furthermore, on top of that, CTO is made to have a thorn-like structure.
It was manufactured by electron beam evaporation to an average thickness of 10,230 mm.

Furthermore, after this, the first lecture will be held at Subono I-5 (l t
A YAG laser with tφ and an output of 1 hl was controlled by a microphone at a scanning speed of 1 m/min.

41+1h with this tin oxide surface I/2011
17 for 30 seconds to activate the surface. Furthermore, it was thoroughly washed with pure water and dried.

The element area (31), <11) was set to 15 mm1.

After this, the publicly known Fumet I" CVD method manoko is 11 Cv1
3/Ii? , -, 1 on the liquefied soot surface shown in Figure 1.
) A non-11i crystalline '21' conductor with one PIN junction was fabricated by closely spaced type '4'-conductors.

Its total thickness was approximately 0.5μ.

After that, the first open groove is monitored on a TV, and from there, the 5011 first element r・(31) is shifted 1-, and the spot diameter is 50μφ, and the second open groove is formed by Ls at the output destination. (18) was prepared as shown in FIG. 2(B).

Another 1 minute in 115 livers? U? The residue was eluted with H. In addition, sufficient cleaning was performed to ensure that no low-grade silicon oxide insulation cavity remained on the side surface of the first electrode.

Furthermore, using this whole as CTO, ITO was added to the average film thickness of 1050 by 7r1 beam evaporation method, and AI was added to 50.
0 people made the second electrode (5 pieces: 1 connector (3o)
was constructed.

Furthermore, the third open groove (2o) is connected to the second open groove (1
8), the first element (31) (
21(C) was obtained.

The output of the laser beam is 0.71Q, and the rest is the second aperture l^r.
The same conditions as for the preparation were used.

Furthermore, immerse the saw in 1/]0111i and dissolve the oxide in the same way.

In this way, FIG. 1(C) was produced.

Thereafter, a silicon nitride film was fabricated at a temperature of 100 OA and 200'ct) by PcvD method or aqueous or xenon-excited FOL-CVD method.

A 25mm1 on a 20cm x 60cm panel
I was able to make 40 rounds of p's rate.

The effective 91 rate of the panel is 8Ml (1,OOm W
/cnI) of 6.7% and cuff output of 3.8W.

The self-effective area is 1I02cnl, and the total area of the panel is 91.
8% could be used effectively.

Sanitomo Can L Dari 2 Thickness as substrate glass: 1. In+n+size 20cm
X 60cm was used. Furthermore, one photoelectric conversion device for a calculator was installed with a size of 4cm x 1. A plurality of Ocms were prepared for the same group. It has a tin oxide surface! 'fil conductive film C
The liver was immersed in an atmosphere (0.1 torr) and heated to 13.5 (iM
Add llz brassma and soak for 30 seconds. After this, a type 1) semiconductor was laminated in a reaction furnace.

Fluorescent phantom '2001x as an effective conversion efficiency of 7.5%
I did a test.

If this surface activation using fluorine plasma was not performed, the improvement in properties was so great that only 4.5% could be obtained.

As a result, a final production yield of 83% was achieved with a conversion efficiency of 5% or more.

This can only be achieved by 40-50% using conventional methods,
Considering that the effective conversion efficiency could not be obtained, it was extremely effective.

The rest is the same as in Example 1.

Example 3 This example is similar to Example I with a 20cm x 60cm
The substrate was made of a flexible aluminum metal foil with a thickness of 150 μm.

Furthermore, aluminum oxide with a thickness of 5 μm was formed as a blocking layer thereon by an anodization method to prevent the substrate metal from being damaged by LS.

Furthermore, this first conductive film was subjected to LS with this tin oxide film doped with fluorine on two sides, and then plasma treatment was performed in combination with ultraviolet light irradiation in a CP113r atmosphere, and further in the same reactor. Type 5ixC+-z about 100 people 11
It was formed. The I-type semiconductor was formed in an adjacent reactor in a multi-chamber system. The rest is the same as in Example 1.

In this method, the price of the substrate, which was 60 yen/W in Example 2, could be reduced to 7 yen/W.

In addition, since each calculator element can be separated by cutting or using scissors, it is extremely easy to work with and is inexpensive.

Furthermore, when cutting from this sea 1-, automatic cutting IUi became possible by LS using strong pulsed light of 10 to 15 W.

In this embodiment, by bonding the protective transparent glass substrate on the −L side of the incident light side, a structure can be created in which the photoelectric conversion device is sandwiched between the flexible substrate and the glass substrate. It has flexibility and can be mass-produced at an extremely low cost. 20cm x 5.1% effective conversion efficiency
This could be obtained as the lower limit of a 60cm f3 panel.

In Example 1, light was incident from the substrate side.

However, in the third embodiment, it goes without saying that light is incident from two sides. Therefore, it goes without saying that compared to Example 1, it is necessary to make efforts to improve the transmittance by using only ITO for the second electrode to create a textured structure with less reflected light, and by setting the average thickness to about 700 mm.

In the present invention, the fluoride solution used was hydrofluoric acid diluted with water. The fluoride gas is anhydrous hydrogen fluoride, CF4. C.I.
Freon gas or Freon liquid such as IF, CAF, CI□ was used.

[Brief explanation of drawings]

FIG. 1 is a group of vertical cross-sectional views showing a method for manufacturing a photoelectric conversion device using the present invention. FIG. 2 shows oxygen concentration profiles of photoelectric conversion devices obtained conventionally and according to the present invention. FIG. 3 is a partial longitudinal sectional view of another photoelectric conversion device using another method of the present invention. Patent applicant Semiconductor Energy Research Institute Co., Ltd. Representative Shunpei Yamazaki = SP) 'j42 (@ 31 7; Kitewori

Claims (1)

[Claims] 1. The conductive film formed on the substrate and having an oxidized soot surface constituting the first electrode of the translucent conductive film is formed by exposing the surface of the conductive film to a gas containing fluorine. A method for manufacturing a semiconductor device, characterized in that it makes the active +9. 2. A first electrode having a surface mainly composed of tin oxide on the insulating surface of the substrate; a non-single crystal semiconductor that is in close contact with the electrode and capable of generating a photovoltaic force when irradiated with light; half λ
, a photoelectric conversion device j in which a plurality of optical transducers 711 and 10 elements each having a second electrode in close contact with the substrate 2 are electrically connected in series and disposed on the substrate 2; iT (7)
, lIt'J ij: In the 7-force method, form the first, i, 9 fTl] pattern on the groups 1 and 1-]-culm and the conductive film in a predetermined shape with 1/-the light. the first conductive film is exposed to a liquid or gas containing hydrogen fluoride to remove the residue of the first groove; A step of removing soot oxide and activating the surface of the oxidized soot; A method for manufacturing a semiconductor device, comprising the step of forming a crystalline semiconductor in close contact with the surface of the activated tin oxide. 3. Patent A'1 Claim 1 or 2:
A method for manufacturing a semiconductor device characterized in that hydrofluoric acid diluted with water is used for the 17th substance containing fluorine. 4. Claims 1 or 2, characterized in that the fluorine-containing gas is activated by electricity or light energy and hydrogen fluoride or freon-based gas is used. Semiconductor device manufacturing method.